CA1123547A - Radiation curable composition - Google Patents
Radiation curable compositionInfo
- Publication number
- CA1123547A CA1123547A CA305,699A CA305699A CA1123547A CA 1123547 A CA1123547 A CA 1123547A CA 305699 A CA305699 A CA 305699A CA 1123547 A CA1123547 A CA 1123547A
- Authority
- CA
- Canada
- Prior art keywords
- radiation curable
- curable composition
- diisocyanate
- acrylate
- polyol
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
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Classifications
-
- 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
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A radiation curable composition produced by the reaction of poly(alkyleneoxy)polyol or polyester polyol, organic diisocyanate, hydroxyalkyl acrylate, at a temperature of from about 30°C to about 80°C, wherein for each hydroxy equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted.
A radiation curable composition produced by the reaction of poly(alkyleneoxy)polyol or polyester polyol, organic diisocyanate, hydroxyalkyl acrylate, at a temperature of from about 30°C to about 80°C, wherein for each hydroxy equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted.
Description
~ 7 10538 BACKGROU~D OF THE INVENT'ION
1. F'ield of the Invention This invention relates to a radiation curable composition produced by the reaction of poly (alkyleneoxy) polyol or polyester pol~ol, organic diisocyanate, hydroxy-alkyl acr~late, at a temperature`of from about 30C to about 80C, wherein ~or each hydroxy equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted.
1. F'ield of the Invention This invention relates to a radiation curable composition produced by the reaction of poly (alkyleneoxy) polyol or polyester pol~ol, organic diisocyanate, hydroxy-alkyl acr~late, at a temperature`of from about 30C to about 80C, wherein ~or each hydroxy equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted.
2. Description of `the'Prior Art Increasingly tough attitudes and restrictions regarding coating effluents allowed to escape from finishing ~actories into the atmosphere, the current trend toward high-speed processing, the increasing use of heat-sensitive substrates, the shortage o space and the high cost and ~uestionable availaLbility o energy have ~; combined ~o prompt considerable ef~orts to develop one-hu~dred percent convertible, radiation-curable ink and coatings systems. In compositions of this type, the ;~ `
diluents are "reactive solvents", i.e., fluid monomers .
~thae ~ndergo reaction to become incorporated into the cured film. The "cure" or polymerization of these systems ~ ~ -is conveniently initiated by exposure of the applied ink or coating to electron radiation or to ultraviolet light.
~lthough a variety o monomer types can be and have been used, best results are obtained with acrylate systems. Thè acrylate`inks/coatings are particularly ' ~ ..
.
~ 3 ~ 10538 outstanding in that they provide ~ood response to radiation, i.e., can be polymerized with a minimal amount of radiation.
A particularly important part of a radiation-curable acrylate system is ~he oligomer or prepolymer. This low molecular weight material normal~y has one or more acryla~e groups per mole, and provides crosslink density (and therefore chemical and physical properties) to the cured product.
Since these systems are primarily acrylates, it is no~ surprising that cured film propertie~ (with allowances for molecular welght and crosslink density dif-ferences) are comparable to the properties of conventional acrylic resins. However, for many applications where radiation-curing would offer process advantages, coatings/
inks with b~tter properties than those normally associated with conventional acrylics are desired or even required.
For these areas, acrylated urethane oligomers o~ the type described in U.S. 3,700,64~ were developed. These materials provide measurably better film properties particu~arly tensile strength, elongation, abrasion resistance and resistance to chemicals and stains.
The oligomers normally used in formulations o~
this type are viscous materials with the result that by the time the system has been diluted to application viscosity ~normally 20-40 per cent oligomer), the oligomer has been reduced to the rank of a minor component, and the "urethane-like'l properties are measurably diminished In addition, the high viscosity of the oligomers makes it very di~icult to prepare the materlals consistently ~3~7 without gelling (prematurely polymerizing) the product.
Also, even after the material has been prepared, it is difficultly permeable by oxygen (air) and therefore has poor stability (short sheIf life) and is difficult to handle.
SUMMARY OF THE INVENTION
It has now been found that radiation curable compositions produced by the reaction of poly(alkyleneoxy) polyol or polyester polyol, organic diisocyanate and hydroxyalkyl acrylate, at a temperature of from 30 - to about 80C wherein for each hydroxy equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted, provide coating com-positions of increased toughness. Also, formulations - ~-based on the poly(alkyleneoxy)polyols provide unexpected high gloss to conventional air drying inks, when applied wet on wet and cured by radiation techniques.
The poly(alkyleneoxy~polyols which can be employed herein are well known in the art, as set forth in U.S. Patent 3,582,501, for example. These include linear and ~ranched poly(alkyleneoxy)polyols ha~ing at least one and preferably a plurality of ether linkages and con-taining at least ~wb hydroxyl groups and being substan~ially free from functional groups other than hydroxy. The poly-(alkyleneoxy~poLyols which`are useful herein include the polyethylene(glycols having average molecular weights o 200, 400 and 600 and the polypropylene glycols having average molecular weights of 400 to 4,000. Polymers and copolymers ~ 5~7 of polyoxyalkylene polyols are also adaptable in the process of this invention as well as the block copolymers of ethylene and propylene oxide. Among the copolymers of polyoxyalkylene polyols, and particularly propylene oxide, that deserve some special mention are the propylene oxide adducts of ethylene glycol, glycerol, 1,2,6-hexanetriol, trimethylolpropane, trimethlolethane, pentaerythritol, sorbitol, tris ~ydroxyphenylpropane), triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine and ethanolamine. Linear and branched copolyethers of ethylene oxide and propylene oxide have also been found to be useful. Preferred copolymers of propylene oxide and ethylene oxide are those containing 10 percent ethylene oxide in molecular weights o 50(), 2000, 3000 and 4000.
Further useful types o polyethers are block copolymers prepared from propylene oxide and ethylene oxide.
The poly(alkyleneoxy)polyols preferably contain 2-4 carbon atoms in the alkylene portion thereof.
The polyester polyols suitable for use herein are known in the art and are readily prepared by reacting at least two bifunctional ingredients; a glycol and a dibasic acid. Representative polyester polyols include those prepared from ethylene glycol and adipic acid;
propylene glycol and adipic acid;.ethylene glycol (80 mol percent), propylene glycol (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), propylene glycol 1,2 (20 mol percent) and azelaic acid, ethylene glycol (80 mol percen~), propylene glycol 1,2 (20 mol percent)
diluents are "reactive solvents", i.e., fluid monomers .
~thae ~ndergo reaction to become incorporated into the cured film. The "cure" or polymerization of these systems ~ ~ -is conveniently initiated by exposure of the applied ink or coating to electron radiation or to ultraviolet light.
~lthough a variety o monomer types can be and have been used, best results are obtained with acrylate systems. Thè acrylate`inks/coatings are particularly ' ~ ..
.
~ 3 ~ 10538 outstanding in that they provide ~ood response to radiation, i.e., can be polymerized with a minimal amount of radiation.
A particularly important part of a radiation-curable acrylate system is ~he oligomer or prepolymer. This low molecular weight material normal~y has one or more acryla~e groups per mole, and provides crosslink density (and therefore chemical and physical properties) to the cured product.
Since these systems are primarily acrylates, it is no~ surprising that cured film propertie~ (with allowances for molecular welght and crosslink density dif-ferences) are comparable to the properties of conventional acrylic resins. However, for many applications where radiation-curing would offer process advantages, coatings/
inks with b~tter properties than those normally associated with conventional acrylics are desired or even required.
For these areas, acrylated urethane oligomers o~ the type described in U.S. 3,700,64~ were developed. These materials provide measurably better film properties particu~arly tensile strength, elongation, abrasion resistance and resistance to chemicals and stains.
The oligomers normally used in formulations o~
this type are viscous materials with the result that by the time the system has been diluted to application viscosity ~normally 20-40 per cent oligomer), the oligomer has been reduced to the rank of a minor component, and the "urethane-like'l properties are measurably diminished In addition, the high viscosity of the oligomers makes it very di~icult to prepare the materlals consistently ~3~7 without gelling (prematurely polymerizing) the product.
Also, even after the material has been prepared, it is difficultly permeable by oxygen (air) and therefore has poor stability (short sheIf life) and is difficult to handle.
SUMMARY OF THE INVENTION
It has now been found that radiation curable compositions produced by the reaction of poly(alkyleneoxy) polyol or polyester polyol, organic diisocyanate and hydroxyalkyl acrylate, at a temperature of from 30 - to about 80C wherein for each hydroxy equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted, provide coating com-positions of increased toughness. Also, formulations - ~-based on the poly(alkyleneoxy)polyols provide unexpected high gloss to conventional air drying inks, when applied wet on wet and cured by radiation techniques.
The poly(alkyleneoxy~polyols which can be employed herein are well known in the art, as set forth in U.S. Patent 3,582,501, for example. These include linear and ~ranched poly(alkyleneoxy)polyols ha~ing at least one and preferably a plurality of ether linkages and con-taining at least ~wb hydroxyl groups and being substan~ially free from functional groups other than hydroxy. The poly-(alkyleneoxy~poLyols which`are useful herein include the polyethylene(glycols having average molecular weights o 200, 400 and 600 and the polypropylene glycols having average molecular weights of 400 to 4,000. Polymers and copolymers ~ 5~7 of polyoxyalkylene polyols are also adaptable in the process of this invention as well as the block copolymers of ethylene and propylene oxide. Among the copolymers of polyoxyalkylene polyols, and particularly propylene oxide, that deserve some special mention are the propylene oxide adducts of ethylene glycol, glycerol, 1,2,6-hexanetriol, trimethylolpropane, trimethlolethane, pentaerythritol, sorbitol, tris ~ydroxyphenylpropane), triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine and ethanolamine. Linear and branched copolyethers of ethylene oxide and propylene oxide have also been found to be useful. Preferred copolymers of propylene oxide and ethylene oxide are those containing 10 percent ethylene oxide in molecular weights o 50(), 2000, 3000 and 4000.
Further useful types o polyethers are block copolymers prepared from propylene oxide and ethylene oxide.
The poly(alkyleneoxy)polyols preferably contain 2-4 carbon atoms in the alkylene portion thereof.
The polyester polyols suitable for use herein are known in the art and are readily prepared by reacting at least two bifunctional ingredients; a glycol and a dibasic acid. Representative polyester polyols include those prepared from ethylene glycol and adipic acid;
propylene glycol and adipic acid;.ethylene glycol (80 mol percent), propylene glycol (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), propylene glycol 1,2 (20 mol percent) and azelaic acid, ethylene glycol (80 mol percen~), propylene glycol 1,2 (20 mol percent)
3.~L~;L~7 10 538 and azelaic acid; ethylene glycol (80 mol percent), propylene glycol 1, 2 (20 mol percent) and sebacic acid;
ethylene glycol (80 mol percent), propylene glycol 1,2 (20 mol percent) and dilinoleic acid (20 mol percent);
adipic acid (80 mol percent), ethylene glycol (80 mol percent), glycerine monoethyl ether (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), butylene glycol 1,4 (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), propylene glycol 1,3 (20 mol percent) and adipic acid; ethylene glycol (80 mol percent)j:
pentane dioL 1,4 (20 mol percent) and adipic acid; ethylene ~ .
glycol (80 mol percent), glycerine monoisopropyl ether (20 mol percent) and adipic acid; ethylene glycol ~80 mol per-cent), propylene glycol 1,2 (20 mol percent)~and maleic acid (from 3 to 6 mol percent) J adipic acid tfrom 97 to 94 mol percent); ethylene glycol (80 mol percent), butylene glycol 1,4 (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), die~hylene glycol (20 mol percen~) and adipic acid; ethylene glycol (rom 90 to 10 mol percent), ` 20 propylene~gl~col 1,2 (from 10 to 90 mol percent) and adipic acid; ethylene:glycol (from 90 to 10 mol percent) J
propylene glycol 1,2 (rom 10 to 90 mol percent) and azelaic acid.
The preferred polyester polyols are prepared from a glycol containing 2 to 4 carbon atoms , The organic dii~o~y~nates suitable for ~se herein are known in the art and include the aliphatic and aromatie diisocyanates. Many such compounds are known to those`skilled in ~hè art and illustrative thereof one can 135~8 mention 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate~
isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, di(2-isocyanatoethyl)-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylate, 3,5,5-triethyl-1-isocyanato-3-isocyanato-methylcyclohexane, 1,6-hexamethylene diisocyana~e, m- and p-xylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexyl-4,4'-methane diisocyanate, tetramethylene diisocyanate, cyclopentylene-1,3-diisocyanate, 1,3-diisocyanate, l,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene' diisocyana~e, hexamethylene diisocyanate,' 3,3'-dimethyl- .:
ethylene glycol (80 mol percent), propylene glycol 1,2 (20 mol percent) and dilinoleic acid (20 mol percent);
adipic acid (80 mol percent), ethylene glycol (80 mol percent), glycerine monoethyl ether (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), butylene glycol 1,4 (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), propylene glycol 1,3 (20 mol percent) and adipic acid; ethylene glycol (80 mol percent)j:
pentane dioL 1,4 (20 mol percent) and adipic acid; ethylene ~ .
glycol (80 mol percent), glycerine monoisopropyl ether (20 mol percent) and adipic acid; ethylene glycol ~80 mol per-cent), propylene glycol 1,2 (20 mol percent)~and maleic acid (from 3 to 6 mol percent) J adipic acid tfrom 97 to 94 mol percent); ethylene glycol (80 mol percent), butylene glycol 1,4 (20 mol percent) and adipic acid; ethylene glycol (80 mol percent), die~hylene glycol (20 mol percen~) and adipic acid; ethylene glycol (rom 90 to 10 mol percent), ` 20 propylene~gl~col 1,2 (from 10 to 90 mol percent) and adipic acid; ethylene:glycol (from 90 to 10 mol percent) J
propylene glycol 1,2 (rom 10 to 90 mol percent) and azelaic acid.
The preferred polyester polyols are prepared from a glycol containing 2 to 4 carbon atoms , The organic dii~o~y~nates suitable for ~se herein are known in the art and include the aliphatic and aromatie diisocyanates. Many such compounds are known to those`skilled in ~hè art and illustrative thereof one can 135~8 mention 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate~
isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, di(2-isocyanatoethyl)-bicyclo (2.2.1) hept-5-ene-2,3-dicarboxylate, 3,5,5-triethyl-1-isocyanato-3-isocyanato-methylcyclohexane, 1,6-hexamethylene diisocyana~e, m- and p-xylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexyl-4,4'-methane diisocyanate, tetramethylene diisocyanate, cyclopentylene-1,3-diisocyanate, 1,3-diisocyanate, l,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene' diisocyana~e, hexamethylene diisocyanate,' 3,3'-dimethyl- .:
4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyLbiphen~lene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy 4,~'-dimethyl 4,4'-biphenylene diisocyanate,' durene'diisocyanate, 1-` phenoxy-2,4-phenylene diisocyanate, 1-~ert-butyl-2,4-phenylene diisocyanate, 2,~,4-trimet'hylhexamethylene : diLsocyanate, and tha like. The foregoing list is ill-ustrative only:and is not intended to cxclude any other zo ~ useful organic diisocyanates known to those skilled in the art, `~ ~ :
~: - : A catal~st may be'op:tio~all~ used.in t~e'present reaction. This catalyst is well known to the ure~hane chemLst and does not require more than a brie~ mention.
: The most common catalysts include triethylene diamine, ; morpholine, N-ethyl-morpholine,~ piperazine, triethanolamine, triethylamine, N,N~N',N'-tetramethylbutane-1,3-diamine, dibutyltin dilaurate,. stannous octoate, stannous laurate, ' dioctyltin diace~ate, lead octoate, stannous oleate)' stannous tallate, dibutyltin oxide, etc The catalysts and the concentrations to b~ used are known to vary depending upon the particular amine or tin catalyst employed.
However, these catalys~s are used in amounts of from 0.0001 to 0.0500 weight percent, preerably from O.OOOS to 0.0100 weight percen~,based on the weight of diisocyanate ~mployed.
The hydroxyalkyl acrylates which can be used herein are well known as diluents in uncured, radiation curable compositions. This component is characteriæed by the following formula:
I 11' CH2 = c-C-o~Rl~OH
wherein R is hydrogen or methyl, Rl is an alkyl or alkoxy group of 2 to 4 carbon atoms, and n is an integer ranging from 1 to 6. The preferred hydroxylalkyl acrylates are 2-hydrox~ethyl acrylate and the hydroxypropyl acrylates.
The reaction of the present invention can be carried out in the presence of a solvent to facilitate stirring and as solvent one can use any conventional solvent or an inter~ediate which is desirably present in t~`subsequently formulated coating or ink but which does not interfere with the reactîon at the present time.
These include allyl acrylate, n-amyl acrylate, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, 2-et~oxyethyl acrylate, isoprop~l acrylate, n-lauryl acrylate, nonyl acrylate, n-octadecyl acrylate, n-octyl ~3~ 10538 acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl acrylate, N-methyl(2-carbamoyloxy)ethyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate; tetraethyleneglycol diacrylate, esterdîol-204-diacrylate, trimethylolpropane triacrylate and the like, the compounds obtained when methacrylyl groups are substituted for the acrylyl groups of the foregoing compounds, N-vinyl pyrrolidone, etc. or mixtures of these. The foregoing list is meant to be illustrative only and is not meant to exclude any solvent known to those skilled in the art as having utility in the production of radiation curable compositions.
The radiation curable c~mpositions of the present invention are produced by the reaction of poly(alkyleneoxy) polyol or polyester polyol, organic di~socyanate, hyd~roxy-alkyl acrylate in contact with catalyst, at a tempQrature of from about 30C to about 80C and preferably from about 45C, to about 60C, wherein for each hydroxy equivalen~ in the polyol, 2.5 to about 8.0 equivalen~s of organic diisocyanate and l.S to about 6.0 equivalents of hydroxyalkyl aerylate is reacted.
Alternatively, the poly(alkyleneoxy)polyol or polyester polyol and hydro~yalkyl acrylate can be added either simultaneously or alternatively to organic diisocy-anate, and optionally, catalyst andlor solvent, at a temperat;ure of from about 30C to about 80C, and pre-ferably from about 45C to about 60C, in the amounts of reactants as previously defined.
The time required for the instant reaction will vary depending upon the specific reactants employed, the _g_ temperature, the slze of the batch and other variables.
Those skilled in the'art are fully familiar with the effects of these variables and will normally stop the reaction when the residual isocyanate level drops below 0.5 per cent.
The coating compositions of this invention can be cured by ionizing or non-ionizing radiation means in-cluding, but not limited to, ul~raviolet and eIectron beam radiation. These curing methods and the equipment that can be used for them are well known to those skilled in ~he art. When the coating composition is~to be'cured by non-ionizing radiation, the'presence of a photoinitiator therein is desirable. Any of the known photoinitiators can be used. Illustrative of suitable photoini~lators one can mention 2,2-diethyoxyacetophenone, 2- or 3- or 4-bromoacetophenone, 3- or 4-allyla~etophenone,' 2-aceto-naph~hone, benzaldehyde, benzoin, the alkyl benzoin e~hers, benæophenone, benzoquinone, l-chloroanthraquinone~ p-diacetyl-benzene, 9,lO dibromoa~thracene, 9,10-dich~oroanthracene,' 4,4-dichlorobenzophenone, thioxanthone, methylthioxanthone, ~, ~ ,~ , -trichloro para t-butyl acetophenone, 4-meth-oxybenzophenone, 3-chloro-8-nonylxanthone, 3-iodo-7-m~th-~
` oxy~anthone, benzaldehyde, carbazole, 4-chloro-4'-benzyl-benzophenoné, fluorene,' fluorenone, L,4-naph~hylphenylketone, 2,3-pentanedione, 2,2-di-sec-butoxy acetophenone, dimethoxyphenyl acetophenone,propiophenone,' chIorothioxanthone, xanthone and the like, or any mixtures of these.' The fore-going list is meant to be illustrative only and is not meant to exclude any suitable'photoinitia~ors known to those skilled in the'ar~. Those'skilled in the'art will'kno~: the' ~- 10538 concentrations at which photoinitiators are efectively employed and generally the concentration will not exceed 15 weight per cent of the radiation curable coating com-position.
Those skilled in the art of photochemistry are ~ully aware that photoactivators can be used in combina-tion with the aforementioned photoinia~ors and that synergistic e~fects are sometimes achieved when such combinations are u~ed. Photoactivators are ~eIl known in the art and require no further description ~o make known what they are and the concentrations at which they are effective. Nonetheless, one can mention as illustrative of suitable photoactivators, methylamine, tributylamine, methyldiethanolamine, 2-aminoeth~lethanolamine, allylamine, cyclohexylamine, cyclopentadienylamine, diphenylamine, ditolylamine, trixylylamine, tribenzylamine, n-cyclohexy-lethylenimine, plperidine, N-methylpiperazine, 2,2-dimethyl-1,3-bis(3-N-morpholinyl) propionyloxypropan~, and the like, or any combination of these. The radiation curable coating compositions can also contain coloran~, fillers, wetting agents, ~latting agents and other additives typically present i~ coating compositions. These are well known and require no further elaboration herein. Also ~nown are the concentrations at whieh they are employed. While it is preferred that the radiation curable coating compositions of this invention be free of conventional solverlts, there can be present in small amounts, prefera~ly less than 5 weight per cent, a conventional soLvent, i desired.
The`concentrations of`the individual components which make up the compositions of this invention can be ~L31.;23~ 10538 varied at the will of the practitioner within the limits set forth above, provided that the total conc~n-tration of acrylate-capped urethane, low molecular weight polyfu~ctional acrylate and monofunctional acrylate is at least 85 weight per cent, and preferably at least 95 weight per cent, of the radiation curable `coating composition.
The foregoing components are combined in any manner suitable for achieving a unlform composition. When the components have been mixed, they c~n be applied to a substrate by means suitable for the appli~ation of coatings, such as, for example, reverse roll coating, direct roll coating, graw re, curtain coating, doctor knife, spraying or brushing.
Example The following examples are merely illus~rative of the present invention and are not intended as a limit-ation on the scope thereof.
Example` I
To a twelve liter four-neck flask fitted with a stirrer, thermometer, condenser and dropping ~unnel was charged 2232 grams of isophorone diisocyanate and 1.5 grams~of stannous octoate catalyst and 450 grams o esterdiol-204-diacrylate. The mixture was heated (hot water ~ath) to a temperature of 36~C at which time 4464 grams of polypropylene glycol (with average molecular weight of 2000) was added over an hour and forty minu~e~.
The reactor was stirred or one hour at 40C. At the end ~7, . ~ :
; ~ ~ ` :
of this time 1848 grams o 2-hydroxyethyl acrylate was charged into the flask over an hour and twenty ~inutes while maintaining the tempexature below 50C. The reactor was stirred for an hour and forty five minutes at 48C prior to adding 1.0 gram of the monomethyl ether of hydroquinone as stabilizer. The material was placed in an oven at 50-55C until the res~dual isocyanate reached a level of 0.1 per cent. The viscosity of this material at ~5C was 22,800 centipoise (BrookfieId Model EVT using ~3 spindle).
Example 2 To a five liter four-neck flask fit~ed with a stirrer, thermometer, condenser and dropping funnel was charged 744 grams o~ isophorone di.isocyan~te ~nd 3 g~ams of ~tannous oc~oate catalyst. The miæture was heated (hot water bath) to a temperature of 50C at which time 1488 grams of polypropylen~ glycol (wit~ average molecular weight of 2000) was added over forty three minutes. At the end o~ this time 766 grams o~ 2-hydroxyethyl acrylate`
was charged into the flask over thirty minutes while maintaining the temperature below 60C. The reaction product was alIowed to set overnight at which time the residual isocyanate leveI was nil.
E a~ple 3 To a five liter ~our-neck flask fitted with a sti.rrer, thermometer, ~ondenser ~nd dropping ~unnel was chàrged 942 gr~ms of isophorone diisocyanate and 3 0 ~ ~ ~ 3 ~7 10538 grams of stannous octoate catalyst. The mixture was heated (hot water bath) to a temperature of 50C at which time 118~ grams of polypropylene glycol (with average molecular weight of 2000) was added over seventy minutes, while maintaining the temperature between 50-55C (ice water bath). At the end of this time ~7~ grams of 2-hydroxyethyl acrylate was charged into the flask over thirty minutes whiLe maintaining the temperature below 55C. The reaction product was allowed to cool overnight and the following day the ree isocyanate leveI was 0.08 per cent.
E am~le 4 To a five liter four-neck flask fitted with a stirrer, thermometer, condenser and dropping funnel was charged L97 grams tolylene diisocyanate, 2.1 grams o~
sta~nou~ octoate c~talyst and 446 grams of N-methyl carbamoyloxy ethyl acrylate. The mixture was heated (hot water bath~ to 45C at which time 1400 grams poly-propylene ~lycol (average molecular weight 4?00) was added over fifty five minutes. At the end o~ this time 188 grams 2-hydroxyethyL acrylate was charged into the ~lask over a ~en minute period. The temperature dur~ng the course af the reaction was kept below 55C by means of a cold water bath. AnaLysis of the product showed that the residual isocyanate level was nil.
To a ive liter four-neck flask fitted with a stirrer, thermometer, condenQer and dropping funnel was charged 320 græm~ tolylene diisocyanate, 2.4 grams stannous ~ .....
~ .
~ ~L~ 1053~
octoate catalyst and 252 grams N-methyl carbamoyloxy-ethyl acrylate. The mixture was heated to 34C at which time 1600 grams polyprop~lene glycol (average molecular weight 4000) was added over an hours time. The mîxture was stirred for thirty minutes at which time 346 grams 2-hydroxyethyl acrylate ~ere added. The temperature during the course of the reaction was kept below 45C.
Analysis of the product showed that the residual isocyanate level was 0.06 per cent.
Example 6 To a five liter four-neck flask fitted with a stirrer, thèrmometer, condenser and dropping funnel was charged 240 grams tolylene diisocyanate, 2.3 grams stannous octaate catalyst and 351 grams N-methyl carbamoyloxy ethyl acrylate. The mixture was heated to 33C at which time a ~lend consisting of 450 grams polypropylene glycol (average molecular weight 2000) and 900 grams polypropylene glycol (average molecular weight 4000) were added over se~enty minutes. At the end of this time 323 ~rams 2-hydroxyethyl acrylate was charged into the flask over a ~ive minute period. The temperature during the course o~
the rea~tion was kept between 35-40C. Analysis of the product showed that the residual isocyanate leveI was 0.08 per cent.
ExampIe 7 To a two liter four neck flask fitted with a stirrer, thermometer, condenser and dropping funneI was charged 342 grams tolylene diisocyan~te and 0.8 grams of stannous oc~oate catalyst. The mixtu~e was heated to ~15-~ ~3 5 ~ 1053~
46C at which time 129 grams of polypropylene oxide triol (average molecular weig~t 253~ was added o~er a thirty minute inter~al at a temperature of 58C. At the end of this time 188 grams of trimethylol~ropane triacrylate was added to the mixture, followed by addition of'282 grams - 2-hydroxyethyl acrylate. The reactor was heId at 60C for four hours and then allowed to cool overnight at room temperature. Analysis of the product the'following day show a residual free isocyanate:level of 0.14 per cent.
' Exam~le 8 To a two liter four neck flask fitted with a stirrer, thermometer, condenser and dropping funnel was charged 374 grams tolylene diisocyanate and 1.2 grams stannous octoate catalyst. The mixture was heated to 45~C at which time 354 grams of a polyethylene oxide triol (average molecular of`708) was added to the reactor over a orty minute'inter~al. At the'end of thi~ time 124 grams 2-hydroxyethyl acrylate was fed to the~mixture' followed by 263 grams of trimethylol~ropa~e trlacrylate ,,' 20 and another 200 grams 2-hydroxyethyl acrylate. The ~' reaction mix was stirred at about 50C for an addiditonal'~
four hours and forty mi~utes at which time`it was allowed to cool overnight. The following day analysis showed that the residual isocyanate level was 0.17 per cent.
Exampl'e 9 To a fi~e liter four neck flask fitted with a stixrer, thermometer, condenser and dropping unnel was charged 586 grams isophorone diisocyanate and 2 grams of stannous octoate catalyst. The mixture was heated to 45C
~: - : A catal~st may be'op:tio~all~ used.in t~e'present reaction. This catalyst is well known to the ure~hane chemLst and does not require more than a brie~ mention.
: The most common catalysts include triethylene diamine, ; morpholine, N-ethyl-morpholine,~ piperazine, triethanolamine, triethylamine, N,N~N',N'-tetramethylbutane-1,3-diamine, dibutyltin dilaurate,. stannous octoate, stannous laurate, ' dioctyltin diace~ate, lead octoate, stannous oleate)' stannous tallate, dibutyltin oxide, etc The catalysts and the concentrations to b~ used are known to vary depending upon the particular amine or tin catalyst employed.
However, these catalys~s are used in amounts of from 0.0001 to 0.0500 weight percent, preerably from O.OOOS to 0.0100 weight percen~,based on the weight of diisocyanate ~mployed.
The hydroxyalkyl acrylates which can be used herein are well known as diluents in uncured, radiation curable compositions. This component is characteriæed by the following formula:
I 11' CH2 = c-C-o~Rl~OH
wherein R is hydrogen or methyl, Rl is an alkyl or alkoxy group of 2 to 4 carbon atoms, and n is an integer ranging from 1 to 6. The preferred hydroxylalkyl acrylates are 2-hydrox~ethyl acrylate and the hydroxypropyl acrylates.
The reaction of the present invention can be carried out in the presence of a solvent to facilitate stirring and as solvent one can use any conventional solvent or an inter~ediate which is desirably present in t~`subsequently formulated coating or ink but which does not interfere with the reactîon at the present time.
These include allyl acrylate, n-amyl acrylate, benzyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, 2-et~oxyethyl acrylate, isoprop~l acrylate, n-lauryl acrylate, nonyl acrylate, n-octadecyl acrylate, n-octyl ~3~ 10538 acrylate, 2-phenoxyethyl acrylate, 2-ethylhexyl acrylate, N-methyl(2-carbamoyloxy)ethyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate; tetraethyleneglycol diacrylate, esterdîol-204-diacrylate, trimethylolpropane triacrylate and the like, the compounds obtained when methacrylyl groups are substituted for the acrylyl groups of the foregoing compounds, N-vinyl pyrrolidone, etc. or mixtures of these. The foregoing list is meant to be illustrative only and is not meant to exclude any solvent known to those skilled in the art as having utility in the production of radiation curable compositions.
The radiation curable c~mpositions of the present invention are produced by the reaction of poly(alkyleneoxy) polyol or polyester polyol, organic di~socyanate, hyd~roxy-alkyl acrylate in contact with catalyst, at a tempQrature of from about 30C to about 80C and preferably from about 45C, to about 60C, wherein for each hydroxy equivalen~ in the polyol, 2.5 to about 8.0 equivalen~s of organic diisocyanate and l.S to about 6.0 equivalents of hydroxyalkyl aerylate is reacted.
Alternatively, the poly(alkyleneoxy)polyol or polyester polyol and hydro~yalkyl acrylate can be added either simultaneously or alternatively to organic diisocy-anate, and optionally, catalyst andlor solvent, at a temperat;ure of from about 30C to about 80C, and pre-ferably from about 45C to about 60C, in the amounts of reactants as previously defined.
The time required for the instant reaction will vary depending upon the specific reactants employed, the _g_ temperature, the slze of the batch and other variables.
Those skilled in the'art are fully familiar with the effects of these variables and will normally stop the reaction when the residual isocyanate level drops below 0.5 per cent.
The coating compositions of this invention can be cured by ionizing or non-ionizing radiation means in-cluding, but not limited to, ul~raviolet and eIectron beam radiation. These curing methods and the equipment that can be used for them are well known to those skilled in ~he art. When the coating composition is~to be'cured by non-ionizing radiation, the'presence of a photoinitiator therein is desirable. Any of the known photoinitiators can be used. Illustrative of suitable photoini~lators one can mention 2,2-diethyoxyacetophenone, 2- or 3- or 4-bromoacetophenone, 3- or 4-allyla~etophenone,' 2-aceto-naph~hone, benzaldehyde, benzoin, the alkyl benzoin e~hers, benæophenone, benzoquinone, l-chloroanthraquinone~ p-diacetyl-benzene, 9,lO dibromoa~thracene, 9,10-dich~oroanthracene,' 4,4-dichlorobenzophenone, thioxanthone, methylthioxanthone, ~, ~ ,~ , -trichloro para t-butyl acetophenone, 4-meth-oxybenzophenone, 3-chloro-8-nonylxanthone, 3-iodo-7-m~th-~
` oxy~anthone, benzaldehyde, carbazole, 4-chloro-4'-benzyl-benzophenoné, fluorene,' fluorenone, L,4-naph~hylphenylketone, 2,3-pentanedione, 2,2-di-sec-butoxy acetophenone, dimethoxyphenyl acetophenone,propiophenone,' chIorothioxanthone, xanthone and the like, or any mixtures of these.' The fore-going list is meant to be illustrative only and is not meant to exclude any suitable'photoinitia~ors known to those skilled in the'ar~. Those'skilled in the'art will'kno~: the' ~- 10538 concentrations at which photoinitiators are efectively employed and generally the concentration will not exceed 15 weight per cent of the radiation curable coating com-position.
Those skilled in the art of photochemistry are ~ully aware that photoactivators can be used in combina-tion with the aforementioned photoinia~ors and that synergistic e~fects are sometimes achieved when such combinations are u~ed. Photoactivators are ~eIl known in the art and require no further description ~o make known what they are and the concentrations at which they are effective. Nonetheless, one can mention as illustrative of suitable photoactivators, methylamine, tributylamine, methyldiethanolamine, 2-aminoeth~lethanolamine, allylamine, cyclohexylamine, cyclopentadienylamine, diphenylamine, ditolylamine, trixylylamine, tribenzylamine, n-cyclohexy-lethylenimine, plperidine, N-methylpiperazine, 2,2-dimethyl-1,3-bis(3-N-morpholinyl) propionyloxypropan~, and the like, or any combination of these. The radiation curable coating compositions can also contain coloran~, fillers, wetting agents, ~latting agents and other additives typically present i~ coating compositions. These are well known and require no further elaboration herein. Also ~nown are the concentrations at whieh they are employed. While it is preferred that the radiation curable coating compositions of this invention be free of conventional solverlts, there can be present in small amounts, prefera~ly less than 5 weight per cent, a conventional soLvent, i desired.
The`concentrations of`the individual components which make up the compositions of this invention can be ~L31.;23~ 10538 varied at the will of the practitioner within the limits set forth above, provided that the total conc~n-tration of acrylate-capped urethane, low molecular weight polyfu~ctional acrylate and monofunctional acrylate is at least 85 weight per cent, and preferably at least 95 weight per cent, of the radiation curable `coating composition.
The foregoing components are combined in any manner suitable for achieving a unlform composition. When the components have been mixed, they c~n be applied to a substrate by means suitable for the appli~ation of coatings, such as, for example, reverse roll coating, direct roll coating, graw re, curtain coating, doctor knife, spraying or brushing.
Example The following examples are merely illus~rative of the present invention and are not intended as a limit-ation on the scope thereof.
Example` I
To a twelve liter four-neck flask fitted with a stirrer, thermometer, condenser and dropping ~unnel was charged 2232 grams of isophorone diisocyanate and 1.5 grams~of stannous octoate catalyst and 450 grams o esterdiol-204-diacrylate. The mixture was heated (hot water ~ath) to a temperature of 36~C at which time 4464 grams of polypropylene glycol (with average molecular weight of 2000) was added over an hour and forty minu~e~.
The reactor was stirred or one hour at 40C. At the end ~7, . ~ :
; ~ ~ ` :
of this time 1848 grams o 2-hydroxyethyl acrylate was charged into the flask over an hour and twenty ~inutes while maintaining the tempexature below 50C. The reactor was stirred for an hour and forty five minutes at 48C prior to adding 1.0 gram of the monomethyl ether of hydroquinone as stabilizer. The material was placed in an oven at 50-55C until the res~dual isocyanate reached a level of 0.1 per cent. The viscosity of this material at ~5C was 22,800 centipoise (BrookfieId Model EVT using ~3 spindle).
Example 2 To a five liter four-neck flask fit~ed with a stirrer, thermometer, condenser and dropping funnel was charged 744 grams o~ isophorone di.isocyan~te ~nd 3 g~ams of ~tannous oc~oate catalyst. The miæture was heated (hot water bath) to a temperature of 50C at which time 1488 grams of polypropylen~ glycol (wit~ average molecular weight of 2000) was added over forty three minutes. At the end o~ this time 766 grams o~ 2-hydroxyethyl acrylate`
was charged into the flask over thirty minutes while maintaining the temperature below 60C. The reaction product was alIowed to set overnight at which time the residual isocyanate leveI was nil.
E a~ple 3 To a five liter ~our-neck flask fitted with a sti.rrer, thermometer, ~ondenser ~nd dropping ~unnel was chàrged 942 gr~ms of isophorone diisocyanate and 3 0 ~ ~ ~ 3 ~7 10538 grams of stannous octoate catalyst. The mixture was heated (hot water bath) to a temperature of 50C at which time 118~ grams of polypropylene glycol (with average molecular weight of 2000) was added over seventy minutes, while maintaining the temperature between 50-55C (ice water bath). At the end of this time ~7~ grams of 2-hydroxyethyl acrylate was charged into the flask over thirty minutes whiLe maintaining the temperature below 55C. The reaction product was allowed to cool overnight and the following day the ree isocyanate leveI was 0.08 per cent.
E am~le 4 To a five liter four-neck flask fitted with a stirrer, thermometer, condenser and dropping funnel was charged L97 grams tolylene diisocyanate, 2.1 grams o~
sta~nou~ octoate c~talyst and 446 grams of N-methyl carbamoyloxy ethyl acrylate. The mixture was heated (hot water bath~ to 45C at which time 1400 grams poly-propylene ~lycol (average molecular weight 4?00) was added over fifty five minutes. At the end o~ this time 188 grams 2-hydroxyethyL acrylate was charged into the ~lask over a ~en minute period. The temperature dur~ng the course af the reaction was kept below 55C by means of a cold water bath. AnaLysis of the product showed that the residual isocyanate level was nil.
To a ive liter four-neck flask fitted with a stirrer, thermometer, condenQer and dropping funnel was charged 320 græm~ tolylene diisocyanate, 2.4 grams stannous ~ .....
~ .
~ ~L~ 1053~
octoate catalyst and 252 grams N-methyl carbamoyloxy-ethyl acrylate. The mixture was heated to 34C at which time 1600 grams polyprop~lene glycol (average molecular weight 4000) was added over an hours time. The mîxture was stirred for thirty minutes at which time 346 grams 2-hydroxyethyl acrylate ~ere added. The temperature during the course of the reaction was kept below 45C.
Analysis of the product showed that the residual isocyanate level was 0.06 per cent.
Example 6 To a five liter four-neck flask fitted with a stirrer, thèrmometer, condenser and dropping funnel was charged 240 grams tolylene diisocyanate, 2.3 grams stannous octaate catalyst and 351 grams N-methyl carbamoyloxy ethyl acrylate. The mixture was heated to 33C at which time a ~lend consisting of 450 grams polypropylene glycol (average molecular weight 2000) and 900 grams polypropylene glycol (average molecular weight 4000) were added over se~enty minutes. At the end of this time 323 ~rams 2-hydroxyethyl acrylate was charged into the flask over a ~ive minute period. The temperature during the course o~
the rea~tion was kept between 35-40C. Analysis of the product showed that the residual isocyanate leveI was 0.08 per cent.
ExampIe 7 To a two liter four neck flask fitted with a stirrer, thermometer, condenser and dropping funneI was charged 342 grams tolylene diisocyan~te and 0.8 grams of stannous oc~oate catalyst. The mixtu~e was heated to ~15-~ ~3 5 ~ 1053~
46C at which time 129 grams of polypropylene oxide triol (average molecular weig~t 253~ was added o~er a thirty minute inter~al at a temperature of 58C. At the end of this time 188 grams of trimethylol~ropane triacrylate was added to the mixture, followed by addition of'282 grams - 2-hydroxyethyl acrylate. The reactor was heId at 60C for four hours and then allowed to cool overnight at room temperature. Analysis of the product the'following day show a residual free isocyanate:level of 0.14 per cent.
' Exam~le 8 To a two liter four neck flask fitted with a stirrer, thermometer, condenser and dropping funnel was charged 374 grams tolylene diisocyanate and 1.2 grams stannous octoate catalyst. The mixture was heated to 45~C at which time 354 grams of a polyethylene oxide triol (average molecular of`708) was added to the reactor over a orty minute'inter~al. At the'end of thi~ time 124 grams 2-hydroxyethyl acrylate was fed to the~mixture' followed by 263 grams of trimethylol~ropa~e trlacrylate ,,' 20 and another 200 grams 2-hydroxyethyl acrylate. The ~' reaction mix was stirred at about 50C for an addiditonal'~
four hours and forty mi~utes at which time`it was allowed to cool overnight. The following day analysis showed that the residual isocyanate level was 0.17 per cent.
Exampl'e 9 To a fi~e liter four neck flask fitted with a stixrer, thermometer, condenser and dropping unnel was charged 586 grams isophorone diisocyanate and 2 grams of stannous octoate catalyst. The mixture was heated to 45C
5 ~ 10538 at which time 904 grams of polypropylene glycol (average molecular weight 1000) was added over fifty five minutes while maintaining the temperature belo~ 55~C. At the end of this timeJ509 grams 2-hydroxyethyl acrylate was charged into the flask over a thirty minute interval.
-The reaction product was cooled and ~he residual isocyanate was determine~ to be nil.
The products produced by the above Examples were ormulated into coating compositions as set forth in Tables I to III.
The following designations and abbreviations are used in the Tables.
A: Product produced by Example :l B: Product produced by Example 2 C: Product produced by Example '3 D: Product produced by Example 4 E: Product produced by Example 5 F: Product produced by Example 6 :G: Product produced by E~ample 7 : 20 H~ Product produced by Example 8 I: Product produced by Eæample 9 BZ: Benzophenone - DBAP: Disec-butoxy acetophenone DEAP: Die~hoxy acetophenone DMPAP: Dimethoxyphenyl acetophenone DRH-651 low viscosity epoxy acrylate supplied by SheIl Chemical Co.
ED-204-DA: ester diol-204 diacr~late . - .. . .
3~ 7 1 o 538 2-EHA: 2-ethylhexyl acrylate HEA: 2-hydroxyethyl acrylate MCEA: N-methyl(2-Carbamoyloxy)e~hyl acrylate MDEOA: Methyl diethanol amine MEK: methyl ethyl ketone Slip Additive A:
Me3SiO ~ ~eSiO (Me2Si)20SiMe3 (I H2)3 (IC3H6)16.4 (fC2H4)22.5 OC4Hg 3.2 Slip Additive B:
Organo modi~ied silicone similar in structure to slip additive A.
TMPTA: . Trimethylolpropane ~riacrylate ~: TABLE I
. . Per Cent.By ~e.ight.
- - -------- . --:~ Com~onents .1 - ~: 2..... 3. 4. 5 . . 6 D ~0 SO -~ ~~~
DEAP
.
-:
~~`~ 10538 35~7 The viscosity of the compositions of Table I was measured using a Zahn cup. Each of the coating compositions was applied to silicone release paper using a No. 20 wire wound rod and cured to a solid state by exposure in a nitrogen atmosphere to medium pressure mercury arc lamps delivering a f`lux of 500 watts per square foot for 1 second. The cured coatings, which were about 3 mils thick, were peeIed from the release paper and subjected to tensil~ testing ~ASTM D-638)~ Tansile strength and elongation of the cured coatings appear beIow. Elongation at break is directly reIated to coating flexibility.
~ 1 2 ~ 4 5 6 2ahn Cup Viscosity, Seconds 182 124 286 232 185 108 Tensile Strength at Break, psi 600 200 1700 900 600 200 Elongatlon at Break, ~/O 65 105 75 115 100 100 TABLE II
~ Per Cent By Weight Components 1 2 3 4 5 6 7 E~-204-DA 30 30 35 35 35 25 30 MCEA ~ - lO 5.8 DEAP 0~9 0.~ 0,9 0.9 0.9 0.9 0.9 Slip Additive A 0.3 0.3 0.3 0.3 0.3 0.3 0.3 M~ 5 5 5 5 5 5 5 2-HEA 17.8 11.8 6.8 6.8 1.8 11.8 -_, 9_ :~ , ~ 3 5 ~
The Brookfield RVT viscosi~y of each radiation curable coating composition was measured using a No. 3 spindle.
The radiation curable coating compositions were then applie~ to Bonderite No. 37 steel panels using a No. 3 wire wound rod. The compositions were cured by exposure in a ni~rogen atmosphere to medium pressure mercury arc lamps delivering a flux of 500 watts per square foot for .4 seconds. As a measure of flexibility of the coating compositions, reverse impact strengths were measured by dropping a five pound rod having a round tip onto the uncoated side of the substrate and recording the dis~ance of drop required to crack the surface; the value is then reported in inch-pounds.
1 2 3 4 5 ' 6 7 Brookield Viscosity, cps 84 114 130 140 230 90 240 ReversP Impact, inch pounds 150 150 150 150 lS0 150 150 TABLE III
Parts By Weight ~y~ 1 2 3 4 C 70 - _ _ ~ 70 _ _ MDE~A 3 ~Z 2 - _ _ Slip Additive B .5 .5 1.0 1.0 ~`- 10538 The Brookfield LVT viscosity of each radiation curable coating composition was measured. The radiation curable coating compositions were ~hen applied wet-on-wet to paperboard,which co~tained a reshly applied conventional air-drying black ink, using a Quick Peek Proofer. The material was then cured by exposure in a nitrogen atmosphere to medium pressure mercury arc lamps delivering a flux of soa watts per square foot for 0.2 seconds. The resulting cured coatings were then visually inspected for hold out (coating absorption into the paperboard)J flow (lack of irregularities of the coatings surface~ and ..
gloss.
Brookfield Viscosity, - - 775 715 centipoise Hold Out Good Good Good Good Flow Out Fair Fair Good Good "
Glo~s Level Good Good Good Good ,
-The reaction product was cooled and ~he residual isocyanate was determine~ to be nil.
The products produced by the above Examples were ormulated into coating compositions as set forth in Tables I to III.
The following designations and abbreviations are used in the Tables.
A: Product produced by Example :l B: Product produced by Example 2 C: Product produced by Example '3 D: Product produced by Example 4 E: Product produced by Example 5 F: Product produced by Example 6 :G: Product produced by E~ample 7 : 20 H~ Product produced by Example 8 I: Product produced by Eæample 9 BZ: Benzophenone - DBAP: Disec-butoxy acetophenone DEAP: Die~hoxy acetophenone DMPAP: Dimethoxyphenyl acetophenone DRH-651 low viscosity epoxy acrylate supplied by SheIl Chemical Co.
ED-204-DA: ester diol-204 diacr~late . - .. . .
3~ 7 1 o 538 2-EHA: 2-ethylhexyl acrylate HEA: 2-hydroxyethyl acrylate MCEA: N-methyl(2-Carbamoyloxy)e~hyl acrylate MDEOA: Methyl diethanol amine MEK: methyl ethyl ketone Slip Additive A:
Me3SiO ~ ~eSiO (Me2Si)20SiMe3 (I H2)3 (IC3H6)16.4 (fC2H4)22.5 OC4Hg 3.2 Slip Additive B:
Organo modi~ied silicone similar in structure to slip additive A.
TMPTA: . Trimethylolpropane ~riacrylate ~: TABLE I
. . Per Cent.By ~e.ight.
- - -------- . --:~ Com~onents .1 - ~: 2..... 3. 4. 5 . . 6 D ~0 SO -~ ~~~
DEAP
.
-:
~~`~ 10538 35~7 The viscosity of the compositions of Table I was measured using a Zahn cup. Each of the coating compositions was applied to silicone release paper using a No. 20 wire wound rod and cured to a solid state by exposure in a nitrogen atmosphere to medium pressure mercury arc lamps delivering a f`lux of 500 watts per square foot for 1 second. The cured coatings, which were about 3 mils thick, were peeIed from the release paper and subjected to tensil~ testing ~ASTM D-638)~ Tansile strength and elongation of the cured coatings appear beIow. Elongation at break is directly reIated to coating flexibility.
~ 1 2 ~ 4 5 6 2ahn Cup Viscosity, Seconds 182 124 286 232 185 108 Tensile Strength at Break, psi 600 200 1700 900 600 200 Elongatlon at Break, ~/O 65 105 75 115 100 100 TABLE II
~ Per Cent By Weight Components 1 2 3 4 5 6 7 E~-204-DA 30 30 35 35 35 25 30 MCEA ~ - lO 5.8 DEAP 0~9 0.~ 0,9 0.9 0.9 0.9 0.9 Slip Additive A 0.3 0.3 0.3 0.3 0.3 0.3 0.3 M~ 5 5 5 5 5 5 5 2-HEA 17.8 11.8 6.8 6.8 1.8 11.8 -_, 9_ :~ , ~ 3 5 ~
The Brookfield RVT viscosi~y of each radiation curable coating composition was measured using a No. 3 spindle.
The radiation curable coating compositions were then applie~ to Bonderite No. 37 steel panels using a No. 3 wire wound rod. The compositions were cured by exposure in a ni~rogen atmosphere to medium pressure mercury arc lamps delivering a flux of 500 watts per square foot for .4 seconds. As a measure of flexibility of the coating compositions, reverse impact strengths were measured by dropping a five pound rod having a round tip onto the uncoated side of the substrate and recording the dis~ance of drop required to crack the surface; the value is then reported in inch-pounds.
1 2 3 4 5 ' 6 7 Brookield Viscosity, cps 84 114 130 140 230 90 240 ReversP Impact, inch pounds 150 150 150 150 lS0 150 150 TABLE III
Parts By Weight ~y~ 1 2 3 4 C 70 - _ _ ~ 70 _ _ MDE~A 3 ~Z 2 - _ _ Slip Additive B .5 .5 1.0 1.0 ~`- 10538 The Brookfield LVT viscosity of each radiation curable coating composition was measured. The radiation curable coating compositions were ~hen applied wet-on-wet to paperboard,which co~tained a reshly applied conventional air-drying black ink, using a Quick Peek Proofer. The material was then cured by exposure in a nitrogen atmosphere to medium pressure mercury arc lamps delivering a flux of soa watts per square foot for 0.2 seconds. The resulting cured coatings were then visually inspected for hold out (coating absorption into the paperboard)J flow (lack of irregularities of the coatings surface~ and ..
gloss.
Brookfield Viscosity, - - 775 715 centipoise Hold Out Good Good Good Good Flow Out Fair Fair Good Good "
Glo~s Level Good Good Good Good ,
Claims (12)
1. A radiation curable composition produced by the reaction of poly(alkyleneoxy)polyol or polyester polyol, organic diisocyanate, hydroxylalkyl acrylate, at a temperature of from about 30° to about 80°C, where-in for each hydroxyl equivalent in the polyol, 2.5 to about 8.0 equivalents of organic diisocyanate and 1.5 to about 6.0 equivalents of hydroxyalkyl acrylate is reacted.
2. A radiation curable composition as claimed in claim 1, wherein said poly(alkyleneoxy)polyol contains 2 to 4 carbon atoms in the alkylene portion thereof.
3. A radiation curable composition as claimed in claim 2, wherein said poly(alkyleneoxy) polyol is polyethylene glycol.
4. A radiation curable composition as claimed in claim 2, wherein said poly(alkyleneoxy) polyol is polypropylene glycol.
5. A radiation curable composition as claimed in claim 1, wherein said polyester polyol is the reaction product of a glycol of 2 to 4 carbon atoms and a dibasic acid.
6. A radiation curable composition as claimed in claim 1, wherein said organic diisocyanate is selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, dicyclohexyl-4,4'-methane diisocyanate, 4,4'-diphenylmethane and 2,2,4-trimethylhexamethylene diisocyanate.
7. A radiation curable composition as claimed in claim 1, wherein said hydroxyalkyl acrylate is characterized by the following formula:
wherein R is hydrogen or methyl, R1 is an alkyl or alkoxy group of 2 to 4 carbon atoms, and n is an integer ranging from 1 to 6.
wherein R is hydrogen or methyl, R1 is an alkyl or alkoxy group of 2 to 4 carbon atoms, and n is an integer ranging from 1 to 6.
8. A radiation curable composition as claimed in claim 7, wherein said hydroxyalkyl acrylate is hydroxy-ethyl acrylate.
9. A radiation curable composition as claimed in claim 7 wherein said hydroxyalkyl acrylate comprises hydroxypropyl acrylate.
10. A radiation curable composition as claimed in claim 1, produced at a temperature of from about 45°C
to about 60°C.
to about 60°C.
11. A radiation curable composition as claimed in claim 1, which is produced in the presence of a solvent.
12. A radiation curable composition as claimed in claim 1, which is produced in the presence of a catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81500977A | 1977-07-12 | 1977-07-12 | |
| US815,009 | 1977-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1123547A true CA1123547A (en) | 1982-05-11 |
Family
ID=25216605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA305,699A Expired CA1123547A (en) | 1977-07-12 | 1978-06-19 | Radiation curable composition |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5418892A (en) |
| BE (1) | BE868906A (en) |
| CA (1) | CA1123547A (en) |
| DE (1) | DE2830369A1 (en) |
| FR (1) | FR2397433A1 (en) |
| GB (1) | GB2002009A (en) |
| SE (1) | SE7807739L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836853A (en) * | 1986-10-24 | 1989-06-06 | Dentsply Gmbh | Algin based dental impression material containing biocidal component |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2905205A1 (en) * | 1979-02-12 | 1980-08-14 | Huels Chemische Werke Ag | METHOD FOR PRODUCING STORAGE-STABLE URETHANE ACRYLIC |
| US4264752A (en) * | 1979-08-08 | 1981-04-28 | Union Carbide Corporation | Radiation-curable acrylated urethane polycarbonate compositions |
| BR8303781A (en) * | 1982-07-28 | 1984-04-24 | Goodyear Tire & Rubber | Unsaturated polyurethane and process for its production |
| GB2150938B (en) * | 1983-12-05 | 1987-04-23 | Tyndale Plains Hunter Limited | Hydrophilic polyurethane acrylate compositions |
| US4598009A (en) * | 1984-09-13 | 1986-07-01 | Armstrong World Industries, Inc. | Embossed material and method for producing the same from a photocrosslinkable polyurethane |
| US5128385A (en) * | 1984-09-13 | 1992-07-07 | Armstrong World Industries, Inc. | Photocrosslinkable thermoplastic urethane coating system |
| GB8621835D0 (en) * | 1986-09-10 | 1986-10-15 | Courtaulds Plc | Urethane polymer films |
| EP0691357A1 (en) * | 1994-06-17 | 1996-01-10 | Polyfibron Technologies, Inc. | Liquid polyurethane (meth)acrylate photopolymer useful for flexographic printing plate |
| JP5273046B2 (en) | 2007-07-30 | 2013-08-28 | 旭硝子株式会社 | Curable resin composition, transparent laminate using the same, and method for producing the same |
| JP5477156B2 (en) * | 2009-05-20 | 2014-04-23 | 旭硝子株式会社 | Curable resin composition for producing transparent laminate, transparent laminate and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509234A (en) * | 1965-08-13 | 1970-04-28 | Ford Motor Co | Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate |
| DE2443785A1 (en) * | 1974-09-13 | 1976-04-01 | Basf Ag | LIQUID, PHOTO-NETWORKABLE MOLDING COMPOUNDS FOR THE PRODUCTION OF RELIEF PRINTED PLATES |
| DE2443786C2 (en) * | 1974-09-13 | 1984-01-19 | Basf Ag, 6700 Ludwigshafen | Liquid, photo-crosslinkable molding compound for the production of relief printing plates |
-
1978
- 1978-06-19 CA CA305,699A patent/CA1123547A/en not_active Expired
- 1978-07-10 FR FR7820500A patent/FR2397433A1/en not_active Withdrawn
- 1978-07-11 SE SE7807739A patent/SE7807739L/en unknown
- 1978-07-11 JP JP8364678A patent/JPS5418892A/en active Pending
- 1978-07-11 BE BE189206A patent/BE868906A/en unknown
- 1978-07-11 DE DE19782830369 patent/DE2830369A1/en active Pending
- 1978-07-11 GB GB7829503A patent/GB2002009A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4836853A (en) * | 1986-10-24 | 1989-06-06 | Dentsply Gmbh | Algin based dental impression material containing biocidal component |
Also Published As
| Publication number | Publication date |
|---|---|
| SE7807739L (en) | 1979-01-13 |
| FR2397433A1 (en) | 1979-02-09 |
| GB2002009A (en) | 1979-02-14 |
| JPS5418892A (en) | 1979-02-13 |
| DE2830369A1 (en) | 1979-01-18 |
| BE868906A (en) | 1979-01-11 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |