CA1127345A - Radiation curable compositions - Google Patents
Radiation curable compositionsInfo
- Publication number
- CA1127345A CA1127345A CA283,688A CA283688A CA1127345A CA 1127345 A CA1127345 A CA 1127345A CA 283688 A CA283688 A CA 283688A CA 1127345 A CA1127345 A CA 1127345A
- Authority
- CA
- Canada
- Prior art keywords
- mol percent
- polyol
- isocyanate
- unsaturated
- isophthalic acid
- 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
Links
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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
-
- 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
Landscapes
- 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)
Abstract
ABSTRACT OF THE DISCLOSURE
Unsaturated addition-polymerizable urethane resins pre-pared from at least one polyisocyanate, at least one monomeric or polymeric polyol, and at least one unsaturated addition-polymeriz-able monomeric organic compound characterized by the presence of a single isocyanate-reactive active hydrogen group, wherein said polyol has a hydroxyl functionality of at least 2.1, and the amount of polyisocyanate is sufficient to provide an NCO:OH ratio, with respect to said polyol, of at least 2.1:1, are characterized by reduced viscosity, improved physical stability, and by improved solubility and compatibility in organic solvents/diluents.
Particularly advantageous resins are obtained by employing iso-cyanate-functional prepolymers as precursors for such unsaturated addition-polymerizable urethane resins.
Unsaturated addition-polymerizable urethane resins pre-pared from at least one polyisocyanate, at least one monomeric or polymeric polyol, and at least one unsaturated addition-polymeriz-able monomeric organic compound characterized by the presence of a single isocyanate-reactive active hydrogen group, wherein said polyol has a hydroxyl functionality of at least 2.1, and the amount of polyisocyanate is sufficient to provide an NCO:OH ratio, with respect to said polyol, of at least 2.1:1, are characterized by reduced viscosity, improved physical stability, and by improved solubility and compatibility in organic solvents/diluents.
Particularly advantageous resins are obtained by employing iso-cyanate-functional prepolymers as precursors for such unsaturated addition-polymerizable urethane resins.
Description
~1~7~4i~
This invention relates to radiation curable coating and ink compositions. More particularly, this invention relates to unsaturated addition-polymerizable urethane resins and to radia-tion curable compositions containing such resins.
Increasing concern with energy, environmental protection, and health factors have cooperated to enhance the potential of radiation curable coatings. In principle, such coatings comprise a polymerizable mixture that can be applied as a thin film to a substrate and polymerized at a rapid rate by exposure to a radia-tion source such as an electron beam, plasma arc, ultra violetlight, and the like. Advantages of radiation curable coatings include a practical method of at least reducing air pollution from volatile vapor loss, rapid cure rates at ambient temperatures, reauced operating costs, the use of heat-sensitive substrates, and improved product performance.
Among the more notable achievements in the field of radiation curing has been the development of the so-called 100 percent reactive solids systems based on unsaturated addition-; polymerizable urethane resin. A characteristic feature of such systems is the substantial absence of conventional inert volatilesolvents. Instead, the systems contain reactive diluents which react during curing to become an integral part of the cured coating.
Such systems have been widely accepted commercially. While such systems provide high-performance coatings which can be cured at high line speeds, they have also provided a new set of problems for the coatings formulators.
While unsaturated addition-polymerizable urethane resins can be prepared by several known reaction routes, the preferred method of preparation for obtaining premium-quality coatings is by capping an isocyanate-functional prepolymer with an appropriate addition-polymerizable monomer having a single isocyan-ate-reactive active hydrogen group, with the reaction being effected in the ~ ~Z73~i plesence of a diluen-t system which is inert with respect to the capping reaction but which is reactive with the unsaturated addition-polymerizable urethane resins at cure conditions. Among the more vexing of the problems associated with radiation curable compositions containing such polymerizable urethane resins, regardless of how the resin is prepared, are the high viscosity of the resin compositions which makes application by conventional industrial techniques extremely difficult, if not impossible; the difficulty of solvating the resinous compounds; physical instability lQ of the compositions which is evidenced by thixotropy and/or cloudiness leading to eventual separation of the compositions into distinct resin-rich and monomer-rich phases; and an incom-patibility between resinous and non-resinous components which is more evident with higher molecular weight components. Because the use of conventional inert solvents/diluents such as are employed with moisture-cure polyurethanes is undesirable, there have been developed the so-called reactive diluent systems, which generally comprise a mixture of monofunctional and polyfunctional unsat-urated addition-polymerizable monomeric compounds which are co-polymerizable with the unsaturated addition-polymerizable urethane resins and thus become part of the cured coating. However, these reactive diluent systems are not without problems. For example, certain of the lower molecular weight monomeric diluents are - quite effective in affording clear coating compositions which can be applied by conventional industrial techniques; however, their use in diluent systems is often undesirable because of their relatively high volatility, even at the relatively low temperatures encountered during the curing cycle, which results in diluent loss, noxious fumes, increased atmospheric emissions, and a fogging above the work surface which interferes with energy transmission and adversely affects rate and degree of cure. These problems which are associated with the higher solvating low molecular weight monomer llZ7;~4~
diluents can be largely overcome by employing as reactive monomer diluents acrylic and methacrylic acid esters containing at least six carbon atoms in the non-acid moiety of the molecule. While such acrylic and methacrylic acid esters are preferred because they do not present the volatility, noxious and curing problems asso-ciated with the lower molecular weight diluents, they are not with-out their problems. Generally, greater amounts of the acrylic and methacrylic acid esters having at least six carbon atoms in the non-acid moiety of the molecule are required for efEective viscoity reduction. Because of their lower solvating power, the problems of physical instability and incompatibility of resin and diluent components are generally greater with diluent systems containing the less-volatile acrylic and methacrylic acid esters.
Thus there remains a need to produce radiation curable compositions ~ which will remain homogeneous, which can be readily and uniformly - applied to substrates and which can be rapidly and fully cured to a dried film having the desired physical and chemical properties.
It is equally important that harmful emissions to the atmosphere, noxiousness and other hazards be at least reduced, if not entirely eliminated.
During the course of extensive studies relating to the physical and chemical nature of radiation curable compositions, particularly such compositions containing unsaturated addition-polymerizable urethane resinsr it was discovered that the composition of the resinous component markedly affects viscosity and physical stability of the compositions, as wèll as solubility and compatibility of the resinous components with respect to the reactive diluent system. More particularly, in accordance with the present invention, it has been discovered that unsaturated addition-polymerizable urethane resins having as characteristic features reduced viscosity, improved physical stability, and which are more readily soluble in or solvatable by and compatible with .
X
- ~lZ~3~
or,ganic solvent/diluent systems can be obtained by employing as precursors at least one organic isocyanate compound having at least two isocyanate groups at least one monomeric or polymeric polyol compound having at least two hydroxyl groups, and at least one unsaturated addition-polymerizable monomeric organic com-pound characterized by -the presence of a single isocyanate-reac-tive active hydrogen group; provided that the amount of isocya-nate compound is sufficient to afford an NCO:OH ratio, with res-pect to the polvol compound, of at least 2.1:1, preferably 2.3-4:
1; and the average hydroxyl Eunctionality of the polyol component `~ is at least 2.1, preferably is in the range from 3.2 to 3.0, and most advantageously is in the range from about 2.3 to about ` 2.7. For brevity, unsaturated addition-polymerizable urethane resins will be referred to hereinafter in the disclosure and claims as unsaturated urethane resins. Radiation curable com-positions containing the unsaturated urethane resins of the in-vention have an increased flowability and a substantially im-proved physical stability, can be readily and uniformly applied to metallic, fabrlc and plastic substrates by conventional indus-trial techniques, and rapidly cure upon exposure to a source of radiation to afford dried films having excellent properties.
Unsaturated urethane resins prepared in accordnace with this invention are readily solvated by and more compatible with acrylic and methacrylic acid esters having at least six carbon atoms in the non-acid moiety of the ester molecule, and permit theuse of such low-volatility diluents at higher diluent levels ; than heretofore. The present invention further provides compo-sitions having a more manageable viscosity at higher resin con-tent than heretofore possible.
More particularly, in accordance with the present in-vention, there are provided unsaturated urethane resins compris-ing the reaction product of i) at least one organic isocyanate compound having at least two isocyanate groups;
ii) from about 30 to 100, preferably 70 to 100, mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
iii) from about 70 to zero, preferably about 30 to zero, mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl yroups; and ; iv) at least one unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group;
said isocyanate compound being present in an amount sufficient to provide an NCO:OH ratio of at least 2.1:1, pre-ferably in the range of 2.3-4:1, with respect to such polymeric and monomeric polyol hydroxyl groups;
said mol percents being based on total mols of such polymeric and monomeric polyol hydroxyl groups;
the average hydroxyl functionality with respect to such monomeric and polymeric polyols is at least 2 1, preferably is in the range from about 2.2 to about 3.0, and advantageously is in the range from about 2.3 to about 2.7;
and wherein the amount of said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reac-tive active hydrogen group is sufficient to provide at least one molar equivalent with respect to isocyanate reactivity, and is preferably sufficient to provide an active hydrogen group:NCO
ratio of at least 1:1 with respect to total excess isocyanate functions present. The invention further provides radiation curable compositions comprising A. at least one unsaturated urethane resin prepared in accordance wlth this invention;
B. a reactive diluent system comprising at least one . - 5 ~
7;~
.
unsaturated addition-polymerizable monomeric compound which is copolymerizable with said unsaturated urethane resin, said di-luent system preferably containing at least one unsaturated addition-polymerizable monofunctional monomeric compound selected from the group consisting of esters having the genreal formula O
;;` 11 CH2 = C - C - O - R, R
wherein R is hydrogen or methyl and R is an aliphatic or cyclo-aliphatic, preferably alkyl or cycloalkyl, group having from 6 to 18, preferably 6 to 9, carbon atoms; and, optionally, C. an effective amount of at least one photoinitiator compound;
the amount of such unsatura~ted urethane resin being in the range from about 30 to about 90, preferably from about 50 to about 75, weight percent, based on total weight of such un-saturated urethane resin and such reactive diluent system. The photoinitiator compound, which will generally be employed when curing is effected with a low energy radiation source such as ultraviolet light radiation, will generally be in the range from about 0.01 to about 30, preferably about 0.1 to about 15, parts by weight per 100 parts by combined weight of unsaturated ure-thane resin and reactive diluent system.
