CA1142543A - Amide acrylate compounds for use in radiation-curable coating compositions - Google Patents
Amide acrylate compounds for use in radiation-curable coating compositionsInfo
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Abstract
ABSTRACT OF THE DISCLOSURE
Amide acrylate compounds are disclosed of the general formula:
Amide acrylate compounds are disclosed of the general formula:
Description
il~Z5~3 DISCLOSURE
This invention relates to a class of highly radiation-sensitive resin compounds known generally as amide acrylates. Coating compositions comprising a resin of this class of compounds polymerize at an excep-tionally high rate to form mar-resistant protective and decorative films when exposed to ionizing radiation or to actinic light. The high rate of film curing is not significantly inhibited by the presence of oxygen so that curing may be achieved under ambient atmospheric air conditions.
The formation of mar-resistant films at a high cure rate without the requirement of a substantlally oxygen-free atmosphere, such as a nitrogen atmosphere, is of tremendous economic advantage inasmuch as high production capacities can be achieved without prohibitively large capital investment.
The class of amide acrylate compounds which provide the afore-mentioned advantages may be defined generally as acrylyloxy-containing compounds having one nitrogen atom and being of the formula:
~f' ~
25 :~3 o /Y
X - C - N (I~
wherein X, Y and Z may each independently be hydrogen, alkyl, aryl, acrylyloxyalkyl, acrylyloxy aliphatic ester formed by reaction of acrylating material with hydroxyl terminated aliphatic ester-containing intermediate resulting from the reaction of inner ester of hydroxy carboxylic acid and amino alcohol, or acrylyloxy aliphatic ether provided that X, Y and Z together have two,three or four acrylyloxy groups. It is intended that generally where the term "amide acrylate" is used such term embraces substituted derivatives of the acrylyloxy radical such as methacrylyloxy radical. A preferred compound is bis(acrylyloxyethyl) formamide represented by the formula:
o ~, /CH2CH20CCH CH2 H - CN \ (II) H2cH2occH=cH2 Another preferred compound is N,N-bis(2-acrylyloxyethyl)4-acrylyloxybutyramide represented by the formula:
o O CH2CH20CCH=CH
' " / 2 CH2=cHcocH2cH2cH2cN O (III) \ CH2cH2occH=cH2 Other preferred acrylyloxy-containing compounds of the class generally described include compounds represented by the following formulae:
" "~ 2CH20CCH CH2 CH2=cHcocH2cH2cH2cH2c~2c ~ o (IV) '' H2CH20CCII=CH2 5 ~3 /CH2CH20CCH=CH2 CH2=cHcocH2cH2ocH2cN o (V) CH2cH2occH=cH2 " " ~ 2 20CCH CH2 CH2~cHcocH2cN\ o (VI) CH2cH2occH=cH2 H2cH2occH=cH2 (VII) CH2cH2occH~cH2 tCH2CH3 ,0, ~cH2cH2occH'cH2 CH3cH2cH2cH2cH ~ CN~ O (VIII) 2cH2occ~l=cH2 ~3~
ll~Z5~3 ~ / 3 CH2=cHcocH2cH2cH2cH2cH2cN \ o (IX) CH2cH2occH=cH2 CH2=cHcoH2c oCH3C~CN o (X) CH2=CHCOH21 CH2CH20CCH=CH2 The amide acrylate compounds shown above may be formed by firstly reacting a compound selected from the group consisting of a carboxylic acid, an ester of a carboxylic acid, a hydroxy acid and an inner ester of a hydroxy carboxylic acid, with an aminoalcohol to form an amide-containing hydroxy group terminated intermediate. The intermediate is then reacted with a compound having acrylic functionality and having a functional group reactive with hydroxy groups of the intermediate to form an acrylate-terminated amide-containing compound.
Suitable starting carboxylic acid compounds for making the amide-containing hydroxy terminated intermediate include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, benzoic acid, the ortho, meta and para isomers of toluic acid, phthalic acid and 2-ethylhexanoic acid. Especially , ~
5 ~3 preferred of these are formic, benzoic, and 2-ethylhexanoic acids.
Suitable also as a class of starting materials are the ester cognates of the aforementioned carboxylic acids. Especially preferred carboxylic acid esters include methyl formate and ethyl acetate.
A third class of useful starting materials comprises hydroxy acids. Preferred compounds of this class include ~-hydroxy acids like glycolic acid. A preferred aromatic hydroxy acid is derived from the re-action of phthalic anhydride and diethylene glycol.
A fourth class of useful starting materials comprises inner esters of hydroxy carboyxlic acids, such as ~-butyrolactone, ~-valerol-actone, and ~-caprolactone.
Suitable aminoalcohol compounds for reaction with the afore-mentioned starting materials to form amlde hydroxy containing intermediates include ethanolamine, diethanolamine, N-methylethanolamine, N-phenylethanol-amine, 2-amino-1-butanol, 4-amino-1-butanol, 2-amino-2-ethyl-1,3-propane-diol, 6-amino-1-hexanol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-3-methyl-1-butanol, 3-amino-3-methyl-1-butanol, 2-amino-4-methyl-1-pentanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 1-amino-2-propanol, 3-amino-l-propanol, and hydroxyalkyl anilines like p-aminobenzyl alcohol.
The intermediate product formed from the aforementioned starting materials comprises one amide group and more than one reactive hydroxyl groups. This amide hydroxy containing product is reacted with a compound having acrylic functionality and having a functional group reactive with hydroxyl groups of the amide intermediate.
Suitable acrylating materials for reacting with the amide inter-mediate include compounds having acrylyl groups or ~-substituted acrylyl groups such as methacrylyl, ethacrylyl and q~chloroacrylyl. These com-pounds must also contain functionality reactive with the amide intermediate hydroxyl 1~
5~3 group. Appropriate specific acrylating materials include acrylic acid, methacrylic acid, ethacrylic acid, ~-chloroacrylic acid and acrylyl chloride, and mixtures of these materials. Preferred compounds are acrylic acid and methacrylic acid.
Amide acrylate compounds of the types described by the aforemention-ed general and specific formulae may be generally prepared by reacting together approximately equimolar amounts of a starting material selected from the designated classes with an aminoalcohol. ~he reactants when heated under refluxing conditions typically form an azeotropic boiling mixture. Volatile products formed by the reaction, such as water, ethanol, methanol, or others, depending upon the choice of reactants, may be collected and removed from the reaction mixture by conventional methods.
The hydroxyl containing amide intermediate compound is then reacted with suitable acrylating materials to form the amide acrylyloxy containing compounds. It is generally preferred that an amount of acrylating compound be mixed with the intermediate which is stoichiometrically equivalent to the reactive hydroxyl group functionality of the intermediate, although an excess or deficiency of acrylating compound is not all harmful.
The amide acrylate monomers prepared as generally described are characterized in having only one amide group per monomer molecule. The monomers may, however, have two, three or four acrylate functional groups per molecule, with a portion of the acrylate group providing an acrylyloxy radical. Amide diacrylate monomers are exemplified by Formulas II, VII, VIII and IX. Formulas III, IV, V and VI represent amide triacrylates.
An amide tetracrylate is represented by Formula X.
The amide acrylate compounds of the invention are useful as radiation-curable resin components of film-forming coating compositions.
The described amide acrylate resins may be homopolymerized, copolymerized or interpolymerized by ionizing radiation or by actinic light~ The compounds of the invention may be copolymerized or interpolymerized with 5~3 other acrylate compounds. Where mixtures of acrylate monomers are desired, alkyl hydroxy containing compounds such as simple glycols may be reacted with an acrylating agent, or with mixtures of acrylating agents, at the same time the hydroxy containing amide intermediates of the invention are acrylated.
For example, trimethylolpropane may be reacted with acrylic acid to form a triacrylate monomer at the same time bis(hydroxyethyl)formamide is acrylated to form the compound of Formula II. This mixture of acrylates may then be exposed to curing conditions to form interpolymerized acrylate polymer films.
Also, mixtures of amide acrylates may be utilized as the resin component of a film-forming composition.
When the amide acrylate resins of the present invention are utilized as film-forming compositions, the amount of resin in the composi-tion can vary from 1 to 100 percent. Usually, the resin concentration ranges from 50 to 70 percent. Where coating compositions of the invention are comprised of less than 100 percent amide acrylate monomer, a copolymerizable reactive solvent selected from any of the conventional ethylenically unsaturated monomer materials that are radiation curable may comprise a major or minor component of the film-forming composition. General classes of such reactive functional monomer compounds include acrylates, styrenes, vinyl amides, esters of vinyl alcohols, maleate esters and fumarate esters. The amount of functional monomer in the composition can vary from zero to 99 percent. Usually, the amount of monomer will range from 30 to 50 percent.
There are distinct advantages provided by coating compositions having amide acrylate compounds of the type disclosed. Generally, these amide acrylate resin materials are of relatively low viscosity and thus impart to coating compositions the properties of ease of application, processing and handling. An additional advantage resides in the extremely fast cure exhi~ited by compositions having the aforementioned amide acrylate compound when the compositions are exposed to radiation. Fast cure, especially under ambient -7~
11'a25'~3 atmospheric conditions, is of significant advantage where the substrates to be coated are of paper or paperboard typically employed for packaging goods where cost of the packaging in relation to that of the goods must be small.
Another desirable property exhibited by amide acrylate-containing coating compositions, especially for those compositions used for coating paper, is the improved flexibility of the cured film coating. Improved flexibility is an unexpected property of amide acrylate-containing coatings since compositions having amide functionality, commonly known as "hard segments", usually impart rigidity to film coatings.
Most of the aforementioned starting materials are suitable to form amide acrylate monomer materials that impart properties of high cure rate and mar-resistance to coating compositions containing the monomer. A few ; amide acrylate related monomers, however, such as diamide acrylates, are known ` to form rather poor films. For example, the reaction of fumaric acid with diethanolamine forms a suitable hydroxy terminated amide intermediate, whereas the acrylated amide product when incorporated into a coating composition cures very poorly.~ Generally, monoamide acrylate monomers, especially those set forth in the examples to follow, are quite suitable for fast curing coating compositions which form flexible, mar-resistant film coatings.
The radiation curable coating composition may consist of sub-stantially only the resin dissolved in the reactive solvent, but other materials are often also present~
When the coating composition is to be cured by exposure to ultraviolet light photoinitiator, photosensitizer or a mixture of photoinitiator and photosensitizer is usually present.
Photoinitiators are compounds which absorb photons and thereby obtain energy to form radical pairs, at least one of which is available to initiate addition polymerization of acrylic or methacrylic groups in the well-known manner. Photosensitizers are compounds which are good absorbers of :
.-8-~1 ~25~3 photons, but which are themselves poor photoinitiators. They absorb photons to produce excited molecules which then interact with a second compound to produce free radicals suitable for initiation of addition polymerization.
The second compound may be a monomer, a polymer or an added initiator. Examples of photoinitiators are benzoin, methyl benzoin ether, butyl benzoin ether, isobutyl benzoin ether, ,-diethoxyacetophenone, a-chloroacetophenone and methylphenyl glyoxylate. Examples of photosensitizers are benzil, 1-naphthaldehyde, anthraquinone, benzophenone, 3-methoxybenzophenone, benzaldehyde and anthrone.
The amount of photoinitiator, photosensitizer or mixture of photoinitiator and photosensitizer present in the radiation curable coating composition can Yary widely. When any of these materials are present, the amount is usually in the range of from about 0.01 to about 10 percent by weight of the binder of the coating composition. Most often the amount is in the range of from about 0.1 to about 5 percent by weight of the binder.
When the coating is to be cured by exposure to ionizîng radiation, these materials are usually omitted from the coating composition, although their presence is permissible~
~ xtender pigments may be present in the composition, and when ultraviolet light is used to cure the film, it is preferred that the extender pigment be substantially transparent to ultraviolet light. Examples of ultraviolet light transparent extender pigments are silica, calcium carbonate, barium sulfate? talc, aluminum silicates, sodium aluminum silicates and potassium aluminum silicates.
Hiding andlor coloring pigment may optionally be present. ~hen the pigment is of the ultraviolet light absorbing type and the coating composition is to be cured by exposure to ultraviolet light, the pigment should be used in amounts which do not preclude curing of the interior of the coating, Examples of hiding pigments are titanium dioxide, antimony oxide, zirconium oxide, zinc sulfide and lithopone. E~amples of coloring pigments are iron oxides, cadmium sulfide, carbon black, phthalocyanine blue, phthalocyanine green, indanthrone blue, ultramarine blue, chromium oxide, burnt umber, benzidine yellow, toluidine red and aluminum powder~ Individual pigments or mixtures of hiding and/or coloring pigments may be used.
Mixtures of extender pigments, hiding pigments and/or coloring pigments may also be employed.
Dyes in their customarily used amounts may be present in the coating composition.
Although not ordinarily desired, minor amounts, usually in the range of from about 0.1 to about 20 percent by weight of the vehicle, of volatile reactive solvent andlor inert volatile organic solvent may be present in the radiation curable coating composition.
Various additional materials ~ay be added to adjust the viscosity of the coating composition. Examples of such materials are fumed silica, castor oil based compositions Ce.g., Thixatrol ST, Baker Castor Oil Company), modified clays, 12-hydroxystearic acid, tetrabutyl orthotitanate and micro-crystalline cellulose. When used, these materials are usually present in an amount in the range of from about 0.5 percent to about 15 percent by weight of the binder.
The radiation curable coating compositions of the invention are usually prepared by simply admixing the solution of resin dissolved in reactive solvent with such other ingredients as may be present. Although mixing is usually accomplished at room temperature, elevated temperatures are sometimes used. The maximum temperature which is usable depends upon the heat stability of the ingredients. Temperatures above about 120C. are only rarely employed.
5~3 The radiation curable coating compositions are used to form cured adherent coatings on substrates. The substrate is coated with the coating composition using substantially any technique known to the art. These include spraying, curtain coatings, dipping, direct roll coatings, reverse roll coating, painting, brushing, printing, drawing and extrusion. The coated substrate is then exposed to radiation of sufficient intensity for a time sufficient to crosslink the coatings. The times of exposure to radiation and the intensity of the radiation to which the coating composition is exposed may vary greatly. Generally, the exposure to radiation should continue until the C-stage is reached when hard, solvent resistant films result. In certain applications, however, it may be desirable for the curing to continue only until the B-stage, viz., gel stage, has been obtained.
Substrates which may be coated with the compositions of this invention may vary widely in their properties~ Organic substrates such as wood, fiberboard, particle board, composition board, paper, cardboard and various polymers such as polyesters, polyamides, cured phenolic resins, cured aminoplasts, acrylics, polyurethanes, and rubber may be used~ Inorganic substrates are exemplified by glass, quartz and ceramic materials. Many metallic substrates may be coated. Exemplary metallic substrates are iron, steel, stainless steel, copper, brass, bronze, aluminum, magnesium, titanium, nickel, chromium, zinc and alloys. Especially suitable substrates are those of paper or paperboard bearing printed or decorative indicia over which a fast-curing protective transparent or pigmented film is formed from compositions containing amide acrylate of the invention. The compositions are also suitable as fi31ers for porous materials like wood.
Cured coatings of the radiation curable coating composition usually have thicknesses in the range of from about 0.001 millimeter to about 3 milli-meters. More often they have thicknesses in the range of from about 0.002 millimeter to about 0.3 millimeter, and most preferred are coatings ranging 5~3 from 0.002 millimeter to 0.08 millimeter. When the radiation curable coating composition is a radiation curable printing ink, the cured coatings usually have thicknesses in the range of from about 0.001 millimeter to about 0.03 millimeter.
The coatings of this invention may be cured by exposure to ionizing radiation, the unit of dose of ionizing radiation being the "rad" which is equal to 100 ergs of energy absorbed from ionizing radiation per gram of material being irradiated. As used throughout the specification and claims, dose is referenced to the bleaching of calibrated blue cellophane film irrespective of the identity of the coating composition being irradiated.
The coatings of the invention may also be cured by exposure to actinic light. Actinic light, as used herein, is electromagnetic radiation having a wavelength of 700 nanometers or less which is capable of producing, either directly or indirectly, free radicals capable of initiating addition polymerization of the coating compositions of the invention. Usually photoinitiator, photosensitizer or mixtures of photoinitiator and photo-sensitizer are present to absorb photons and produce the free radicals, although in some cases, these materials are not needed. Actinic light possesses insufficient energy to produce ions in a medium composed of common elements such as air or water and hence, has an energy below about 10 electron volts. The most commonly used form of actinic light is ultraviolet light, viz., electromagnetic radiation having a wavelength in the range of from about 180 nanometers to about 400 nanometers, although actinic light of greater or shorter wavelength may also be used effectively.
Any suitable source which emits ultraviolet light may be used in the practice of this in~ention. Suitable sources are set forth in ~.S. Patent No. 4,017,652 to ~erald W. Gruber.
The times of exposure to actinic light and the intensity of actinic light to which the coating composition is exposed may vary greatly.
In keeping with the general principles heretofore set forth, the exposure to actinic light should usually continue until the C-stage is obtained.
However, for certain applications, the exposure may be stopped when the B-stage has been achieved.
The following examples, setting forth specific reactant quantities and conditions, specify certain additives, such as catalysts, diluents and surfactants for preparation of the amide acrylate compounds of the present invention. Unless otherwise indicated, all parts and percentages are by weight, and all viscosity values are from measurements of undiluted samples on the Cardner-Holt viscosity scale. These embodiments are not to be construed, however, as limiting the invention since there are numerous variations and modifications possible.
EXAMPLE I
A reaction vessel is equipped with an agitator, a heater, cooling means, a thermometer and a condensing apparatus designed for refluxing an azeotropic mixture, commonly known as a Dean-Stark trap. The vessel is charged with 544 parts of an intermediate reaction product, conventionally prepared by the reaction of equimolar amounts of formic acid and diethanol-amine, together with 233 parts l,l,l-trimethylolpropane, 785 yarts glacial acrylic acid, 86 parts of a 0.1 percent solution of phenothiazine in toluene, 14 parts butylstannoic acid, 0.7 part hydroquinone and 386 parts toluene.
The Dean-Stark trap is filled with toluene to aid in separation of the water component from the water-toluene azeotrope. With the apparatus set for maxi-mum agitation and maximum azeotropic reflux, the reaction mixture is heated to abou~ 107C. in 20 minutes and then to about 110C. in a subsequent one-hour heating period. Water of reaction, separated from the volatile azeotrope and ~13-collected in the Dean-Stark trap, amounts to about 32 parts after the initial one hour and 20 minute heating period. The reaction mixture is then heated for eight hours and 30 minutes at 110-121C., with care being taken that the temperature of the reaction mixture does not exceed 127C. At the end of the heating period, approximately 168 parts water is collected from the reaction vessel. The reaction mixture is then cooled to 49-52C. and filtered through a nylon bag into a storage container.
An airtight reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and vacuum distillation apparatus is charged with about 181 parts of the reaction product from the aforementioned storage container. With application of a vacuum to the reaction vessel measured as 20-23 millimeters of mercury absolute pressure, the reaction product is heated to about 77C. in two hours and 30 minutes. Approximately 34 parts of distillate, comprising mainly toluene, i~ collected during this initial heating period. The reaction product is then heated an additional hour at about 80C. under 18 millimeters of vacuum. The amount of distillate collected remains at about 34 parts thus indicating removal of most of the volatile solvent from the reaction product. The product is then cooled to about 52C. and filtered through a 10 micron GAF filter into a storage container.
EXAMPLE II
A reaction vessel is equipped with an agitator, a heater, cooling means, a thermometer and a condensing apparatus. The vessel is charged with 134 parts diethanolamine and then under a nitrogen blanket the charge is heated to about o7~C. over a period of about three hours~ While maintaining the temperature of the reaction vessel at about 67C., 115 parts ~-butyro-lactone is gradually added to the first charge over a period of about one hour, with approximately 30 parts of the ~-butyrolactone being added each quarter hour.
The reaction mixture is then held at 65-68C~ for seven hours after which a -14_ 114ZS~3 viscosity of Y+ is achieved~ The reaction product, identified as N,N-bis[2-hydroxyethyl-(~-hydroxy butyramide)3, is then cooled to about 52C. and filtered through a nylon bag into a storage container.
Into another reaction vessel equipped as before and having a Dean-Stark trap, there is introduced 95 parts of the aforementioned reaction product together with 2 parts 97 percent formic acid. The reaction mixture is then agitated for 15 minutes. To the reaction vessel at a temperature of about 10C. there are added 2 parts butylstannoic acid, 0.018 part pheno-thiazine, 0.95 part di-t-butyl-p-cresol ("Ionol" lnhibiting agent; Shell Oil Co.), 0.068 part hydroquinone, 92 parts glacial acetic acid and 29 parts toluene. The reaction mixture is then heated to about 121C. in about 90 minutes at which time the apparatus is set for maximum agitation and maximum azeotropic reflux. For a period of approximately 12 hours, the reaction mixture is maintained at a temperature of 116-139C. during which time maximum reflux conditions are maintained. Approximately every 30 minutes during the reflux period, the acid value (measured as milliequivalents of titrated KOH per gram of sample~ of the reaction mixture and the quantity of by-product water from the azeotropic distillation are measured. At the end of the reflux period, the acid value is 28~9 while approximately 22 parts water is collected. The reaction mixture is then cooled to about 52DC. before filtering through a 50 micron GAF filter into storage containers.
Approximately 195 parts of the unstripped resin-solvent mixture prepared above is p'aced in a ~essel equipped with heating means and vacuum distlllation apparatus. The mixture is heated while a vacuum is simultaneously established in the reaction vessel~ The temperature is maintained at 60-63DC.
under vacuum conditions for about two hours, after which time approximately 18 parts of volatile distillate is collected.
11'~'~5~3 EXA~LE III
A reaction vessel is equipped with an agitator, a heater, cooling means, a thermometer and a condensing apparatus. The vessel is charged with 104 parts ~-caprolactone and then under a nitrogen blanket the charge is heated to about 52C. over a period of 30 minutes. Then over a period of 50 minutes 95 parts of preheated diethanolamine is gradually added to the first charge, with care being taken during the exothermic reaction so that reaction mixture does not exceed 57C. The temperature of the reaction mixture is then increased to 60-63C. and maintained at that temperature for about two hours and 40 minutes. Then 17 parts more c-caprolactone is added to the reaction mixture, with gradual heating over a period of one hour to raise the temperature to 68-71C. The reaction mixture is held at 68-71C. for four hours after which time a base value is obtained of 18.2 (expressed as milliequivalents of back-titrated K0~ per gram of sample?. The amide triol intermediate product is then cooled to room temperature.
Into another reaction vessel equippe~ as before and having a Dean-Stark trap for removing water from an azeotropic mixture, there is introduced 109 parts of the aforementioned intermediate product together with 98 parts glacial acrylic acid, 2 parts butylstannoic acid, 0.013 part phenothiazine, 0.2 part hydroquinone and 39 parts toluene. The reaction mixture is then heated to about 114C. in about 45 minutes at which time the apparatus is set for maximum agitation and maximum azeotropic reflux. For a period of approximately 10 hours, the reaction mixture is maintained at a temperature of 111-126C. during which time maximum reflux conditions are maintained.
Approximately every hour during the reflux period, the acid value of the reaction mixture and the quantity of by-product water from the azeotropic distillation are measured. At the end of the reflux period, the acid value is 48.7 while approximately 19 parts water is collected. The reaction mixture i5 then coo~ed -16~
ll~ZS~3 to about 52C. before filtering through a 25 micron GAF filter into storage containers.
Approximately 227 parts of the unstripped resin-solvent mixture prepared above is placed in a vessel equipped with heating means and vacuum distillation apparatus. The mixture is heated while a vacuum is simultaneously established in the reaction vessel. The temperature is maintained at 77-81C.
under vacuum conditions for about three and 3/4 hours, after which time approximately 29 parts of volatile distillate is collected.
EXAMPLE IV
Into a reaction vessel equipped as in Example I, there is charged 88 parts 90 percent formic acid together with 130 parts N-methylethanolamine.
The mixture is refluxed in accordance with conventional methods, approximately 33 parts water being collected~ To the reaction vessel is added 135 parts glacial acrylic acid, 2.5 parts butylstannoic acid and 6 parts hydroquinone.
The mixture is heated and reacted under conditions similar to those in Example I, after which reaction 27 parts water is collected. Then 2 parts sodium acetate is added and the mixture is agitated for about one hour.
Then as done in Example I, volatile solvent is removed from the reaction mixture by the aforementioned stripping process.
~XA~PLE V
Into a reaction vessel equipped as in Exa~ple I, there is charged 207 parts of a triol amide having a molecular weight of 207 (Eastman Kodak, Inc.~. There is also added to the vessel 230 parts glacial acrylic acid, 6.6 parts hydroquinone, 0.7 part di-t-butyl-p-cresol, 4.4 parts butylstannoic acld and 100 parts toluene. After reaction for seven and one-half hours under conditions similar to those set forth before, about 53 parts 25'~3 water is collected. The reaction mixture is neutralized with an ion exchange resin, filtered and solvent is removed by the aforementioned stripping methods.
EXAMPLE YI
Into a reaction vessel equipped as in Example I, there are charged 105 parts diethanolamine, 120 parts 70 percent glycolic acid and 100 parts toluene. The mixture is refluxed for four hours under conditions similar to those set forth in Example I, at the end of which time about 54 parts of water is collected. Then there are added to the vessel 237 parts glacial acrylic acid, 4.1 parts butylstannoic acid, 6 parts hydroquinone, 1 part di-t-butyl-p-cresol and 150 parts toluene. The mixture is then refluxed for five hours after which time the reaction mixture is diluted to 30 percent solids with toluene, washed with 20 percent sodium hydroxide, dried with sodium sulphate and filtered under suction~ There is then added 0.1 percent hydroquinone and the mixture is stripped of volatile solvent as before.
EXAMPLE VII
Into a reaction vessel equipped as in Example II, there are charged 105 parts diethanolamine, 134.2 parts benzoic acid and 100 parts toluene~ The reaction mixtu~e is refluxed under a nitrogen blanket for four and o~e-half hours under conditions as set forth before, after which time 18 parts of water is collected~ Then to the reaction vessel there are charged 158 parts glacial acrylic acid, 3~7 parts butylstannoic acid, 5 parts hydroquinone, 0.7 part di-t-butyl-p-cresol and 150 parts toluene. The mixture is refluxed about five hours after which time 3~ parts water is collected.
The product is then diluted to 50 percent solids with toluene, washed with 20 percent sodium hydroxide, dried with sodium sulphate and filtered under suction~ Volatile solvent is removed from the product by the aforementioned stripping method.
~18_ 114ZS~3 EXA~IPLE VIII
Into a reaction vessel equipped as in Example I, there are charged 105 parts diethanolamine, 158.4 parts 2-ethylhexanoic acid and 50 parts toluene. The mixture is refluxed under conditions similar to those set forth before, after which time 18 parts water is collected.
Then to the reaction vessel is charged 158.4 parts glacial acrylic acid, 4 parts butylstannoic acid, 5.6 parts hydroquinone, 1 part di-t-butyl-p-cresol and 150 parts toluene. The mixture is refluxed according to condi-tions set forth before and the reaction product is then diluted to 30 percent solids with toluene, washed with 20 percent sodium hydroxide, dried with sodium sulphate and filtered under suction. Approximately 0.1 percent hydroquinone is added to the product which is thereafter stripped of volatile solvent as before~
EXA~LE IX
Into a vessel equipped as in Example I, there are charged 240 parts methyl formate and 210 parts diethanolamine. The mixture is refluxed for about 40 minutes under conditions as set out before. Then in another similarly equipped reaction vessel 200 parts of the product from the previous reaction, namely, bis(hydroxyethyl)formamide, is reacted with 216 parts acrylic acid and 0.2 part phenothiazine in 350 parts trichloroethylene so~vent over a period of 11 and one-half hours, after which time about 29 parts of water of reaction is collected~ From the reaction product, identified as bis(acrylyloxyethyl)formamide, 210 parts volatile solvent is removed by the aforementioned conventional method. To the reaction product havin~ an initial acid value of 150 is then added 56 parts triethylorthoformate. The mixture is then heated at 60-70C. for one hour at which time an acid value of the mixture of 102 is obtained.
~lq--114Z5~3 EXAMPLE X
Into a reaction vessel equipped as in Example I, there is charged 133 parts bis-2-hydroxyethylformamide together with 220 parts triethylamine, 0.015 part di-t-butyl-p-cresol, 0.015 part phenothiazine and 200 parts toluene solvent. Reaction is allowed to proceed under agitation and with the gradual addition of 181 parts acrylyl chloride over a three hour period with the temperature being maintained by cooling means to about 25C. After the addition is completed, agitation is continued with the temperature being maintained at about 25C. which is followed thereafter by filtration and removal of the solvent by conventional stripping methods.
EXAMPLE XI
- Into a reaction vessel equipped as in Example I, there is charged 75 parts N-methylethanolamine. With care being taken to control the exothermic reaction, 176 parts ethyl acetate is added dropwise to the reaction vessel. The reaction mixture is heated and refluxed at 85-87C. for 15 minutes with ethanol distillate being collected, with a base value of 149 obtained thereafter. Then 100 parts ethyl acetate is added to the reaction mixture and refluxing is continued three more hours, with a base value of 83 being obtained. Ano~her three hours of refluxing yields a base value for the reaction mixture of 67. Then refluxing is continued until a temperature of 94C. is reached at which time 100 parts more ethyl acetate is added.
Refluxing is continued three more hours after which time a base value of 49 is obtained. Volatile solvent is removed from the reaction mixture by conventional methods.
From the reaction product obtained above, 94 parts is charged into a reaction vessel equipped as before, together with 58 parts acrylic acid, 0.03 part of 0.1 percent phenothiazine solution, 0~02 part hydroquinone, ~2Q-11~25'~3 200 parts methyl isobutyl ketone and 100 parts toluene. The reaction mixture is refluxed at 114-117C. for five and one-half hours after which time 11 parts water of reaction is collected. The mixture is then allowed to cool and stand overnight. Refluxing is then continued at 117-119 C. for about six more hours after which time 3 more parts water of reaction is collected.
EXAMPLE XII
Into a reaction vessel equipped as in Example I, there is charged 150 parts N-methylethanolamine which is heated to about 50 C. Thereafter 250 parts ~ -caprolactone is added dropwise to the reaction mixture over a two-hour period. The temperature of the reaction mixture is held at about 50 C.for one hour and then maintained at about 60C. for two hours. The base value of the reaction mixture is found to be 42; then 15 parts more ~ -caprolactone is added to the reaction mixture. The temperature of the reaction mixture is then held at 60C. for 90 minutes after which time a base value of 24.9 is obtained. Then the mixture is held at 60C., for another hour after which time a base value of 24.9 is again obtained. Another 15 parts -caprolactone is then added to the reaction mixture with the temperature being held at 60 C., after which time a base value of 19.9 is obtained. The reaction mixture is then cooled and to the vessel are charged 288 parts acrylic acid, 10 parts 77 percent formic acid, 25 parts 0.1 percent phenothiazine solution, 4 parts butylstannoic acid, 0.03 part hydroquinone and 250 parts toluene solvent. The reaction mixture is then refluxed for eight hours with 60 parts water of reaction being collected. The mixture is then filtered and volatile solvent is removed by conventional stripping methods.
EXAMP~E XIII
Into a reaction vessel equipped as in Example I, there are charged ~; 134 parts dimethylolpropionic acid, 0.5 part methanesulphonic acid and 400 - parts methanol. The reaction mixture is refluxed 15 hours after which time ll'~;~Si~3 an acid value of about 14.5 is obtained. Then 200 parts toluene, 105 parts diethanolamine and 8 parts sodium methoxide (25 percent in methanol) is added to the reaction mixture. The mixture is refluxed for about one hour with the reaction mixture temperature going from 70C. initially to 150C. finally, after which time roughly 475 parts volatile solvent is collected consisting of approximately two-thirds methanol and one-third toluene. A base value of 244 is then obtained for the reaction mixture. Then about 176 parts toluene is added to the reaction mixture, and refluxing is continued for three hours and 40 minutes more at a temperature of about 113-134 C., after which time a base value of 177 is obtained. The reaction mixture is then refluxed an additional five and one-half hours. Then the reaction vessel is charged with 210 parts acrylic acid, 5 parts butylstannoic acid, 0.03 part phenothiazine solution, 0.2 part hydroquinone and 87 parts toluene. The reaction mixture is then refluxed for eight hours after which time 31 parts water of reaction is collected. Volatile solvent is then removed from the reaction mixture by conventional methods.
EXAMPLE XIV
Into a reaction vessel equipped as in Example I, there is charged 263 parts diethanolamine together with 45 parts toluene. Over a period of 30 minutes, 136 parts 85 percent formic acid is added dropwise to the reaction vessel with no heat being applied during the exothermic reaction.
Thereafter, heat is applied to the reaction vessel to maintain refluxing con-ditions for eight hours, during which time the temperature ranges from 101-113 C.
At the end of the reflux period, approximately 61 parts water is collected.
Volatile solvent is then removed from the reaction product by conventional methods.
Into a second reaction vessel similarly equipped, there are charged 172 parts methacrylic acid, 133 parts of the previously prepared reaction 25 ~3 product, 2 parts butylstannoic acid, 0.5 part di-t-butyl-p-cresol, 0.1 part hydroquinone, 0.02 part thenothiazine and 200 parts toluene. The reaction mixture is refluxed for eight and three-quarter hours at 118-126 C., with 28 parts water being collected. The reaction mixture is then cooled, filtered and stripped of volatile solvent by conventional methods.
EXAMPLE XV
Into a reaction vessel equipped as in Example I, there are charged 220 parts ~ -valerolactone and 210 parts diethanolamine. Under a nitrogen blanket, the reaction mixture is heated at about 100 C. for two hours and 10 minutes, after which time a viscosity of L is measured on an undiluted sample. The reaction mixture is cooled, allowed to sit overnight and is then heated for one hour at about 100C., after which time a viscosity of V is measured.
Into a second reaction vessel similarly equipped, 14 parts of 97 percent formic acid is gradually added over a period of lS minutes to 245 parts of the previously prepared reaction product having a solids fraction of 75.7 percent. Then to the reaction mixture are added 297 parts acrylic acid, 5.4 parts butylstannoic acid, 0.05 part phenothiazine, 0.27 part hydroquinone, 2.5 part di-t-butyl-p-cresol and 82 parts toluene. The reaction mixture is heated for about two hours at 123-130 C., after which time 29 parts water is collected. Then the reaction mixture is cooled and allowed to sit overnight and is thereafter heated for a period of about seven hours at 130-140 C., after which time an additional 30 parts water is collected.
The reaction mixture is cooled and allowed to stand for about 65 hours at room temperature under ambient conditions. Then the mixture is heated for about one hour at about 140 C., after which time an additional 2 parts water is collected. Then by conventional methods, the reaction mixture is filtered, stripped and refiltered with a viscosity of C being measured on an undiluted ., 5 ~ 3 sample of the reaction product.
EXAMPLE XVI
Coating compositions having amide acrylate monomer derived as set forth in previous examples are prepared according to the following general formulation:
Composition #l Parts amide acrylate monomer of 40 Example XIV
hydroxyethyl acrylate 8 benzophenone 0.8 , . -24-Composition #2 Parts amide acrylate monomer of Example I 5 amide acrylate monomer of Example XV 5 hydroxyethylacrylate 3 benzophenone 0.26 The above compositions are coated onto aluminum panels, 4 inches by 12 inches in size, with a wire-wound draw-down bar to a film thickness of about 0.9 mil. The panels are sub;ected to ultraviolet radiation from a single 200 watt per inch mercury vapor lamp placed at a distance of three inches from a conveyor carrying the panels. The panels are exposed to the UV radiation under ambient atmospheric conditions.
It is found that panels coated with composition #l and traveling at conveyor speeds of up to 60 feet per minute cured mar-free by the finger-nail test, while panels traveling at 100 feet per minute under the W lamp have film coatings which mar.
Panels coated with composition ~2 are cured under identical conditions except that UY exposure occurs under a nitrogen atmosphere with a conveyor speed of 20 feet per minute. The cured film coatings show a slight mar under the fingernail test.
According to the provisions of the Patent Statutes, there are described above the invention and what are now considered to be its best embodiments. However, within the scope of the appended claims, it is to be understood that the invention can be practiced otherwise than as specifically described.
T~
This invention relates to a class of highly radiation-sensitive resin compounds known generally as amide acrylates. Coating compositions comprising a resin of this class of compounds polymerize at an excep-tionally high rate to form mar-resistant protective and decorative films when exposed to ionizing radiation or to actinic light. The high rate of film curing is not significantly inhibited by the presence of oxygen so that curing may be achieved under ambient atmospheric air conditions.
The formation of mar-resistant films at a high cure rate without the requirement of a substantlally oxygen-free atmosphere, such as a nitrogen atmosphere, is of tremendous economic advantage inasmuch as high production capacities can be achieved without prohibitively large capital investment.
The class of amide acrylate compounds which provide the afore-mentioned advantages may be defined generally as acrylyloxy-containing compounds having one nitrogen atom and being of the formula:
~f' ~
25 :~3 o /Y
X - C - N (I~
wherein X, Y and Z may each independently be hydrogen, alkyl, aryl, acrylyloxyalkyl, acrylyloxy aliphatic ester formed by reaction of acrylating material with hydroxyl terminated aliphatic ester-containing intermediate resulting from the reaction of inner ester of hydroxy carboxylic acid and amino alcohol, or acrylyloxy aliphatic ether provided that X, Y and Z together have two,three or four acrylyloxy groups. It is intended that generally where the term "amide acrylate" is used such term embraces substituted derivatives of the acrylyloxy radical such as methacrylyloxy radical. A preferred compound is bis(acrylyloxyethyl) formamide represented by the formula:
o ~, /CH2CH20CCH CH2 H - CN \ (II) H2cH2occH=cH2 Another preferred compound is N,N-bis(2-acrylyloxyethyl)4-acrylyloxybutyramide represented by the formula:
o O CH2CH20CCH=CH
' " / 2 CH2=cHcocH2cH2cH2cN O (III) \ CH2cH2occH=cH2 Other preferred acrylyloxy-containing compounds of the class generally described include compounds represented by the following formulae:
" "~ 2CH20CCH CH2 CH2=cHcocH2cH2cH2cH2c~2c ~ o (IV) '' H2CH20CCII=CH2 5 ~3 /CH2CH20CCH=CH2 CH2=cHcocH2cH2ocH2cN o (V) CH2cH2occH=cH2 " " ~ 2 20CCH CH2 CH2~cHcocH2cN\ o (VI) CH2cH2occH=cH2 H2cH2occH=cH2 (VII) CH2cH2occH~cH2 tCH2CH3 ,0, ~cH2cH2occH'cH2 CH3cH2cH2cH2cH ~ CN~ O (VIII) 2cH2occ~l=cH2 ~3~
ll~Z5~3 ~ / 3 CH2=cHcocH2cH2cH2cH2cH2cN \ o (IX) CH2cH2occH=cH2 CH2=cHcoH2c oCH3C~CN o (X) CH2=CHCOH21 CH2CH20CCH=CH2 The amide acrylate compounds shown above may be formed by firstly reacting a compound selected from the group consisting of a carboxylic acid, an ester of a carboxylic acid, a hydroxy acid and an inner ester of a hydroxy carboxylic acid, with an aminoalcohol to form an amide-containing hydroxy group terminated intermediate. The intermediate is then reacted with a compound having acrylic functionality and having a functional group reactive with hydroxy groups of the intermediate to form an acrylate-terminated amide-containing compound.
Suitable starting carboxylic acid compounds for making the amide-containing hydroxy terminated intermediate include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, benzoic acid, the ortho, meta and para isomers of toluic acid, phthalic acid and 2-ethylhexanoic acid. Especially , ~
5 ~3 preferred of these are formic, benzoic, and 2-ethylhexanoic acids.
Suitable also as a class of starting materials are the ester cognates of the aforementioned carboxylic acids. Especially preferred carboxylic acid esters include methyl formate and ethyl acetate.
A third class of useful starting materials comprises hydroxy acids. Preferred compounds of this class include ~-hydroxy acids like glycolic acid. A preferred aromatic hydroxy acid is derived from the re-action of phthalic anhydride and diethylene glycol.
A fourth class of useful starting materials comprises inner esters of hydroxy carboyxlic acids, such as ~-butyrolactone, ~-valerol-actone, and ~-caprolactone.
Suitable aminoalcohol compounds for reaction with the afore-mentioned starting materials to form amlde hydroxy containing intermediates include ethanolamine, diethanolamine, N-methylethanolamine, N-phenylethanol-amine, 2-amino-1-butanol, 4-amino-1-butanol, 2-amino-2-ethyl-1,3-propane-diol, 6-amino-1-hexanol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-3-methyl-1-butanol, 3-amino-3-methyl-1-butanol, 2-amino-4-methyl-1-pentanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 1-amino-2-propanol, 3-amino-l-propanol, and hydroxyalkyl anilines like p-aminobenzyl alcohol.
The intermediate product formed from the aforementioned starting materials comprises one amide group and more than one reactive hydroxyl groups. This amide hydroxy containing product is reacted with a compound having acrylic functionality and having a functional group reactive with hydroxyl groups of the amide intermediate.
Suitable acrylating materials for reacting with the amide inter-mediate include compounds having acrylyl groups or ~-substituted acrylyl groups such as methacrylyl, ethacrylyl and q~chloroacrylyl. These com-pounds must also contain functionality reactive with the amide intermediate hydroxyl 1~
5~3 group. Appropriate specific acrylating materials include acrylic acid, methacrylic acid, ethacrylic acid, ~-chloroacrylic acid and acrylyl chloride, and mixtures of these materials. Preferred compounds are acrylic acid and methacrylic acid.
Amide acrylate compounds of the types described by the aforemention-ed general and specific formulae may be generally prepared by reacting together approximately equimolar amounts of a starting material selected from the designated classes with an aminoalcohol. ~he reactants when heated under refluxing conditions typically form an azeotropic boiling mixture. Volatile products formed by the reaction, such as water, ethanol, methanol, or others, depending upon the choice of reactants, may be collected and removed from the reaction mixture by conventional methods.
The hydroxyl containing amide intermediate compound is then reacted with suitable acrylating materials to form the amide acrylyloxy containing compounds. It is generally preferred that an amount of acrylating compound be mixed with the intermediate which is stoichiometrically equivalent to the reactive hydroxyl group functionality of the intermediate, although an excess or deficiency of acrylating compound is not all harmful.
The amide acrylate monomers prepared as generally described are characterized in having only one amide group per monomer molecule. The monomers may, however, have two, three or four acrylate functional groups per molecule, with a portion of the acrylate group providing an acrylyloxy radical. Amide diacrylate monomers are exemplified by Formulas II, VII, VIII and IX. Formulas III, IV, V and VI represent amide triacrylates.
An amide tetracrylate is represented by Formula X.
The amide acrylate compounds of the invention are useful as radiation-curable resin components of film-forming coating compositions.
The described amide acrylate resins may be homopolymerized, copolymerized or interpolymerized by ionizing radiation or by actinic light~ The compounds of the invention may be copolymerized or interpolymerized with 5~3 other acrylate compounds. Where mixtures of acrylate monomers are desired, alkyl hydroxy containing compounds such as simple glycols may be reacted with an acrylating agent, or with mixtures of acrylating agents, at the same time the hydroxy containing amide intermediates of the invention are acrylated.
For example, trimethylolpropane may be reacted with acrylic acid to form a triacrylate monomer at the same time bis(hydroxyethyl)formamide is acrylated to form the compound of Formula II. This mixture of acrylates may then be exposed to curing conditions to form interpolymerized acrylate polymer films.
Also, mixtures of amide acrylates may be utilized as the resin component of a film-forming composition.
When the amide acrylate resins of the present invention are utilized as film-forming compositions, the amount of resin in the composi-tion can vary from 1 to 100 percent. Usually, the resin concentration ranges from 50 to 70 percent. Where coating compositions of the invention are comprised of less than 100 percent amide acrylate monomer, a copolymerizable reactive solvent selected from any of the conventional ethylenically unsaturated monomer materials that are radiation curable may comprise a major or minor component of the film-forming composition. General classes of such reactive functional monomer compounds include acrylates, styrenes, vinyl amides, esters of vinyl alcohols, maleate esters and fumarate esters. The amount of functional monomer in the composition can vary from zero to 99 percent. Usually, the amount of monomer will range from 30 to 50 percent.
There are distinct advantages provided by coating compositions having amide acrylate compounds of the type disclosed. Generally, these amide acrylate resin materials are of relatively low viscosity and thus impart to coating compositions the properties of ease of application, processing and handling. An additional advantage resides in the extremely fast cure exhi~ited by compositions having the aforementioned amide acrylate compound when the compositions are exposed to radiation. Fast cure, especially under ambient -7~
11'a25'~3 atmospheric conditions, is of significant advantage where the substrates to be coated are of paper or paperboard typically employed for packaging goods where cost of the packaging in relation to that of the goods must be small.
Another desirable property exhibited by amide acrylate-containing coating compositions, especially for those compositions used for coating paper, is the improved flexibility of the cured film coating. Improved flexibility is an unexpected property of amide acrylate-containing coatings since compositions having amide functionality, commonly known as "hard segments", usually impart rigidity to film coatings.
Most of the aforementioned starting materials are suitable to form amide acrylate monomer materials that impart properties of high cure rate and mar-resistance to coating compositions containing the monomer. A few ; amide acrylate related monomers, however, such as diamide acrylates, are known ` to form rather poor films. For example, the reaction of fumaric acid with diethanolamine forms a suitable hydroxy terminated amide intermediate, whereas the acrylated amide product when incorporated into a coating composition cures very poorly.~ Generally, monoamide acrylate monomers, especially those set forth in the examples to follow, are quite suitable for fast curing coating compositions which form flexible, mar-resistant film coatings.
The radiation curable coating composition may consist of sub-stantially only the resin dissolved in the reactive solvent, but other materials are often also present~
When the coating composition is to be cured by exposure to ultraviolet light photoinitiator, photosensitizer or a mixture of photoinitiator and photosensitizer is usually present.
Photoinitiators are compounds which absorb photons and thereby obtain energy to form radical pairs, at least one of which is available to initiate addition polymerization of acrylic or methacrylic groups in the well-known manner. Photosensitizers are compounds which are good absorbers of :
.-8-~1 ~25~3 photons, but which are themselves poor photoinitiators. They absorb photons to produce excited molecules which then interact with a second compound to produce free radicals suitable for initiation of addition polymerization.
The second compound may be a monomer, a polymer or an added initiator. Examples of photoinitiators are benzoin, methyl benzoin ether, butyl benzoin ether, isobutyl benzoin ether, ,-diethoxyacetophenone, a-chloroacetophenone and methylphenyl glyoxylate. Examples of photosensitizers are benzil, 1-naphthaldehyde, anthraquinone, benzophenone, 3-methoxybenzophenone, benzaldehyde and anthrone.
The amount of photoinitiator, photosensitizer or mixture of photoinitiator and photosensitizer present in the radiation curable coating composition can Yary widely. When any of these materials are present, the amount is usually in the range of from about 0.01 to about 10 percent by weight of the binder of the coating composition. Most often the amount is in the range of from about 0.1 to about 5 percent by weight of the binder.
When the coating is to be cured by exposure to ionizîng radiation, these materials are usually omitted from the coating composition, although their presence is permissible~
~ xtender pigments may be present in the composition, and when ultraviolet light is used to cure the film, it is preferred that the extender pigment be substantially transparent to ultraviolet light. Examples of ultraviolet light transparent extender pigments are silica, calcium carbonate, barium sulfate? talc, aluminum silicates, sodium aluminum silicates and potassium aluminum silicates.
Hiding andlor coloring pigment may optionally be present. ~hen the pigment is of the ultraviolet light absorbing type and the coating composition is to be cured by exposure to ultraviolet light, the pigment should be used in amounts which do not preclude curing of the interior of the coating, Examples of hiding pigments are titanium dioxide, antimony oxide, zirconium oxide, zinc sulfide and lithopone. E~amples of coloring pigments are iron oxides, cadmium sulfide, carbon black, phthalocyanine blue, phthalocyanine green, indanthrone blue, ultramarine blue, chromium oxide, burnt umber, benzidine yellow, toluidine red and aluminum powder~ Individual pigments or mixtures of hiding and/or coloring pigments may be used.
Mixtures of extender pigments, hiding pigments and/or coloring pigments may also be employed.
Dyes in their customarily used amounts may be present in the coating composition.
Although not ordinarily desired, minor amounts, usually in the range of from about 0.1 to about 20 percent by weight of the vehicle, of volatile reactive solvent andlor inert volatile organic solvent may be present in the radiation curable coating composition.
Various additional materials ~ay be added to adjust the viscosity of the coating composition. Examples of such materials are fumed silica, castor oil based compositions Ce.g., Thixatrol ST, Baker Castor Oil Company), modified clays, 12-hydroxystearic acid, tetrabutyl orthotitanate and micro-crystalline cellulose. When used, these materials are usually present in an amount in the range of from about 0.5 percent to about 15 percent by weight of the binder.
The radiation curable coating compositions of the invention are usually prepared by simply admixing the solution of resin dissolved in reactive solvent with such other ingredients as may be present. Although mixing is usually accomplished at room temperature, elevated temperatures are sometimes used. The maximum temperature which is usable depends upon the heat stability of the ingredients. Temperatures above about 120C. are only rarely employed.
5~3 The radiation curable coating compositions are used to form cured adherent coatings on substrates. The substrate is coated with the coating composition using substantially any technique known to the art. These include spraying, curtain coatings, dipping, direct roll coatings, reverse roll coating, painting, brushing, printing, drawing and extrusion. The coated substrate is then exposed to radiation of sufficient intensity for a time sufficient to crosslink the coatings. The times of exposure to radiation and the intensity of the radiation to which the coating composition is exposed may vary greatly. Generally, the exposure to radiation should continue until the C-stage is reached when hard, solvent resistant films result. In certain applications, however, it may be desirable for the curing to continue only until the B-stage, viz., gel stage, has been obtained.
Substrates which may be coated with the compositions of this invention may vary widely in their properties~ Organic substrates such as wood, fiberboard, particle board, composition board, paper, cardboard and various polymers such as polyesters, polyamides, cured phenolic resins, cured aminoplasts, acrylics, polyurethanes, and rubber may be used~ Inorganic substrates are exemplified by glass, quartz and ceramic materials. Many metallic substrates may be coated. Exemplary metallic substrates are iron, steel, stainless steel, copper, brass, bronze, aluminum, magnesium, titanium, nickel, chromium, zinc and alloys. Especially suitable substrates are those of paper or paperboard bearing printed or decorative indicia over which a fast-curing protective transparent or pigmented film is formed from compositions containing amide acrylate of the invention. The compositions are also suitable as fi31ers for porous materials like wood.
Cured coatings of the radiation curable coating composition usually have thicknesses in the range of from about 0.001 millimeter to about 3 milli-meters. More often they have thicknesses in the range of from about 0.002 millimeter to about 0.3 millimeter, and most preferred are coatings ranging 5~3 from 0.002 millimeter to 0.08 millimeter. When the radiation curable coating composition is a radiation curable printing ink, the cured coatings usually have thicknesses in the range of from about 0.001 millimeter to about 0.03 millimeter.
The coatings of this invention may be cured by exposure to ionizing radiation, the unit of dose of ionizing radiation being the "rad" which is equal to 100 ergs of energy absorbed from ionizing radiation per gram of material being irradiated. As used throughout the specification and claims, dose is referenced to the bleaching of calibrated blue cellophane film irrespective of the identity of the coating composition being irradiated.
The coatings of the invention may also be cured by exposure to actinic light. Actinic light, as used herein, is electromagnetic radiation having a wavelength of 700 nanometers or less which is capable of producing, either directly or indirectly, free radicals capable of initiating addition polymerization of the coating compositions of the invention. Usually photoinitiator, photosensitizer or mixtures of photoinitiator and photo-sensitizer are present to absorb photons and produce the free radicals, although in some cases, these materials are not needed. Actinic light possesses insufficient energy to produce ions in a medium composed of common elements such as air or water and hence, has an energy below about 10 electron volts. The most commonly used form of actinic light is ultraviolet light, viz., electromagnetic radiation having a wavelength in the range of from about 180 nanometers to about 400 nanometers, although actinic light of greater or shorter wavelength may also be used effectively.
Any suitable source which emits ultraviolet light may be used in the practice of this in~ention. Suitable sources are set forth in ~.S. Patent No. 4,017,652 to ~erald W. Gruber.
The times of exposure to actinic light and the intensity of actinic light to which the coating composition is exposed may vary greatly.
In keeping with the general principles heretofore set forth, the exposure to actinic light should usually continue until the C-stage is obtained.
However, for certain applications, the exposure may be stopped when the B-stage has been achieved.
The following examples, setting forth specific reactant quantities and conditions, specify certain additives, such as catalysts, diluents and surfactants for preparation of the amide acrylate compounds of the present invention. Unless otherwise indicated, all parts and percentages are by weight, and all viscosity values are from measurements of undiluted samples on the Cardner-Holt viscosity scale. These embodiments are not to be construed, however, as limiting the invention since there are numerous variations and modifications possible.
EXAMPLE I
A reaction vessel is equipped with an agitator, a heater, cooling means, a thermometer and a condensing apparatus designed for refluxing an azeotropic mixture, commonly known as a Dean-Stark trap. The vessel is charged with 544 parts of an intermediate reaction product, conventionally prepared by the reaction of equimolar amounts of formic acid and diethanol-amine, together with 233 parts l,l,l-trimethylolpropane, 785 yarts glacial acrylic acid, 86 parts of a 0.1 percent solution of phenothiazine in toluene, 14 parts butylstannoic acid, 0.7 part hydroquinone and 386 parts toluene.
The Dean-Stark trap is filled with toluene to aid in separation of the water component from the water-toluene azeotrope. With the apparatus set for maxi-mum agitation and maximum azeotropic reflux, the reaction mixture is heated to abou~ 107C. in 20 minutes and then to about 110C. in a subsequent one-hour heating period. Water of reaction, separated from the volatile azeotrope and ~13-collected in the Dean-Stark trap, amounts to about 32 parts after the initial one hour and 20 minute heating period. The reaction mixture is then heated for eight hours and 30 minutes at 110-121C., with care being taken that the temperature of the reaction mixture does not exceed 127C. At the end of the heating period, approximately 168 parts water is collected from the reaction vessel. The reaction mixture is then cooled to 49-52C. and filtered through a nylon bag into a storage container.
An airtight reaction vessel equipped with an agitator, a heater, cooling means, a thermometer and vacuum distillation apparatus is charged with about 181 parts of the reaction product from the aforementioned storage container. With application of a vacuum to the reaction vessel measured as 20-23 millimeters of mercury absolute pressure, the reaction product is heated to about 77C. in two hours and 30 minutes. Approximately 34 parts of distillate, comprising mainly toluene, i~ collected during this initial heating period. The reaction product is then heated an additional hour at about 80C. under 18 millimeters of vacuum. The amount of distillate collected remains at about 34 parts thus indicating removal of most of the volatile solvent from the reaction product. The product is then cooled to about 52C. and filtered through a 10 micron GAF filter into a storage container.
EXAMPLE II
A reaction vessel is equipped with an agitator, a heater, cooling means, a thermometer and a condensing apparatus. The vessel is charged with 134 parts diethanolamine and then under a nitrogen blanket the charge is heated to about o7~C. over a period of about three hours~ While maintaining the temperature of the reaction vessel at about 67C., 115 parts ~-butyro-lactone is gradually added to the first charge over a period of about one hour, with approximately 30 parts of the ~-butyrolactone being added each quarter hour.
The reaction mixture is then held at 65-68C~ for seven hours after which a -14_ 114ZS~3 viscosity of Y+ is achieved~ The reaction product, identified as N,N-bis[2-hydroxyethyl-(~-hydroxy butyramide)3, is then cooled to about 52C. and filtered through a nylon bag into a storage container.
Into another reaction vessel equipped as before and having a Dean-Stark trap, there is introduced 95 parts of the aforementioned reaction product together with 2 parts 97 percent formic acid. The reaction mixture is then agitated for 15 minutes. To the reaction vessel at a temperature of about 10C. there are added 2 parts butylstannoic acid, 0.018 part pheno-thiazine, 0.95 part di-t-butyl-p-cresol ("Ionol" lnhibiting agent; Shell Oil Co.), 0.068 part hydroquinone, 92 parts glacial acetic acid and 29 parts toluene. The reaction mixture is then heated to about 121C. in about 90 minutes at which time the apparatus is set for maximum agitation and maximum azeotropic reflux. For a period of approximately 12 hours, the reaction mixture is maintained at a temperature of 116-139C. during which time maximum reflux conditions are maintained. Approximately every 30 minutes during the reflux period, the acid value (measured as milliequivalents of titrated KOH per gram of sample~ of the reaction mixture and the quantity of by-product water from the azeotropic distillation are measured. At the end of the reflux period, the acid value is 28~9 while approximately 22 parts water is collected. The reaction mixture is then cooled to about 52DC. before filtering through a 50 micron GAF filter into storage containers.
Approximately 195 parts of the unstripped resin-solvent mixture prepared above is p'aced in a ~essel equipped with heating means and vacuum distlllation apparatus. The mixture is heated while a vacuum is simultaneously established in the reaction vessel~ The temperature is maintained at 60-63DC.
under vacuum conditions for about two hours, after which time approximately 18 parts of volatile distillate is collected.
11'~'~5~3 EXA~LE III
A reaction vessel is equipped with an agitator, a heater, cooling means, a thermometer and a condensing apparatus. The vessel is charged with 104 parts ~-caprolactone and then under a nitrogen blanket the charge is heated to about 52C. over a period of 30 minutes. Then over a period of 50 minutes 95 parts of preheated diethanolamine is gradually added to the first charge, with care being taken during the exothermic reaction so that reaction mixture does not exceed 57C. The temperature of the reaction mixture is then increased to 60-63C. and maintained at that temperature for about two hours and 40 minutes. Then 17 parts more c-caprolactone is added to the reaction mixture, with gradual heating over a period of one hour to raise the temperature to 68-71C. The reaction mixture is held at 68-71C. for four hours after which time a base value is obtained of 18.2 (expressed as milliequivalents of back-titrated K0~ per gram of sample?. The amide triol intermediate product is then cooled to room temperature.
Into another reaction vessel equippe~ as before and having a Dean-Stark trap for removing water from an azeotropic mixture, there is introduced 109 parts of the aforementioned intermediate product together with 98 parts glacial acrylic acid, 2 parts butylstannoic acid, 0.013 part phenothiazine, 0.2 part hydroquinone and 39 parts toluene. The reaction mixture is then heated to about 114C. in about 45 minutes at which time the apparatus is set for maximum agitation and maximum azeotropic reflux. For a period of approximately 10 hours, the reaction mixture is maintained at a temperature of 111-126C. during which time maximum reflux conditions are maintained.
Approximately every hour during the reflux period, the acid value of the reaction mixture and the quantity of by-product water from the azeotropic distillation are measured. At the end of the reflux period, the acid value is 48.7 while approximately 19 parts water is collected. The reaction mixture i5 then coo~ed -16~
ll~ZS~3 to about 52C. before filtering through a 25 micron GAF filter into storage containers.
Approximately 227 parts of the unstripped resin-solvent mixture prepared above is placed in a vessel equipped with heating means and vacuum distillation apparatus. The mixture is heated while a vacuum is simultaneously established in the reaction vessel. The temperature is maintained at 77-81C.
under vacuum conditions for about three and 3/4 hours, after which time approximately 29 parts of volatile distillate is collected.
EXAMPLE IV
Into a reaction vessel equipped as in Example I, there is charged 88 parts 90 percent formic acid together with 130 parts N-methylethanolamine.
The mixture is refluxed in accordance with conventional methods, approximately 33 parts water being collected~ To the reaction vessel is added 135 parts glacial acrylic acid, 2.5 parts butylstannoic acid and 6 parts hydroquinone.
The mixture is heated and reacted under conditions similar to those in Example I, after which reaction 27 parts water is collected. Then 2 parts sodium acetate is added and the mixture is agitated for about one hour.
Then as done in Example I, volatile solvent is removed from the reaction mixture by the aforementioned stripping process.
~XA~PLE V
Into a reaction vessel equipped as in Exa~ple I, there is charged 207 parts of a triol amide having a molecular weight of 207 (Eastman Kodak, Inc.~. There is also added to the vessel 230 parts glacial acrylic acid, 6.6 parts hydroquinone, 0.7 part di-t-butyl-p-cresol, 4.4 parts butylstannoic acld and 100 parts toluene. After reaction for seven and one-half hours under conditions similar to those set forth before, about 53 parts 25'~3 water is collected. The reaction mixture is neutralized with an ion exchange resin, filtered and solvent is removed by the aforementioned stripping methods.
EXAMPLE YI
Into a reaction vessel equipped as in Example I, there are charged 105 parts diethanolamine, 120 parts 70 percent glycolic acid and 100 parts toluene. The mixture is refluxed for four hours under conditions similar to those set forth in Example I, at the end of which time about 54 parts of water is collected. Then there are added to the vessel 237 parts glacial acrylic acid, 4.1 parts butylstannoic acid, 6 parts hydroquinone, 1 part di-t-butyl-p-cresol and 150 parts toluene. The mixture is then refluxed for five hours after which time the reaction mixture is diluted to 30 percent solids with toluene, washed with 20 percent sodium hydroxide, dried with sodium sulphate and filtered under suction~ There is then added 0.1 percent hydroquinone and the mixture is stripped of volatile solvent as before.
EXAMPLE VII
Into a reaction vessel equipped as in Example II, there are charged 105 parts diethanolamine, 134.2 parts benzoic acid and 100 parts toluene~ The reaction mixtu~e is refluxed under a nitrogen blanket for four and o~e-half hours under conditions as set forth before, after which time 18 parts of water is collected~ Then to the reaction vessel there are charged 158 parts glacial acrylic acid, 3~7 parts butylstannoic acid, 5 parts hydroquinone, 0.7 part di-t-butyl-p-cresol and 150 parts toluene. The mixture is refluxed about five hours after which time 3~ parts water is collected.
The product is then diluted to 50 percent solids with toluene, washed with 20 percent sodium hydroxide, dried with sodium sulphate and filtered under suction~ Volatile solvent is removed from the product by the aforementioned stripping method.
~18_ 114ZS~3 EXA~IPLE VIII
Into a reaction vessel equipped as in Example I, there are charged 105 parts diethanolamine, 158.4 parts 2-ethylhexanoic acid and 50 parts toluene. The mixture is refluxed under conditions similar to those set forth before, after which time 18 parts water is collected.
Then to the reaction vessel is charged 158.4 parts glacial acrylic acid, 4 parts butylstannoic acid, 5.6 parts hydroquinone, 1 part di-t-butyl-p-cresol and 150 parts toluene. The mixture is refluxed according to condi-tions set forth before and the reaction product is then diluted to 30 percent solids with toluene, washed with 20 percent sodium hydroxide, dried with sodium sulphate and filtered under suction. Approximately 0.1 percent hydroquinone is added to the product which is thereafter stripped of volatile solvent as before~
EXA~LE IX
Into a vessel equipped as in Example I, there are charged 240 parts methyl formate and 210 parts diethanolamine. The mixture is refluxed for about 40 minutes under conditions as set out before. Then in another similarly equipped reaction vessel 200 parts of the product from the previous reaction, namely, bis(hydroxyethyl)formamide, is reacted with 216 parts acrylic acid and 0.2 part phenothiazine in 350 parts trichloroethylene so~vent over a period of 11 and one-half hours, after which time about 29 parts of water of reaction is collected~ From the reaction product, identified as bis(acrylyloxyethyl)formamide, 210 parts volatile solvent is removed by the aforementioned conventional method. To the reaction product havin~ an initial acid value of 150 is then added 56 parts triethylorthoformate. The mixture is then heated at 60-70C. for one hour at which time an acid value of the mixture of 102 is obtained.
~lq--114Z5~3 EXAMPLE X
Into a reaction vessel equipped as in Example I, there is charged 133 parts bis-2-hydroxyethylformamide together with 220 parts triethylamine, 0.015 part di-t-butyl-p-cresol, 0.015 part phenothiazine and 200 parts toluene solvent. Reaction is allowed to proceed under agitation and with the gradual addition of 181 parts acrylyl chloride over a three hour period with the temperature being maintained by cooling means to about 25C. After the addition is completed, agitation is continued with the temperature being maintained at about 25C. which is followed thereafter by filtration and removal of the solvent by conventional stripping methods.
EXAMPLE XI
- Into a reaction vessel equipped as in Example I, there is charged 75 parts N-methylethanolamine. With care being taken to control the exothermic reaction, 176 parts ethyl acetate is added dropwise to the reaction vessel. The reaction mixture is heated and refluxed at 85-87C. for 15 minutes with ethanol distillate being collected, with a base value of 149 obtained thereafter. Then 100 parts ethyl acetate is added to the reaction mixture and refluxing is continued three more hours, with a base value of 83 being obtained. Ano~her three hours of refluxing yields a base value for the reaction mixture of 67. Then refluxing is continued until a temperature of 94C. is reached at which time 100 parts more ethyl acetate is added.
Refluxing is continued three more hours after which time a base value of 49 is obtained. Volatile solvent is removed from the reaction mixture by conventional methods.
From the reaction product obtained above, 94 parts is charged into a reaction vessel equipped as before, together with 58 parts acrylic acid, 0.03 part of 0.1 percent phenothiazine solution, 0~02 part hydroquinone, ~2Q-11~25'~3 200 parts methyl isobutyl ketone and 100 parts toluene. The reaction mixture is refluxed at 114-117C. for five and one-half hours after which time 11 parts water of reaction is collected. The mixture is then allowed to cool and stand overnight. Refluxing is then continued at 117-119 C. for about six more hours after which time 3 more parts water of reaction is collected.
EXAMPLE XII
Into a reaction vessel equipped as in Example I, there is charged 150 parts N-methylethanolamine which is heated to about 50 C. Thereafter 250 parts ~ -caprolactone is added dropwise to the reaction mixture over a two-hour period. The temperature of the reaction mixture is held at about 50 C.for one hour and then maintained at about 60C. for two hours. The base value of the reaction mixture is found to be 42; then 15 parts more ~ -caprolactone is added to the reaction mixture. The temperature of the reaction mixture is then held at 60C. for 90 minutes after which time a base value of 24.9 is obtained. Then the mixture is held at 60C., for another hour after which time a base value of 24.9 is again obtained. Another 15 parts -caprolactone is then added to the reaction mixture with the temperature being held at 60 C., after which time a base value of 19.9 is obtained. The reaction mixture is then cooled and to the vessel are charged 288 parts acrylic acid, 10 parts 77 percent formic acid, 25 parts 0.1 percent phenothiazine solution, 4 parts butylstannoic acid, 0.03 part hydroquinone and 250 parts toluene solvent. The reaction mixture is then refluxed for eight hours with 60 parts water of reaction being collected. The mixture is then filtered and volatile solvent is removed by conventional stripping methods.
EXAMP~E XIII
Into a reaction vessel equipped as in Example I, there are charged ~; 134 parts dimethylolpropionic acid, 0.5 part methanesulphonic acid and 400 - parts methanol. The reaction mixture is refluxed 15 hours after which time ll'~;~Si~3 an acid value of about 14.5 is obtained. Then 200 parts toluene, 105 parts diethanolamine and 8 parts sodium methoxide (25 percent in methanol) is added to the reaction mixture. The mixture is refluxed for about one hour with the reaction mixture temperature going from 70C. initially to 150C. finally, after which time roughly 475 parts volatile solvent is collected consisting of approximately two-thirds methanol and one-third toluene. A base value of 244 is then obtained for the reaction mixture. Then about 176 parts toluene is added to the reaction mixture, and refluxing is continued for three hours and 40 minutes more at a temperature of about 113-134 C., after which time a base value of 177 is obtained. The reaction mixture is then refluxed an additional five and one-half hours. Then the reaction vessel is charged with 210 parts acrylic acid, 5 parts butylstannoic acid, 0.03 part phenothiazine solution, 0.2 part hydroquinone and 87 parts toluene. The reaction mixture is then refluxed for eight hours after which time 31 parts water of reaction is collected. Volatile solvent is then removed from the reaction mixture by conventional methods.
EXAMPLE XIV
Into a reaction vessel equipped as in Example I, there is charged 263 parts diethanolamine together with 45 parts toluene. Over a period of 30 minutes, 136 parts 85 percent formic acid is added dropwise to the reaction vessel with no heat being applied during the exothermic reaction.
Thereafter, heat is applied to the reaction vessel to maintain refluxing con-ditions for eight hours, during which time the temperature ranges from 101-113 C.
At the end of the reflux period, approximately 61 parts water is collected.
Volatile solvent is then removed from the reaction product by conventional methods.
Into a second reaction vessel similarly equipped, there are charged 172 parts methacrylic acid, 133 parts of the previously prepared reaction 25 ~3 product, 2 parts butylstannoic acid, 0.5 part di-t-butyl-p-cresol, 0.1 part hydroquinone, 0.02 part thenothiazine and 200 parts toluene. The reaction mixture is refluxed for eight and three-quarter hours at 118-126 C., with 28 parts water being collected. The reaction mixture is then cooled, filtered and stripped of volatile solvent by conventional methods.
EXAMPLE XV
Into a reaction vessel equipped as in Example I, there are charged 220 parts ~ -valerolactone and 210 parts diethanolamine. Under a nitrogen blanket, the reaction mixture is heated at about 100 C. for two hours and 10 minutes, after which time a viscosity of L is measured on an undiluted sample. The reaction mixture is cooled, allowed to sit overnight and is then heated for one hour at about 100C., after which time a viscosity of V is measured.
Into a second reaction vessel similarly equipped, 14 parts of 97 percent formic acid is gradually added over a period of lS minutes to 245 parts of the previously prepared reaction product having a solids fraction of 75.7 percent. Then to the reaction mixture are added 297 parts acrylic acid, 5.4 parts butylstannoic acid, 0.05 part phenothiazine, 0.27 part hydroquinone, 2.5 part di-t-butyl-p-cresol and 82 parts toluene. The reaction mixture is heated for about two hours at 123-130 C., after which time 29 parts water is collected. Then the reaction mixture is cooled and allowed to sit overnight and is thereafter heated for a period of about seven hours at 130-140 C., after which time an additional 30 parts water is collected.
The reaction mixture is cooled and allowed to stand for about 65 hours at room temperature under ambient conditions. Then the mixture is heated for about one hour at about 140 C., after which time an additional 2 parts water is collected. Then by conventional methods, the reaction mixture is filtered, stripped and refiltered with a viscosity of C being measured on an undiluted ., 5 ~ 3 sample of the reaction product.
EXAMPLE XVI
Coating compositions having amide acrylate monomer derived as set forth in previous examples are prepared according to the following general formulation:
Composition #l Parts amide acrylate monomer of 40 Example XIV
hydroxyethyl acrylate 8 benzophenone 0.8 , . -24-Composition #2 Parts amide acrylate monomer of Example I 5 amide acrylate monomer of Example XV 5 hydroxyethylacrylate 3 benzophenone 0.26 The above compositions are coated onto aluminum panels, 4 inches by 12 inches in size, with a wire-wound draw-down bar to a film thickness of about 0.9 mil. The panels are sub;ected to ultraviolet radiation from a single 200 watt per inch mercury vapor lamp placed at a distance of three inches from a conveyor carrying the panels. The panels are exposed to the UV radiation under ambient atmospheric conditions.
It is found that panels coated with composition #l and traveling at conveyor speeds of up to 60 feet per minute cured mar-free by the finger-nail test, while panels traveling at 100 feet per minute under the W lamp have film coatings which mar.
Panels coated with composition ~2 are cured under identical conditions except that UY exposure occurs under a nitrogen atmosphere with a conveyor speed of 20 feet per minute. The cured film coatings show a slight mar under the fingernail test.
According to the provisions of the Patent Statutes, there are described above the invention and what are now considered to be its best embodiments. However, within the scope of the appended claims, it is to be understood that the invention can be practiced otherwise than as specifically described.
T~
Claims (18)
1. An amide acrylate compound having one nitrogen atom and being of the formula:
wherein X, Y and Z may each independently be H, alkyl, aryl, acrylyloxyalkyl, acrylyloxy aliphatic ester formed by reaction of acrylating material with hydroxyl terminated aliphatic ester-containing intermediate resulting from the reaction of inner ester of hydroxy carboxylic acid and amino alcohol, or acrylyloxy aliphatic ether, provided that X, Y and Z together have two, three or four acrylyloxy groups.
wherein X, Y and Z may each independently be H, alkyl, aryl, acrylyloxyalkyl, acrylyloxy aliphatic ester formed by reaction of acrylating material with hydroxyl terminated aliphatic ester-containing intermediate resulting from the reaction of inner ester of hydroxy carboxylic acid and amino alcohol, or acrylyloxy aliphatic ether, provided that X, Y and Z together have two, three or four acrylyloxy groups.
2. The amide acrylate compound of claim 1, wherein X is hydrogen, Y and Z are each .
3. The amide acrylate compound of claim 1, wherein X is .
Y and Z are each .
Y and Z are each .
4, The amide acrylate compound of claim 1, wherein X is Y and Z are each .
The amide acrylate compound of claim 1, wherein X is Y and Z are each .
6. The amide acrylate compound of claim 1, wherein X is Y and Z are each .
7. The amide acrylate compound of claim 1, wherein X is Y and Z are each .
8. The amide acrylate compound of claim 1, wherein X is Y and Z are each .
9. The amide acrylate compound of claim 1, wherein X is Y is -CH3 Z is .
10. The amide acrylate compound of claim 1, wherein Y and Z are each .
11. A method for preparing an amide acrylate compound having one nitrogen atom and being of the formula:
wherein X, Y and Z may each independently be H, alkyl, aryl, acrylyloxyalkyl, acrylyloxy aliphatic ester formed by reaction of acrylating material with hydroxyl terminated aliphatic ester-containing intermediate resulting from the reaction of inner ester of hydroxy carboxylic acid and amino alcohol, or acrylyloxy aliphatic ether, provided that X, Y and Z together have two, three or four acrylyloxy groups, said method comprising:
(a) reacting a compound selected from the group consisting of a carboxylic acid, an ester of a carboxylic acid, a hydroxy acid and an inner ester of a hydroxy carboxylic acid with an aminoalcohol to form an amide-containing hydroxy-group terminated intermediate; and (b) reacting said intermediate with an acrylic group-containing compound to form said amide acrylate compound.
wherein X, Y and Z may each independently be H, alkyl, aryl, acrylyloxyalkyl, acrylyloxy aliphatic ester formed by reaction of acrylating material with hydroxyl terminated aliphatic ester-containing intermediate resulting from the reaction of inner ester of hydroxy carboxylic acid and amino alcohol, or acrylyloxy aliphatic ether, provided that X, Y and Z together have two, three or four acrylyloxy groups, said method comprising:
(a) reacting a compound selected from the group consisting of a carboxylic acid, an ester of a carboxylic acid, a hydroxy acid and an inner ester of a hydroxy carboxylic acid with an aminoalcohol to form an amide-containing hydroxy-group terminated intermediate; and (b) reacting said intermediate with an acrylic group-containing compound to form said amide acrylate compound.
12. The method of claim 11, wherein said carboxylic acid is selected from the group consisting of formic acid, 2-ethylhexanoic acid and benzoic acid.
13. The method of claim 11, wherein said ester of a carboxylic acid is selected from the group consisting of methyl formate and ethyl acetate.
14. The method of claim 11, wherein said hydroxy acid is hydroxy-acetic acid.
15. The method of claim 11, wherein said inner ester of a hydroxy carboxylic acid is selected from the group consisting of Y -butyrolactone, .gamma. -valerolactone and .epsilon.-caprolactone.
16. The method of claim 11, wherein said aminoalcohol is selected from the group consisting of diethanolamine and N-methylethanolamine.
17. The method of claim 11, wherein said acrylic group-containing compound is selected from the group consisting of acrylic acid and methacrylic acid.
18. The method of claim 11, wherein said intermediate and said acrylic group-containing compound are reacted together in the presence of butylstannoic acid catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82185677A | 1977-08-04 | 1977-08-04 | |
| US821,856 | 1977-08-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142543A true CA1142543A (en) | 1983-03-08 |
Family
ID=25234468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000307235A Expired CA1142543A (en) | 1977-08-04 | 1978-07-12 | Amide acrylate compounds for use in radiation-curable coating compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1142543A (en) |
-
1978
- 1978-07-12 CA CA000307235A patent/CA1142543A/en not_active Expired
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