Unsaturated urethane resins are well known in the art.
Such resins comprise the reaction product of at least one organic isocyanate having at least two isocyanate groups, at least one monomeric or polymeric organic compound characterized by the presence of at least two isocyanate-reactive active hydrogen groups, and at least one unsaturated addition-polymerizable mono-meric organic compound having a single isocyanate-reactive active - hydrogen group,- there being an excess of organic isocyanate com-pound with respect to said organic compounds containing at ~7 ~lZ~5 least two isocyanate-reactive active hvdrogen groups. Unsaturat-ed urethane resins can be prepared by several known reaction routes, with the method wherein an isocyanate-functional prepoly-mer, obtained by reacting an excess of organic isocyanate having at least two isocyanate groups with organic compounds having at least two active hydrogen groups, is reacted with an appro-priate unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group, such as 2-hydroxyethyl acrylate, being presently preferred. The vari-ous methods of preparing unsaturated urethane resins and prepoly-mer precursors are sufficiently well known as to require no fur-ther elaboration herein. The unsaturated urethane resins of this invention can be prepared by any of the known methods, with such resins prepared through the route of isocyanate-functional prepolymers being especially preferred.
Unsaturated urethane resins which are suitable for use in the practice of this invention have as a first characteristic feature, at least one, preferably at least two, polymerizable ethylenically unsaturated group(s) having the structure =C = C .
The polymerizable ethylenically unsaturated moiety is preferably a terminal vinyl group having the structure CH2 = C . Especially preferred unsaturated urethane resins are the acrylyl urethane resins, i.e. unsaturated urethane resins containing a polymeriz-able acrylyl, methacrylyl, acrylamide, methyacrylamide, and the like, moiety in the molecule, characterized by the presence of at least one, preferably at least two, terminal ethylenically un-saturated group(s) having the structure CH2 = C
The unsaturated urethane resins of the invention are further characterized in that they are obtained from organic polyisocyanate and organic polyol precursor compounds, as these compounds have been previously defined, at the NCO:OH ratios and hvdroxyl functionalities previously set forth. It will be 1~ 3~
appreciated by the person skilled in the art that there must be emploved a finite amount of at least one monomeric or polymeric organic polyol having at least three hydroxyl groups if the requirement of a hydroxyl functionality of at least 2.1 is to be satisfied. The invention thus encompasses mixtures of polyols, including mixtures of polyols haviny two hydroxyl groups and polyols having at least three hydroxyl groups.
The polyisocyanate which can be employed in formin~
the isocyanate-functional prepolymer can be any organic isocyanate having at least two free isocyanate groups. Included within the preview of suitable polyisocyanates are aliphatic, cycloaliphatic, and aromatic polyisocyanates, as these terms are generally in-terpreted in the art. Thus it willbe appreciated that any of the known polyisocyanates such as alkyl and alkylene polyisocya-nates, cycloalkyl and cycloalkylene polyisocyanates, aryl and arylene polyisocyanates, and combinations such as alkylene, cyclo-alkylene and alkylene arylene polyisocyanates, can be employed in the practice of the present invention.
Suitable polyisocyanates include, without limitation, tolylene-2,4-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-di-isocyanate, hexamethvlene-1,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, triphenylmethane-4,4',4"-triisocvanate, poly-methylene polyphenylisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, naphthalene-1,4-diisocyanate, diphenylene-4,4'-diisocyanate, 3,3'-bi-tolylene-4,4'-diisocvanate, 1,4-cyclohexy-lene dimeth'ylene diisocyanate, xylylene-1,4-diisocyanate, xyly-lene-1,3-diisocyanate, cyclohexyl-1,4-diisocyanate, 4,4'-methyl-ene-bis(cyclohexyl isocyanate), 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, the product obtained by reactin~ trimethylol propane and 2,4-tolylene diisocyanate in a molar ratio of 1:3, and the like.
~-2~3~5 Polyol compounds having at least two hydroxyl groups per molecule which are suitable for use in preparing the herein described unsaturated urethane resins comprise from about 30 to 100, preferably about 70 to 100, mol percent of at least one polymeric polyol and from about 70 to zero, preferably about 30 to zero mol percent of at least one monomeric polyol, including mixtures of such polyols. Polymeric and monomeric polyols are so well-known in the art that no need is seen to describe these materials in any detail. The polymeric polyhydroxy compounds can be dihydroxylated and polyhydroxylated polyethers and poly-esters, including polyesters derived from caprolactone compounds, i.e., polyca~rola:cto~e polyols. The polyether and polyester poly-ols can be diols, triols, tetrols, and the like, with polyester polyols comprising the reaction product of i) at least one glycol selected from the group consis-ting of 1,3-butylene glycol and neopentryl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv~ from about zero to about ~0, preferably from about zero to about 30, mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of glycol and polyol, the amount of isophthalic acid being in the range of from about 1 to about 50, preferably about 5 to about 20 mQl percent, based on total mols of adipic acid and isophthalic acid, being especially preferred, with such polyester polyols having an aver-age hydroxyl functionality of at least 2.1 being most advanta-geous. Similarly, the monomeric polyols which can replace up to about 70 mol percent of the polymeric polyol compounds can be diols, triols, tetrols and the like and include, without limi-- tation thereto,-compounds such as ethylene glycol, propylene g:Lycol, diethylene glycol, glycerol, dipropylene glycol, erythri-3~5 ..
tol, pentaerythritol, trimethylol propane, neopentyl glycol,and the like. Polyols employed in the practice of the invention will have molecular weights in the range from about 60 to about ~,000, with molecular weights in the range from about 500 to about 2,000 being presently preferred. The polymeric polyols and method of preparing such compounds are well known in the art and require no further elaboration.
Unsaturated addition-polymerizable monomeric organic compounds having a single isocya~ate-reactive active hydrogen group which can be employed in the practice of the present in-vention include any of such compounds which have been previously used to introduce an unsaturated polymerizable moiety into a molecule via reaction between the ac-tive hydrogen group and a re-active isocyanate moiety. Preferably, the active hydrogen group is hydroxy. Illustrative of unsaturated addition-polymerizable monomeric organic compounds having a single isocyanate-reactive active hydrogen group are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl metha-crylate, N-hydroxymethyl acrylamine, N-hydroxymethyl metha-crylamide, diethylene glycol monoacrylate, diethylene glycolmonomethacrylate, glycerine dimethacrylate, trimethylol propane dimethacrylate, and the like. The amount of such compounds will be sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate functionality, and pre-ferably is sufficient to afford an active hydrogen group:NCO
ratio, with respect to the amount of total free hydroxyl func-tions, of at least 1:1, with a small excess, 10 mol percent or less, being especially preferred.
As has been indicated, the herein described unsatur-ated urethane resins are preferably obtained by reacting atleast one isocyanate-functional prepolymer with at least one unsaturated addition-polymerizable m~momeric organic compound having a 'X; - 10 -7~5 single isocyanate-reactive active hydrogen group, with unsa-turated urethane resins having substantially no free isocyanate functionality being especially preferred. Suitable prepolymers can be prepared according to known methods from the above listed precursors, keeping in mind the requirements for NCO:OH ratio and average hydroxyl functionality. Such prepolymers can be prepared neat, but are preferably prepared in the presence of a diluent phase which is copolymerizable with the unsaturated urethane resin but is inert with respect to the prepolymer re-action and the subsequent reaction between the prepolymer andthe unsaturated addition-polymerizable monomeric organic com-pound having a single lsocyanate-reactive active hydrogen group.
As noted, the radiation curable compositions of the present invention comprise a mixture of i) at least one unsaturated urethane resin prepared in accordance with this invention;
ii) a reactive diluent system comprising at least one unsaturated addition-polymerizable monomeric compound which is copolymerizable with said unsaturated urethane resin, and preferably containing at least one acrylic and/or methacrylic acid ester containing at least 6 carbon atoms in the non-acid moiety; and, optionally, iii) an effective amount of at least one photoini-tiator compound, within the compositional parameters previously set forth.
Reactive diluent systems which can be employed in the radiation curable compositions of this invention include any of such systems which have been or are being used for this purpose. Broadly, suitable reactive diluent systems comprise at least one unsaturated addition-polymerizable monomer which is copolyrneriza~le with -the unsaturated urethane resin upon ex-posure to radiation. The reactive diluent can be monofunctional .,~,~, , - 1 1 -~Z~ s5 or polyfunctional. A single polyfunctional diluent can be used, as can mixtures thereof; or a combination of one or more mono-functional reactive diluents and one or more polyEunctional reactive diluents can be used. Such combinations of mono- and polyfunctional reactive diluents are presently preferred. General-ly, the reactive diluent system will comprise from about 10 to about 65, preferably about 25 to about 50, weight percent, based on total weight of unsaturated urethane resin and reactive di-luent, of the radiation curable compositions of the invention.
Particularly preferred reactive diluents are unsaturated addition-polymerizable monofunctional monomeric compounds selected from the group consisting of esters having the general formula O
CH2 = C - C - O - R, 1o wherein R and R are as previously defined. Representative of such preferred reactive monomeric diluents, without limitation thereto, are hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, stearyl acrylate, and the corresponding methacrylates. Illustrative of other reactive monofunctional and polyfunctional monomeric diluents which can be employed are styrene, methyl methacrylate, butyl acrylate, isobutyl acrylate, 2-phenoxy acrylate, 2-methoxyethyl acrylate,
This invention relates to radiation curable coating and ink compositions. More particularly, this invention relates to unsaturated addition-polymerizable urethane resins and to radia-tion curable compositions containing such resins.
Increasing concern with energy, environmental protection, and health factors have cooperated to enhance the potential of radiation curable coatings. In principle, such coatings comprise a polymerizable mixture that can be applied as a thin film to a substrate and polymerized at a rapid rate by exposure to a radia-tion source such as an electron beam, plasma arc, ultra violetlight, and the like. Advantages of radiation curable coatings include a practical method of at least reducing air pollution from volatile vapor loss, rapid cure rates at ambient temperatures, reauced operating costs, the use of heat-sensitive substrates, and improved product performance.
Among the more notable achievements in the field of radiation curing has been the development of the so-called 100 percent reactive solids systems based on unsaturated addition-; polymerizable urethane resin. A characteristic feature of such systems is the substantial absence of conventional inert volatilesolvents. Instead, the systems contain reactive diluents which react during curing to become an integral part of the cured coating.
Such systems have been widely accepted commercially. While such systems provide high-performance coatings which can be cured at high line speeds, they have also provided a new set of problems for the coatings formulators.
While unsaturated addition-polymerizable urethane resins can be prepared by several known reaction routes, the preferred method of preparation for obtaining premium-quality coatings is by capping an isocyanate-functional prepolymer with an appropriate addition-polymerizable monomer having a single isocyan-ate-reactive active hydrogen group, with the reaction being effected in the ~ ~Z73~i plesence of a diluen-t system which is inert with respect to the capping reaction but which is reactive with the unsaturated addition-polymerizable urethane resins at cure conditions. Among the more vexing of the problems associated with radiation curable compositions containing such polymerizable urethane resins, regardless of how the resin is prepared, are the high viscosity of the resin compositions which makes application by conventional industrial techniques extremely difficult, if not impossible; the difficulty of solvating the resinous compounds; physical instability lQ of the compositions which is evidenced by thixotropy and/or cloudiness leading to eventual separation of the compositions into distinct resin-rich and monomer-rich phases; and an incom-patibility between resinous and non-resinous components which is more evident with higher molecular weight components. Because the use of conventional inert solvents/diluents such as are employed with moisture-cure polyurethanes is undesirable, there have been developed the so-called reactive diluent systems, which generally comprise a mixture of monofunctional and polyfunctional unsat-urated addition-polymerizable monomeric compounds which are co-polymerizable with the unsaturated addition-polymerizable urethane resins and thus become part of the cured coating. However, these reactive diluent systems are not without problems. For example, certain of the lower molecular weight monomeric diluents are - quite effective in affording clear coating compositions which can be applied by conventional industrial techniques; however, their use in diluent systems is often undesirable because of their relatively high volatility, even at the relatively low temperatures encountered during the curing cycle, which results in diluent loss, noxious fumes, increased atmospheric emissions, and a fogging above the work surface which interferes with energy transmission and adversely affects rate and degree of cure. These problems which are associated with the higher solvating low molecular weight monomer llZ7;~4~
diluents can be largely overcome by employing as reactive monomer diluents acrylic and methacrylic acid esters containing at least six carbon atoms in the non-acid moiety of the molecule. While such acrylic and methacrylic acid esters are preferred because they do not present the volatility, noxious and curing problems asso-ciated with the lower molecular weight diluents, they are not with-out their problems. Generally, greater amounts of the acrylic and methacrylic acid esters having at least six carbon atoms in the non-acid moiety of the molecule are required for efEective viscoity reduction. Because of their lower solvating power, the problems of physical instability and incompatibility of resin and diluent components are generally greater with diluent systems containing the less-volatile acrylic and methacrylic acid esters.
Thus there remains a need to produce radiation curable compositions ~ which will remain homogeneous, which can be readily and uniformly - applied to substrates and which can be rapidly and fully cured to a dried film having the desired physical and chemical properties.
It is equally important that harmful emissions to the atmosphere, noxiousness and other hazards be at least reduced, if not entirely eliminated.
During the course of extensive studies relating to the physical and chemical nature of radiation curable compositions, particularly such compositions containing unsaturated addition-polymerizable urethane resinsr it was discovered that the composition of the resinous component markedly affects viscosity and physical stability of the compositions, as wèll as solubility and compatibility of the resinous components with respect to the reactive diluent system. More particularly, in accordance with the present invention, it has been discovered that unsaturated addition-polymerizable urethane resins having as characteristic features reduced viscosity, improved physical stability, and which are more readily soluble in or solvatable by and compatible with .
X
- ~lZ~3~
or,ganic solvent/diluent systems can be obtained by employing as precursors at least one organic isocyanate compound having at least two isocyanate groups at least one monomeric or polymeric polyol compound having at least two hydroxyl groups, and at least one unsaturated addition-polymerizable monomeric organic com-pound characterized by -the presence of a single isocyanate-reac-tive active hydrogen group; provided that the amount of isocya-nate compound is sufficient to afford an NCO:OH ratio, with res-pect to the polvol compound, of at least 2.1:1, preferably 2.3-4:
1; and the average hydroxyl Eunctionality of the polyol component `~ is at least 2.1, preferably is in the range from 3.2 to 3.0, and most advantageously is in the range from about 2.3 to about ` 2.7. For brevity, unsaturated addition-polymerizable urethane resins will be referred to hereinafter in the disclosure and claims as unsaturated urethane resins. Radiation curable com-positions containing the unsaturated urethane resins of the in-vention have an increased flowability and a substantially im-proved physical stability, can be readily and uniformly applied to metallic, fabrlc and plastic substrates by conventional indus-trial techniques, and rapidly cure upon exposure to a source of radiation to afford dried films having excellent properties.
Unsaturated urethane resins prepared in accordnace with this invention are readily solvated by and more compatible with acrylic and methacrylic acid esters having at least six carbon atoms in the non-acid moiety of the ester molecule, and permit theuse of such low-volatility diluents at higher diluent levels ; than heretofore. The present invention further provides compo-sitions having a more manageable viscosity at higher resin con-tent than heretofore possible.
More particularly, in accordance with the present in-vention, there are provided unsaturated urethane resins compris-ing the reaction product of i) at least one organic isocyanate compound having at least two isocyanate groups;
ii) from about 30 to 100, preferably 70 to 100, mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
iii) from about 70 to zero, preferably about 30 to zero, mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl yroups; and ; iv) at least one unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group;
said isocyanate compound being present in an amount sufficient to provide an NCO:OH ratio of at least 2.1:1, pre-ferably in the range of 2.3-4:1, with respect to such polymeric and monomeric polyol hydroxyl groups;
said mol percents being based on total mols of such polymeric and monomeric polyol hydroxyl groups;
the average hydroxyl functionality with respect to such monomeric and polymeric polyols is at least 2 1, preferably is in the range from about 2.2 to about 3.0, and advantageously is in the range from about 2.3 to about 2.7;
and wherein the amount of said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reac-tive active hydrogen group is sufficient to provide at least one molar equivalent with respect to isocyanate reactivity, and is preferably sufficient to provide an active hydrogen group:NCO
ratio of at least 1:1 with respect to total excess isocyanate functions present. The invention further provides radiation curable compositions comprising A. at least one unsaturated urethane resin prepared in accordance wlth this invention;
B. a reactive diluent system comprising at least one . - 5 ~
7;~
.
unsaturated addition-polymerizable monomeric compound which is copolymerizable with said unsaturated urethane resin, said di-luent system preferably containing at least one unsaturated addition-polymerizable monofunctional monomeric compound selected from the group consisting of esters having the genreal formula O
;;` 11 CH2 = C - C - O - R, R
wherein R is hydrogen or methyl and R is an aliphatic or cyclo-aliphatic, preferably alkyl or cycloalkyl, group having from 6 to 18, preferably 6 to 9, carbon atoms; and, optionally, C. an effective amount of at least one photoinitiator compound;
the amount of such unsatura~ted urethane resin being in the range from about 30 to about 90, preferably from about 50 to about 75, weight percent, based on total weight of such un-saturated urethane resin and such reactive diluent system. The photoinitiator compound, which will generally be employed when curing is effected with a low energy radiation source such as ultraviolet light radiation, will generally be in the range from about 0.01 to about 30, preferably about 0.1 to about 15, parts by weight per 100 parts by combined weight of unsaturated ure-thane resin and reactive diluent system.
Unsaturated urethane resins are well known in the art.
Such resins comprise the reaction product of at least one organic isocyanate having at least two isocyanate groups, at least one monomeric or polymeric organic compound characterized by the presence of at least two isocyanate-reactive active hydrogen groups, and at least one unsaturated addition-polymerizable mono-meric organic compound having a single isocyanate-reactive active - hydrogen group,- there being an excess of organic isocyanate com-pound with respect to said organic compounds containing at ~7 ~lZ~5 least two isocyanate-reactive active hvdrogen groups. Unsaturat-ed urethane resins can be prepared by several known reaction routes, with the method wherein an isocyanate-functional prepoly-mer, obtained by reacting an excess of organic isocyanate having at least two isocyanate groups with organic compounds having at least two active hydrogen groups, is reacted with an appro-priate unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group, such as 2-hydroxyethyl acrylate, being presently preferred. The vari-ous methods of preparing unsaturated urethane resins and prepoly-mer precursors are sufficiently well known as to require no fur-ther elaboration herein. The unsaturated urethane resins of this invention can be prepared by any of the known methods, with such resins prepared through the route of isocyanate-functional prepolymers being especially preferred.
Unsaturated urethane resins which are suitable for use in the practice of this invention have as a first characteristic feature, at least one, preferably at least two, polymerizable ethylenically unsaturated group(s) having the structure =C = C .
The polymerizable ethylenically unsaturated moiety is preferably a terminal vinyl group having the structure CH2 = C . Especially preferred unsaturated urethane resins are the acrylyl urethane resins, i.e. unsaturated urethane resins containing a polymeriz-able acrylyl, methacrylyl, acrylamide, methyacrylamide, and the like, moiety in the molecule, characterized by the presence of at least one, preferably at least two, terminal ethylenically un-saturated group(s) having the structure CH2 = C
The unsaturated urethane resins of the invention are further characterized in that they are obtained from organic polyisocyanate and organic polyol precursor compounds, as these compounds have been previously defined, at the NCO:OH ratios and hvdroxyl functionalities previously set forth. It will be 1~ 3~
appreciated by the person skilled in the art that there must be emploved a finite amount of at least one monomeric or polymeric organic polyol having at least three hydroxyl groups if the requirement of a hydroxyl functionality of at least 2.1 is to be satisfied. The invention thus encompasses mixtures of polyols, including mixtures of polyols haviny two hydroxyl groups and polyols having at least three hydroxyl groups.
The polyisocyanate which can be employed in formin~
the isocyanate-functional prepolymer can be any organic isocyanate having at least two free isocyanate groups. Included within the preview of suitable polyisocyanates are aliphatic, cycloaliphatic, and aromatic polyisocyanates, as these terms are generally in-terpreted in the art. Thus it willbe appreciated that any of the known polyisocyanates such as alkyl and alkylene polyisocya-nates, cycloalkyl and cycloalkylene polyisocyanates, aryl and arylene polyisocyanates, and combinations such as alkylene, cyclo-alkylene and alkylene arylene polyisocyanates, can be employed in the practice of the present invention.
Suitable polyisocyanates include, without limitation, tolylene-2,4-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-di-isocyanate, hexamethvlene-1,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, triphenylmethane-4,4',4"-triisocvanate, poly-methylene polyphenylisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, naphthalene-1,4-diisocyanate, diphenylene-4,4'-diisocyanate, 3,3'-bi-tolylene-4,4'-diisocvanate, 1,4-cyclohexy-lene dimeth'ylene diisocyanate, xylylene-1,4-diisocyanate, xyly-lene-1,3-diisocyanate, cyclohexyl-1,4-diisocyanate, 4,4'-methyl-ene-bis(cyclohexyl isocyanate), 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, the product obtained by reactin~ trimethylol propane and 2,4-tolylene diisocyanate in a molar ratio of 1:3, and the like.
~-2~3~5 Polyol compounds having at least two hydroxyl groups per molecule which are suitable for use in preparing the herein described unsaturated urethane resins comprise from about 30 to 100, preferably about 70 to 100, mol percent of at least one polymeric polyol and from about 70 to zero, preferably about 30 to zero mol percent of at least one monomeric polyol, including mixtures of such polyols. Polymeric and monomeric polyols are so well-known in the art that no need is seen to describe these materials in any detail. The polymeric polyhydroxy compounds can be dihydroxylated and polyhydroxylated polyethers and poly-esters, including polyesters derived from caprolactone compounds, i.e., polyca~rola:cto~e polyols. The polyether and polyester poly-ols can be diols, triols, tetrols, and the like, with polyester polyols comprising the reaction product of i) at least one glycol selected from the group consis-ting of 1,3-butylene glycol and neopentryl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv~ from about zero to about ~0, preferably from about zero to about 30, mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of glycol and polyol, the amount of isophthalic acid being in the range of from about 1 to about 50, preferably about 5 to about 20 mQl percent, based on total mols of adipic acid and isophthalic acid, being especially preferred, with such polyester polyols having an aver-age hydroxyl functionality of at least 2.1 being most advanta-geous. Similarly, the monomeric polyols which can replace up to about 70 mol percent of the polymeric polyol compounds can be diols, triols, tetrols and the like and include, without limi-- tation thereto,-compounds such as ethylene glycol, propylene g:Lycol, diethylene glycol, glycerol, dipropylene glycol, erythri-3~5 ..
tol, pentaerythritol, trimethylol propane, neopentyl glycol,and the like. Polyols employed in the practice of the invention will have molecular weights in the range from about 60 to about ~,000, with molecular weights in the range from about 500 to about 2,000 being presently preferred. The polymeric polyols and method of preparing such compounds are well known in the art and require no further elaboration.
Unsaturated addition-polymerizable monomeric organic compounds having a single isocya~ate-reactive active hydrogen group which can be employed in the practice of the present in-vention include any of such compounds which have been previously used to introduce an unsaturated polymerizable moiety into a molecule via reaction between the ac-tive hydrogen group and a re-active isocyanate moiety. Preferably, the active hydrogen group is hydroxy. Illustrative of unsaturated addition-polymerizable monomeric organic compounds having a single isocyanate-reactive active hydrogen group are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl metha-crylate, N-hydroxymethyl acrylamine, N-hydroxymethyl metha-crylamide, diethylene glycol monoacrylate, diethylene glycolmonomethacrylate, glycerine dimethacrylate, trimethylol propane dimethacrylate, and the like. The amount of such compounds will be sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate functionality, and pre-ferably is sufficient to afford an active hydrogen group:NCO
ratio, with respect to the amount of total free hydroxyl func-tions, of at least 1:1, with a small excess, 10 mol percent or less, being especially preferred.
As has been indicated, the herein described unsatur-ated urethane resins are preferably obtained by reacting atleast one isocyanate-functional prepolymer with at least one unsaturated addition-polymerizable m~momeric organic compound having a 'X; - 10 -7~5 single isocyanate-reactive active hydrogen group, with unsa-turated urethane resins having substantially no free isocyanate functionality being especially preferred. Suitable prepolymers can be prepared according to known methods from the above listed precursors, keeping in mind the requirements for NCO:OH ratio and average hydroxyl functionality. Such prepolymers can be prepared neat, but are preferably prepared in the presence of a diluent phase which is copolymerizable with the unsaturated urethane resin but is inert with respect to the prepolymer re-action and the subsequent reaction between the prepolymer andthe unsaturated addition-polymerizable monomeric organic com-pound having a single lsocyanate-reactive active hydrogen group.
As noted, the radiation curable compositions of the present invention comprise a mixture of i) at least one unsaturated urethane resin prepared in accordance with this invention;
ii) a reactive diluent system comprising at least one unsaturated addition-polymerizable monomeric compound which is copolymerizable with said unsaturated urethane resin, and preferably containing at least one acrylic and/or methacrylic acid ester containing at least 6 carbon atoms in the non-acid moiety; and, optionally, iii) an effective amount of at least one photoini-tiator compound, within the compositional parameters previously set forth.
Reactive diluent systems which can be employed in the radiation curable compositions of this invention include any of such systems which have been or are being used for this purpose. Broadly, suitable reactive diluent systems comprise at least one unsaturated addition-polymerizable monomer which is copolyrneriza~le with -the unsaturated urethane resin upon ex-posure to radiation. The reactive diluent can be monofunctional .,~,~, , - 1 1 -~Z~ s5 or polyfunctional. A single polyfunctional diluent can be used, as can mixtures thereof; or a combination of one or more mono-functional reactive diluents and one or more polyEunctional reactive diluents can be used. Such combinations of mono- and polyfunctional reactive diluents are presently preferred. General-ly, the reactive diluent system will comprise from about 10 to about 65, preferably about 25 to about 50, weight percent, based on total weight of unsaturated urethane resin and reactive di-luent, of the radiation curable compositions of the invention.
Particularly preferred reactive diluents are unsaturated addition-polymerizable monofunctional monomeric compounds selected from the group consisting of esters having the general formula O
CH2 = C - C - O - R, 1o wherein R and R are as previously defined. Representative of such preferred reactive monomeric diluents, without limitation thereto, are hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, stearyl acrylate, and the corresponding methacrylates. Illustrative of other reactive monofunctional and polyfunctional monomeric diluents which can be employed are styrene, methyl methacrylate, butyl acrylate, isobutyl acrylate, 2-phenoxy acrylate, 2-methoxyethyl acrylate,
2-(N,N-diethylamino)-ethyl acrylate, the corresponding metha-crylates, acrylonitrile, methyl acrylonitrile, methacrylamide, neopentyl glycol diacrylate, ethylene glycol diacrylate, hexylene glycol diacrylate, diethylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol di-, tri-, or tetra-acrylate, the corresponding methacrylates, vinyl pyrrolidone, and the like.
At the present time, it is preferred that the reactive diluent system contain at least 50 weight percen-t of at least one acrylic and/or methacrylic acid ester haviny at least 6 carbon atoms in l~Z73~5 thenon-acid moieLy, with such acrylic acid esters being preferred.
Generally, the reactive diluent system will comprise from about 10 to about 70, preferably about 25 to about 50, weigh-t percent, based on total weight of unsaturated urethane resin and reactive diluent system, of the radiation curable compositions of the invention. Reactive diluent systems are well known to those skilled in the art of radiation curing and the selection of an approproate diluent system in any given instance is sufficient-ly encompassed by such knowledge as to require no further dis-cussion here.
As previously indicated, a photoinitiator system willgenerally be employed when curing is effected by exposure to low energy radiation sources such as ultra violet light. Any of the known photoinitiators can be used within the concentra-tion ranges previously set forth. Illustrative photoinitiators, without limitation thereto, include benzophenone, benzoin, acetophenone, benzoin methyl ether, Michler's ketone, benzoin butyl ether, xanthone, thioxianthone, propiophenone, fluorenone, carbazole, diethoxyacetophenone, the 2-, 3- and 4-methylaceto-phenones and methoxyacetophenones, the 2- and 3-chloroxanthones and chlorothioxanthones, 2-acetyl-4-methylphenyl acetate, 2,2'-dimethoxy-2-phenylacetophenone, benzaldehyde, fluorene, anthro-quinone, triphenylamine, 3-and4-allylacetophenone, p-diacetyl-benzene, 3-chloro-2-nonylxanthone, and the like, and mixtures thereof.
The invention compositions can also include pigments, fillers, wetting agents, flatting agents, flow control agents, and other additives typically present in coating compositions.
In some applications, the inclusion of minor amounts of inert solvents can be advantageous. Such additive materials are well known to those skilled in the ar~ and do not requile further ela-boration herein. Also well known are the concentrations at . - 13 -1~27~
which such additives are used.
m e radiation curable ccm~ositions of this invention are charac-terized by improved flowability, fluidity and ph~sical stability. The compositions of this invention can be applied to wood, metal, fabric and plastic substrates in an economical and efficient manner using conventional industrial techniques and provide smooth, uniform films which are rapidly cured to dried films having excellent physical and chemical properties.
e improved coating compositions of this invention can be ap-plied and cured by any of the conventional known methods. Application can be by roll coating, curtain coating, airless spray, dipping or by any other procedure. The cure can be effected by exposure to any high energy source, such as ionizing radiation, or low energy source, such as ultraviolet light radiation. The equipment utilized for curing, as well as the appropriate time for curing, and the conditions under which the curing is effected are well-known to those skilled in the art of radiation curing and do not require further elaboration herein.
The invention is illustrated in greater detail bv the following Examples, but these examples are not to be constructed as limiting the present invention. All parts, percentages and the like are in parts by weight, unless otherwise indicated.
Several unsaturated urethane resins are prepared in 2-ethylhexyl acrylate reactive monomer diluent at a resin concentration of 70 percent em-ploying as precursor compounds polyester polyols, 4,4'-methylene-Bis (cyclo-hexyl'isocyanate), and 2-hydroxyethyl acrylate. In each instance the polyester polyol is reacted with the isocyanate ccmpound at NCO:OH ratios of 1.5:1, 2:1, 2.5:1, 3:1 and 3.5"1 to form an isocyanate-functional pre-polymer; and the prepolymer is reacted with 2-hydroxyethyl acryl-ate to form an ethylenically unsaturated acrylyl urethane having at least two terminal vinyl groups and substantially no free isocyanate functions. m e polyester polyols have hydroxyl functionalities f(O~I) of 2.0, 2.3, 2.5, 2.7 and 3Ø The resins are evaluated with respect to viscosity at '~ .
l~LZ~ 5 : ` . '' 70% resin concentration; nhvsical stahility and ccm~Htibilitv in 2-ethylhexyl acrylate reactive- monomer diluent. The results are reported in Table I, with the unsaturated urethane resin being identified in relation to the polyester polyol from which it is made.
Resin Polyester f(OH) NCO:OH Viscosity Physical a ComPati- b polyol CPs Stabilitybility 1 A 2.0 1.590,000 P 5 2 A 2.0 2.030,000 F 4
At the present time, it is preferred that the reactive diluent system contain at least 50 weight percen-t of at least one acrylic and/or methacrylic acid ester haviny at least 6 carbon atoms in l~Z73~5 thenon-acid moieLy, with such acrylic acid esters being preferred.
Generally, the reactive diluent system will comprise from about 10 to about 70, preferably about 25 to about 50, weigh-t percent, based on total weight of unsaturated urethane resin and reactive diluent system, of the radiation curable compositions of the invention. Reactive diluent systems are well known to those skilled in the art of radiation curing and the selection of an approproate diluent system in any given instance is sufficient-ly encompassed by such knowledge as to require no further dis-cussion here.
As previously indicated, a photoinitiator system willgenerally be employed when curing is effected by exposure to low energy radiation sources such as ultra violet light. Any of the known photoinitiators can be used within the concentra-tion ranges previously set forth. Illustrative photoinitiators, without limitation thereto, include benzophenone, benzoin, acetophenone, benzoin methyl ether, Michler's ketone, benzoin butyl ether, xanthone, thioxianthone, propiophenone, fluorenone, carbazole, diethoxyacetophenone, the 2-, 3- and 4-methylaceto-phenones and methoxyacetophenones, the 2- and 3-chloroxanthones and chlorothioxanthones, 2-acetyl-4-methylphenyl acetate, 2,2'-dimethoxy-2-phenylacetophenone, benzaldehyde, fluorene, anthro-quinone, triphenylamine, 3-and4-allylacetophenone, p-diacetyl-benzene, 3-chloro-2-nonylxanthone, and the like, and mixtures thereof.
The invention compositions can also include pigments, fillers, wetting agents, flatting agents, flow control agents, and other additives typically present in coating compositions.
In some applications, the inclusion of minor amounts of inert solvents can be advantageous. Such additive materials are well known to those skilled in the ar~ and do not requile further ela-boration herein. Also well known are the concentrations at . - 13 -1~27~
which such additives are used.
m e radiation curable ccm~ositions of this invention are charac-terized by improved flowability, fluidity and ph~sical stability. The compositions of this invention can be applied to wood, metal, fabric and plastic substrates in an economical and efficient manner using conventional industrial techniques and provide smooth, uniform films which are rapidly cured to dried films having excellent physical and chemical properties.
e improved coating compositions of this invention can be ap-plied and cured by any of the conventional known methods. Application can be by roll coating, curtain coating, airless spray, dipping or by any other procedure. The cure can be effected by exposure to any high energy source, such as ionizing radiation, or low energy source, such as ultraviolet light radiation. The equipment utilized for curing, as well as the appropriate time for curing, and the conditions under which the curing is effected are well-known to those skilled in the art of radiation curing and do not require further elaboration herein.
The invention is illustrated in greater detail bv the following Examples, but these examples are not to be constructed as limiting the present invention. All parts, percentages and the like are in parts by weight, unless otherwise indicated.
Several unsaturated urethane resins are prepared in 2-ethylhexyl acrylate reactive monomer diluent at a resin concentration of 70 percent em-ploying as precursor compounds polyester polyols, 4,4'-methylene-Bis (cyclo-hexyl'isocyanate), and 2-hydroxyethyl acrylate. In each instance the polyester polyol is reacted with the isocyanate ccmpound at NCO:OH ratios of 1.5:1, 2:1, 2.5:1, 3:1 and 3.5"1 to form an isocyanate-functional pre-polymer; and the prepolymer is reacted with 2-hydroxyethyl acryl-ate to form an ethylenically unsaturated acrylyl urethane having at least two terminal vinyl groups and substantially no free isocyanate functions. m e polyester polyols have hydroxyl functionalities f(O~I) of 2.0, 2.3, 2.5, 2.7 and 3Ø The resins are evaluated with respect to viscosity at '~ .
l~LZ~ 5 : ` . '' 70% resin concentration; nhvsical stahility and ccm~Htibilitv in 2-ethylhexyl acrylate reactive- monomer diluent. The results are reported in Table I, with the unsaturated urethane resin being identified in relation to the polyester polyol from which it is made.
Resin Polyester f(OH) NCO:OH Viscosity Physical a ComPati- b polyol CPs Stabilitybility 1 A 2.0 1.590,000 P 5 2 A 2.0 2.030,000 F 4
3 A 2.0 2.56,400 F 3
4 A 2.0 3.06,600 G 2 A 2.0 3.54,500 G
6 B 2.3 1.5100,000 P 5 7 B 2.3 2.044,000 F 3 8 B 2.3 2.522,000 E S
9 B 2.3 3.010,000 E S
B 2.3 3.55,600 E S
11 B 2.5 1.5GEL
12 B 2.5 2.066,000 F 3 13 B 2.5 2.524,500 E S
14 B 2.5 3.0i2,500 E S
B 2.5 3.510,000 E S
16 B 2.7 1.5GEL
17 B 2.7 2.075,000 -F 4 18 B 2.7 2.547,000 G
19 B 2.7 3.020,000 E S
B 2.7 3.513;000 E S
21 B 3.0 1.5GEL
22 B 3.0 2.0GEL
23 B 3.0 2.560,000 ~F 3 24 B 3.0 3.035,000 G 2 B 3.0 3.517,000 E ~ S
26 C 3.0 1.5GEL
27 C 3.0 2.0100,000 G 2 28 C 3.0 2.522,000 E S
2~ C 3.0 3.0 10,000 E S
A : 1,3-Butylene Glycol/Adipic Acid (90)/Isophthalic Acid (10) Polyester Polyol B : 1,3-Butylene Glycol/Adipic Acid (90)/Isophthalic Acid (10)~
Glycerine Polyester Polyol C : Polycaprolactone triol polyester polyol ~L~2734~
TABLE 1 (Cont'd) a : P = Poor, F = Fair, G = Good, E = Excellent b : Compatibilitv increases as cardinal number decreases, e.g., 3 is more compatible than 5 but less compatible than 1, S is soluble and fully compatible.
The data demonstrates the significant viscosity re-ductions which are obtained at NCO:OH ratios in excess of 2.1:1.
For example, an increase in NCO:OH ratio from 2:1 to 2.5:1 re-sults in an approximate two-fold decrease in viscosity; a fur-ther increase in NCO:OH ratio from 2.5:1 to 3:1 results in ano-ther two-fold decrease in viscosity; and even lower viscosities are~obtained at an NCO:OH ratio of 3.5:1. It is to be noted that viscosity tends to increase, at constant NCO:OH ratio, with increasing hydroxyl functionality and that viscosity decreases, at constant hydroxyl functionality, with increasing NCO:OH ratio.
It is also to be noted that resin-diluent compatibility and phy-sical stability of the compositions containing unsaturated ure-thaneresins become increasingly better as the NCO:OH ratio in-creases at constant hydroxyl functionality. It is further noted that excellent compositions with respect to manageable viscosi-ty, physical stability and resin~diluent compatibility can be con-sistently obtained at NCO:OH ratios of about 2.3:1 to 4:1 and higher, at substantially all hydroxy functionalities in the range between about 2.3 to about 2.7. The data demonstrates that at NCO:OH ratios below about 2.3:1 and at hydroxy functionalities below about 2.3 and above about 2.7, some experimentation may be necessary in obtaining compositions having the desired charac-teristics.
EXAMPLE II
To a composition containing 70 percent Resin 8 (hy-droxy functionality 2.3 and NCO:OH ratio 2.5) in 2-ehtylhexyl acrylate reactive monomer diluent, there is added the adduct of 2 moles 2-hydroxyethyl acrylate and 4,4'-methylene-bistcyclo-~,~
~ - 16 -~ ~L27;~
hexyl isocyanate) in an amount sufficient to simulate an NCO:OH
ratio of 3:1. No significant change in viscosity, physical stability or compatibility is noted, thus demonstrating that the benefits of this invention can onlv be attained by synthesizing the unsaturated urethane resins in accordance with the concepts of the invention.
E~AMPLE III
Several formulations are prepared employing selected unsaturated urethane resins from Example I as follows:
Composition A B C D E F
Resin 9 70 Resin 14 - 70 Resin 19 - - 70 ; Resin 20 ~ ~ ~ 70 ~esin 25 - - - - 70 Resin 29 - - - - - 70 2-Ethylhexyl Acrylate30 30 30 30 30 30 Benzoin Ether-type Photoinitiator Viscosity, CPS, Thousands10 12.5 20 13 17 10 The compositions are coated onto aluminum substrates and cured by exposure to ultraviolet radiation (200 watts/inch mercury lamp) at a line speed of 50 feet per minute for three passes. The compositions are easily applied and cure to dried smooth, uni-form films which are tough and flexible and have excellent chemical and physical properties.
EXAMPLE IV
A series of unsaturated urethane resins are prepared in 2-ethylhexyl acrylate reactive monomer diluent at a resin concentration of 70 percent employing as precursor compounds~
polyester polyol, 4,4'-methylene-bis(cyclohexyl isocyanate), and 2-hydroxyethyl acrylate. In each instance, the polyester polyol coMpound is reacted with the isocyanate compound at an NCO:OII
.~
~lZ73~
ratio of 2.5:1 to form an isocyanate-functional prepolymer; and the prepolymer ls fully capped with 2-hydroxyethyl acrylate to form an ethylenically unsaturated acrylyl urethane having at least two terminal vinyl groups and substantially no free iso-cyanate functions. The resins are evaluated with respect to solubility in 2-ehtylhexyl aerylate-reactive monomer diluent and physical stability, ineluding thixotropy and cloudiness, in 2-ethylhexyl acrylate reactive monomer diluent. The precursor materials and the results of the resin evaluation are reported in Table II.
TAsLE II
Resin Evaluation 2-Hydroxyethyl Acrylate 4,4'-~ethylene-Bis(C~clohexyl Isocyanate) Polyester Polyol 1 Diethylene Glycol/Adipic Acid Insoluble 2 1,6-Hexanediol/Trimethylol Propane/Adipic Acid mixotropic 3 1,3-Butylene Glycol/TrLmethylol Propane/Adipic Acid Thixotropic 4 1,4-Butanediol/Glycerine/Adipic Acid (90)/
Isophthalic Acid (10~ Insoluble
6 B 2.3 1.5100,000 P 5 7 B 2.3 2.044,000 F 3 8 B 2.3 2.522,000 E S
9 B 2.3 3.010,000 E S
B 2.3 3.55,600 E S
11 B 2.5 1.5GEL
12 B 2.5 2.066,000 F 3 13 B 2.5 2.524,500 E S
14 B 2.5 3.0i2,500 E S
B 2.5 3.510,000 E S
16 B 2.7 1.5GEL
17 B 2.7 2.075,000 -F 4 18 B 2.7 2.547,000 G
19 B 2.7 3.020,000 E S
B 2.7 3.513;000 E S
21 B 3.0 1.5GEL
22 B 3.0 2.0GEL
23 B 3.0 2.560,000 ~F 3 24 B 3.0 3.035,000 G 2 B 3.0 3.517,000 E ~ S
26 C 3.0 1.5GEL
27 C 3.0 2.0100,000 G 2 28 C 3.0 2.522,000 E S
2~ C 3.0 3.0 10,000 E S
A : 1,3-Butylene Glycol/Adipic Acid (90)/Isophthalic Acid (10) Polyester Polyol B : 1,3-Butylene Glycol/Adipic Acid (90)/Isophthalic Acid (10)~
Glycerine Polyester Polyol C : Polycaprolactone triol polyester polyol ~L~2734~
TABLE 1 (Cont'd) a : P = Poor, F = Fair, G = Good, E = Excellent b : Compatibilitv increases as cardinal number decreases, e.g., 3 is more compatible than 5 but less compatible than 1, S is soluble and fully compatible.
The data demonstrates the significant viscosity re-ductions which are obtained at NCO:OH ratios in excess of 2.1:1.
For example, an increase in NCO:OH ratio from 2:1 to 2.5:1 re-sults in an approximate two-fold decrease in viscosity; a fur-ther increase in NCO:OH ratio from 2.5:1 to 3:1 results in ano-ther two-fold decrease in viscosity; and even lower viscosities are~obtained at an NCO:OH ratio of 3.5:1. It is to be noted that viscosity tends to increase, at constant NCO:OH ratio, with increasing hydroxyl functionality and that viscosity decreases, at constant hydroxyl functionality, with increasing NCO:OH ratio.
It is also to be noted that resin-diluent compatibility and phy-sical stability of the compositions containing unsaturated ure-thaneresins become increasingly better as the NCO:OH ratio in-creases at constant hydroxyl functionality. It is further noted that excellent compositions with respect to manageable viscosi-ty, physical stability and resin~diluent compatibility can be con-sistently obtained at NCO:OH ratios of about 2.3:1 to 4:1 and higher, at substantially all hydroxy functionalities in the range between about 2.3 to about 2.7. The data demonstrates that at NCO:OH ratios below about 2.3:1 and at hydroxy functionalities below about 2.3 and above about 2.7, some experimentation may be necessary in obtaining compositions having the desired charac-teristics.
EXAMPLE II
To a composition containing 70 percent Resin 8 (hy-droxy functionality 2.3 and NCO:OH ratio 2.5) in 2-ehtylhexyl acrylate reactive monomer diluent, there is added the adduct of 2 moles 2-hydroxyethyl acrylate and 4,4'-methylene-bistcyclo-~,~
~ - 16 -~ ~L27;~
hexyl isocyanate) in an amount sufficient to simulate an NCO:OH
ratio of 3:1. No significant change in viscosity, physical stability or compatibility is noted, thus demonstrating that the benefits of this invention can onlv be attained by synthesizing the unsaturated urethane resins in accordance with the concepts of the invention.
E~AMPLE III
Several formulations are prepared employing selected unsaturated urethane resins from Example I as follows:
Composition A B C D E F
Resin 9 70 Resin 14 - 70 Resin 19 - - 70 ; Resin 20 ~ ~ ~ 70 ~esin 25 - - - - 70 Resin 29 - - - - - 70 2-Ethylhexyl Acrylate30 30 30 30 30 30 Benzoin Ether-type Photoinitiator Viscosity, CPS, Thousands10 12.5 20 13 17 10 The compositions are coated onto aluminum substrates and cured by exposure to ultraviolet radiation (200 watts/inch mercury lamp) at a line speed of 50 feet per minute for three passes. The compositions are easily applied and cure to dried smooth, uni-form films which are tough and flexible and have excellent chemical and physical properties.
EXAMPLE IV
A series of unsaturated urethane resins are prepared in 2-ethylhexyl acrylate reactive monomer diluent at a resin concentration of 70 percent employing as precursor compounds~
polyester polyol, 4,4'-methylene-bis(cyclohexyl isocyanate), and 2-hydroxyethyl acrylate. In each instance, the polyester polyol coMpound is reacted with the isocyanate compound at an NCO:OII
.~
~lZ73~
ratio of 2.5:1 to form an isocyanate-functional prepolymer; and the prepolymer ls fully capped with 2-hydroxyethyl acrylate to form an ethylenically unsaturated acrylyl urethane having at least two terminal vinyl groups and substantially no free iso-cyanate functions. The resins are evaluated with respect to solubility in 2-ehtylhexyl aerylate-reactive monomer diluent and physical stability, ineluding thixotropy and cloudiness, in 2-ethylhexyl acrylate reactive monomer diluent. The precursor materials and the results of the resin evaluation are reported in Table II.
TAsLE II
Resin Evaluation 2-Hydroxyethyl Acrylate 4,4'-~ethylene-Bis(C~clohexyl Isocyanate) Polyester Polyol 1 Diethylene Glycol/Adipic Acid Insoluble 2 1,6-Hexanediol/Trimethylol Propane/Adipic Acid mixotropic 3 1,3-Butylene Glycol/TrLmethylol Propane/Adipic Acid Thixotropic 4 1,4-Butanediol/Glycerine/Adipic Acid (90)/
Isophthalic Acid (10~ Insoluble
5 1,3-Butylene Glycol/Glycerine/Adipic Acid (90)/
Isophthalic Acid (10) Soluble
Isophthalic Acid (10) Soluble
6 1,3-Butylene Glycol/Glycerine/Adipic Acid Insoluble
7 1,3-Butylene Glyeol/Glycerine/Adipic Acid (75)/
Isophthalic Acid (25? Cloudy a
Isophthalic Acid (25? Cloudy a
8 1,3-Butylen~ Glycol/~lvcerine/Adipic Acid (80)/ a Isophthalic Acid (20) Cloudy
9 1,4-Cyclohexanedi~ethylol/Glycerine/Adipic Acid (90~/
Isophthalic Acid (10) Insoluble 1,3-Butylene Glycol (50)/Neopentyl Glycol (50)/
Glyeerine/Aclipic Acid (90)/Iso~hthalic Acid (10) Soluble 11 1,3-Butylene Glyeol (50~/1,6-Hexanediol (50)/
Glycerine/Adipic Acid (90)/Iso~hthalie Acid (10) Thixotropic 12 Neopentyl Glycol/Glycerine/Adipic Acid (90)/
Isophthalic Acid (10) Soluble 13 Polycaprolactone Polyol Soluble b a. When diluted to 60% resin concentration, time to form separate monomer-rich and r~sin-rich phases i~ 730 days.
b. Wllen diluted to 80% resin concentration, time to form separate mon~mer-rich and resin-rich phases is 24 hours.
.~
~ ~73~5 The data demonstrates that unsaturated urethane resins ~hich are.obtained ~rom polyester polyols derived from 1,3-butylene glycol and/or neopentyl glycol, adipic acid, isophthalic acid, and, optionally, at least one polyol having at least three hy-droxyl~ groups have a lower viscosity and improved physical stability. The data further demonstrates the necessity of employ-ing both adipic a.cid and isophthalic acid as well as 1,3-butylene glycol and/or neopentyl glycol.
EXAMPLE V
.~ 10 To the unsaturated urethane resin-containing composi-tions from Example IV derived from polyester polyols 5, 10, 12 and 13 there is added an effective amount of benzoin ether-type photoinitiator. The compositions are coated onto aluminum panels and cured by exposure to ultraviolet radiation (200 watts/inch mercury lamp) at a line speed of 50 feet per minute for three passes. Compositions 5, 10 and 12 are less viscous than is com-position 13. Film properties of cured films from compositions 5, 10, 12 and 13 are substantially equivalent.
~ . - 19 -
Isophthalic Acid (10) Insoluble 1,3-Butylene Glycol (50)/Neopentyl Glycol (50)/
Glyeerine/Aclipic Acid (90)/Iso~hthalic Acid (10) Soluble 11 1,3-Butylene Glyeol (50~/1,6-Hexanediol (50)/
Glycerine/Adipic Acid (90)/Iso~hthalie Acid (10) Thixotropic 12 Neopentyl Glycol/Glycerine/Adipic Acid (90)/
Isophthalic Acid (10) Soluble 13 Polycaprolactone Polyol Soluble b a. When diluted to 60% resin concentration, time to form separate monomer-rich and r~sin-rich phases i~ 730 days.
b. Wllen diluted to 80% resin concentration, time to form separate mon~mer-rich and resin-rich phases is 24 hours.
.~
~ ~73~5 The data demonstrates that unsaturated urethane resins ~hich are.obtained ~rom polyester polyols derived from 1,3-butylene glycol and/or neopentyl glycol, adipic acid, isophthalic acid, and, optionally, at least one polyol having at least three hy-droxyl~ groups have a lower viscosity and improved physical stability. The data further demonstrates the necessity of employ-ing both adipic a.cid and isophthalic acid as well as 1,3-butylene glycol and/or neopentyl glycol.
EXAMPLE V
.~ 10 To the unsaturated urethane resin-containing composi-tions from Example IV derived from polyester polyols 5, 10, 12 and 13 there is added an effective amount of benzoin ether-type photoinitiator. The compositions are coated onto aluminum panels and cured by exposure to ultraviolet radiation (200 watts/inch mercury lamp) at a line speed of 50 feet per minute for three passes. Compositions 5, 10 and 12 are less viscous than is com-position 13. Film properties of cured films from compositions 5, 10, 12 and 13 are substantially equivalent.
~ . - 19 -
Claims (30)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
Unsaturated addition-polymerizable urethane resins characterized by the presence of at least one ethylenically unsaturated terminal group having the structure CH2 = C?, said unsaturated urethane resins comprising the re-action product of i) at least one organic isocyanate compound having at least two isocyanate groups;
ii) at least one polyester polyol having at least two hydroxy groups, said polyester polyol comprising the reaction product of a) at least one glycol selected from the group consisting of 1,3-butylene glycol and neopentyl glycol;
b) adipic acid;
c) isophthalic acid; and d) zero to 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of glycol and aliphatic polyol;
the amount of isophthalic acid being in the range from about
1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid; and iii) at least one unsaturated addition-polymerizable monomeric com-pound having a single isocyanate-reactive active hydrogen group;
there being present an excess of isocyanate compound with respecl to the hydroxyl groups of said polyester polyol, said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group being present in an amount sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate reactivity.
there being present an excess of isocyanate compound with respecl to the hydroxyl groups of said polyester polyol, said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group being present in an amount sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate reactivity.
2. Unsaturated urethane resins according to Claim 1, wherein the amount of isophthalic acid is in the range from about 5 to about 25 mol percent.
3. Unsaturated urethane resins according to Claim 1, comprising the reaction product of A) at least one isocyanate-functional prepolymer, said prepolymer comprising the reaction product of a) at least one organic isocyanate compound having at least two isocyanate groups;
b) at least one polyester polyol having at least two hydroxyl groups, said polyester polyol comprising the reaction product of i) at least one gylcol selected from the group consisting of 1,3-butyleneglycol and neopentyl glycol;
ii) adipic acid; iii) isophthalic acid; and iv) zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl goups, said mol percent being based on total mols of hydroxyl goups of such glycol and aliphatic polyol; the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid; the amount of such isocyanate compound being sufficient to provide an excess of isocyanate groups with respect to hydroxyl groups of such polyester polyol; and B) at least one unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group; the amount of such unsaturated addition-poly-merizable monomeric compound having a single isocyanate-reactive active hydrogen group being sufficient to provide at least one molar equivalent of active hydrogen group with respect to the isocyanate groups of such prepolymer.
b) at least one polyester polyol having at least two hydroxyl groups, said polyester polyol comprising the reaction product of i) at least one gylcol selected from the group consisting of 1,3-butyleneglycol and neopentyl glycol;
ii) adipic acid; iii) isophthalic acid; and iv) zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl goups, said mol percent being based on total mols of hydroxyl goups of such glycol and aliphatic polyol; the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid; the amount of such isocyanate compound being sufficient to provide an excess of isocyanate groups with respect to hydroxyl groups of such polyester polyol; and B) at least one unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group; the amount of such unsaturated addition-poly-merizable monomeric compound having a single isocyanate-reactive active hydrogen group being sufficient to provide at least one molar equivalent of active hydrogen group with respect to the isocyanate groups of such prepolymer.
4. Unsaturated urethane resins according to claim 3 wherein the amount of isophthalic acid is in the range from about 5 to about 25 mol percent.
5. Unsaturated addition-polymerizable urethane resins characterized by the presence of at least one ethylenically unsaturated group having the structure , said unsaturated urethane resins comprising the raction product of i) at least one organic isocyanate compound having at least two isocyanate groups;
ii) from about 30 to 100 mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
iii) from about 70 to zero mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl groups; and iv) at least one unsaturated addition-polymerizable monomeric com-pound having a single isocyanate-reactive active hydrogen group; wherein said isocyanate compound being present in an amount sufficient to provide an NCO:OH ratio of at least 2.1:1, with respect to such polymeric and monomeric polyol hydroxyl groups;
said mol percents being based on total mols of such polymeric and monomeric polyol hydroxyl groups;
the average hydroxyl functionality, with respect to such polymeric and monomeric polyols, is at least 2.1, and the amount of said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group is sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate reactivity.
ii) from about 30 to 100 mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
iii) from about 70 to zero mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl groups; and iv) at least one unsaturated addition-polymerizable monomeric com-pound having a single isocyanate-reactive active hydrogen group; wherein said isocyanate compound being present in an amount sufficient to provide an NCO:OH ratio of at least 2.1:1, with respect to such polymeric and monomeric polyol hydroxyl groups;
said mol percents being based on total mols of such polymeric and monomeric polyol hydroxyl groups;
the average hydroxyl functionality, with respect to such polymeric and monomeric polyols, is at least 2.1, and the amount of said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group is sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate reactivity.
6, Unsaturated urethane resins according to claim 5 comprising the re-action product of i) at least one isocyanate-functional prepolymer, said prepolymer comprising the reaction product of a) at least one organic isocyanate compound having at least two isocyanate groups;
b) from about 30 to 100 mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
c) from about 70 to zero mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl groups, and ii) at least one unsaturated addition-polymerizable monomeric com-pound having a single isocyanate-reactive active hydrogen group.
b) from about 30 to 100 mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
c) from about 70 to zero mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl groups, and ii) at least one unsaturated addition-polymerizable monomeric com-pound having a single isocyanate-reactive active hydrogen group.
7, Unsaturated urethane resins according to claim 5 wherein said poly-meric polyol comprises the reaction product of i) at least one glycol selected from the group consisting of 1, 3-butylene glycol and neopentyl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
8. Unsaturated urethane resins according to claim 5 where said NCO:OH ratio is in the range of 2,3-4:1 and said hydroxyl functionality is in the range from about 2. 3 to about 2.7.
9. Unsaturated urethane resins according to claim 8 wherein said ethylenically unsaturated group is a terminal vinyl group having the structure CH2 = C?.
10. Unsaturated urethane resins according to claim 9 wherein said polymeric polyol comprises the reaction product of i) at least one glycol selected from the group consisting of 1. 3-butylene glycol and neopentyl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
11. Unsaturated urethane resins according to claim 10 wherein the amount of isophthalic acid is in the range from about 5 to about 25 mol percent.
12. A coating composition comprising A. at least one unsaturated urethane resin comprising the reaction product of i) at least one organic isocyanate compound having at least two isocyanate groups;
ii) from about 30 to 100 mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
iii) from about 70 to zero mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl groups; and iv) at least one unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group; wherein said isocyanate compound being present in an amount suffi-cient to provide an NCO:OH ratio of at least 2.1:1, with respect to such poly-meric and monomeric polyol hydroxyl groups, said mol percents being based on total mols of such poly-meric and monomeric polyol hydroxyl groups;
the average hydroxyl functionality, with respect to such polymeric and polymeric polyols, is at least 2.1, and the amount of said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group is sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate reactivity; and B. A reactive diluent system comprising at least one unsaturated addition-polymerizable monomeric cornpound which is copolymerizable with said unsaturated urethane resin;
the amount of unsaturated urethane resin being in the range from about 30 to about 90 weight percent, based on total weight of unsaturated urethane resin and reactive diluent system.
ii) from about 30 to 100 mol percent of at least one polymeric polyol characterized by the presence of at least two hydroxyl groups;
iii) from about 70 to zero mol percent of at least one monomeric polyol characterized by the presence of at least two hydroxyl groups; and iv) at least one unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group; wherein said isocyanate compound being present in an amount suffi-cient to provide an NCO:OH ratio of at least 2.1:1, with respect to such poly-meric and monomeric polyol hydroxyl groups, said mol percents being based on total mols of such poly-meric and monomeric polyol hydroxyl groups;
the average hydroxyl functionality, with respect to such polymeric and polymeric polyols, is at least 2.1, and the amount of said unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive active hydrogen group is sufficient to provide at least one molar equivalent of active hydrogen group with respect to isocyanate reactivity; and B. A reactive diluent system comprising at least one unsaturated addition-polymerizable monomeric cornpound which is copolymerizable with said unsaturated urethane resin;
the amount of unsaturated urethane resin being in the range from about 30 to about 90 weight percent, based on total weight of unsaturated urethane resin and reactive diluent system.
13. A coating composition according to claim 12 wherein said diluent system contains at least one unsaturated addition-polymerizable monofunc-tional monomeric compound selected from the group consisting of esters having the general formula ;
wherein R0 is hydrogen or methyl and R is an aliphatic or cyclo-aliphatic group having from 6 to 18 carbon atoms.
wherein R0 is hydrogen or methyl and R is an aliphatic or cyclo-aliphatic group having from 6 to 18 carbon atoms.
14. A coating composition according to claim 12 wherein said polymeric polyol cormprises the reaction product of i) at least one glycol selected from the group consisting of 1,3-butylene glycol and neopentyl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
15. A composition according to claim 12 wherein said unsaturated ure-thane resin comprises the reaction product of i) at least one isocyanate-functional prepolymer, said prepolymer comprising the reaction product of a) at least one organic isocyanate compound having at least two isocyanate groups;
b) from about 30 to 100 mol percent of at least one poly-meric polyol characterized by the presence of at least two hydroxyl groups;
c) from about 70 to zero mol percent of at leas t one monomeric polyol characterized by the presence of at least two hydroxyl groups; and ii) at least one unsaturated addition-polymerizable monomeric compound having a single isocyante-reactive active hydrogen group.
b) from about 30 to 100 mol percent of at least one poly-meric polyol characterized by the presence of at least two hydroxyl groups;
c) from about 70 to zero mol percent of at leas t one monomeric polyol characterized by the presence of at least two hydroxyl groups; and ii) at least one unsaturated addition-polymerizable monomeric compound having a single isocyante-reactive active hydrogen group.
16. A coating composition according to claim 15 wherein said polymeric polyol comprises the reaction product of i) at least one glycol selected from the group consisting of 1, 3-butylene glycol and neopentyl glycol;
ii) adipic acid;
iii) is ophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
ii) adipic acid;
iii) is ophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
17. A coating composition according to claim 16 wherein the amount of isophthalic acid is in the range from about 5 to about 25 mol percent.
18. A coating composition according to claim 12 wherein said NCO:OH
ratio is in the range of about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7
ratio is in the range of about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7
19. A coating composition according to claim 14 wherein said NCO:OH
ratio is in the range from about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7.
ratio is in the range from about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7.
20. A coating composition according to claim 12 containing an effective amount of at least one photoinitiator compound.
21. A coating composition according to claim 20 wherein said NCO:OH
ratio is in the range from about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7.
ratio is in the range from about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7.
22. A coating composition according to claim 20 wherein said polymeric polyol comprises the reaction product of i) at least one glycol selected from the group consisting of 1,3-butylene glycol and neopentyl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
23. A coating composition according to claim 22 wherein the amount of isophthalic acid is in the range from about 5 to about 25 mol percent.
24. Coating compositions according to claim 20 wherein said diluent system contains at least one unsaturated addition-polymerizable monofunctional monomeric compound selected from the group consisting of esters having the general formula ;
wherein R0 is hydrogen or methyl and R is an aliphatic or cyclo-aliphatic group having from 6 to 18 carbon atoms.
wherein R0 is hydrogen or methyl and R is an aliphatic or cyclo-aliphatic group having from 6 to 18 carbon atoms.
25. Coating compositions according to claim 24 wherein said polymeric polyol comprises the reaction product of i) at least one glycol selected from the group consisting of 1, 3-butylene glycol and neopentyl glycol;
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
ii) adipic acid;
iii) isophthalic acid; and iv) from zero to about 50 mol percent of at least one aliphatic polyol having at least three hydroxyl groups, said mol percent being based on total mols of hydroxyl groups of such glycol and such aliphatic polyol;
the amount of isophthalic acid being in the range from about 1 to about 50 mol percent, based on total mols of adipic acid and isophthalic acid.
26. Coating compositions according to claim 24 wherein said NCO:OH ratio is in the range from about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7.
27. Unsaturated urethane resins according to claim 25 wherein said NCO:OH ratio is in the range from about 2.3:1 to about 4:1 and said hydroxyl functionality is in the range from about 2.3 to about 2.7.
28. Coating compositions according to claim 27 wherein the amount of isophthalic acid is in the range from about 5 to about 25 mol percent.
29. A method for coating a substrate comprising apply-ing to said substrate a coating composition according to claim 20; and exposing said coated substrate to ultraviolet irradiation for a time sufficient to cure said coating to a hard mar-resistant surface.
30. A coated substrate having a hard mar-resistant surface, said coating being an ultra-violet irradiation cured coating composition as claimed in claim 20.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71077576A | 1976-08-02 | 1976-08-02 | |
| US710,775 | 1976-08-02 | ||
| US05/710,776 US4112017A (en) | 1976-07-23 | 1976-08-02 | Radiation curable coating compositions |
| US710,776 | 1976-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127345A true CA1127345A (en) | 1982-07-06 |
Family
ID=27108521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,688A Expired CA1127345A (en) | 1976-08-02 | 1977-07-28 | Radiation curable compositions |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5317694A (en) |
| AU (1) | AU516173B2 (en) |
| CA (1) | CA1127345A (en) |
| DE (1) | DE2734237A1 (en) |
| FR (1) | FR2360620A1 (en) |
| GB (1) | GB1590412A (en) |
| SE (1) | SE7708525L (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2425094B1 (en) * | 1978-05-01 | 1985-07-19 | Minnesota Mining & Mfg | PHOTOPOLYMERIZABLE 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 |
| JPS60235822A (en) * | 1984-05-10 | 1985-11-22 | Toagosei Chem Ind Co Ltd | Curable resin composition |
| US4771078A (en) * | 1985-11-12 | 1988-09-13 | The Goodyear Tire & Rubber Company | Method of producing a foam from a radiation-curable composition |
| GB8621835D0 (en) * | 1986-09-10 | 1986-10-15 | Courtaulds Plc | Urethane polymer films |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2443786C2 (en) * | 1974-09-13 | 1984-01-19 | Basf Ag, 6700 Ludwigshafen | Liquid, photo-crosslinkable molding compound for the production of relief printing plates |
-
1977
- 1977-07-22 GB GB3081477A patent/GB1590412A/en not_active Expired
- 1977-07-25 SE SE7708525A patent/SE7708525L/en not_active Application Discontinuation
- 1977-07-27 AU AU27361/77A patent/AU516173B2/en not_active Expired
- 1977-07-28 CA CA283,688A patent/CA1127345A/en not_active Expired
- 1977-07-29 DE DE19772734237 patent/DE2734237A1/en not_active Withdrawn
- 1977-08-01 FR FR7723611A patent/FR2360620A1/en not_active Withdrawn
- 1977-08-01 JP JP9245977A patent/JPS5317694A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| SE7708525L (en) | 1978-02-03 |
| FR2360620A1 (en) | 1978-03-03 |
| JPS5317694A (en) | 1978-02-17 |
| AU516173B2 (en) | 1981-05-21 |
| DE2734237A1 (en) | 1978-02-09 |
| AU2736177A (en) | 1979-02-01 |
| GB1590412A (en) | 1981-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4112017A (en) | Radiation curable coating compositions | |
| CA1080887A (en) | Radiation curable coating compositions containing an acrylate-capped, polyether urethane and a polysiloxane | |
| CA1129583A (en) | Actinic radiation-curable formulations | |
| US4425472A (en) | Radiation-curable compositions | |
| US4246379A (en) | Radiation curable coating compositions | |
| US4072770A (en) | U.V. curable poly(ester-urethane) polyacrylate polymers and wet look coatings therefrom | |
| US4065587A (en) | U.V. Curable poly(ether-urethane) polyacrylates and wet-look polymers prepared therefrom | |
| US4003751A (en) | Coating and ink compositions | |
| US4164486A (en) | Radiation-curable prepolymer | |
| US4358476A (en) | Radiation-curable compositions containing water | |
| CA1259725A (en) | Post-formable radiation-curing coatings | |
| JP2540708B2 (en) | Radiation curable composition and method of use | |
| EP0357110A1 (en) | Two component coating curable at ambient temperature via a Diels-Alder reaction | |
| EP0508409B1 (en) | Photocurable resin composition | |
| US4143013A (en) | Radiation curable coating compositions | |
| JPH0724411A (en) | Coating method using radioactive hardenable composition | |
| CA1102039A (en) | Radiation curable coating cmpositions containing unsaturated addition - polymerizable urethane resin | |
| CA1127345A (en) | Radiation curable compositions | |
| JP2837144B2 (en) | Active energy ray-curable aqueous resin composition | |
| US4780487A (en) | Radiation curable coating compositions | |
| CA1119345A (en) | Low toxicity viscosity reduction of radiation-reactive curable coating compositions | |
| JPS61130337A (en) | Ethylenic unsaturated polyester | |
| CA2032977A1 (en) | Photo-curable urethane-containing compositions | |
| JP3189275B2 (en) | Active energy ray-curable resin composition | |
| USRE30212E (en) | Coating and ink compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |