Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
1997-10-27
2001-05-15
Acquah, Samuel A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S272000, C528S295300, C528S295500, C528S300000
Reexamination Certificate
active
06232433
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to radiation curable polyesters, to polymerizable compositions, and to methods of coating.
BACKGROUND OF THE INVENTION
The technology for the production radiation curable coatings using acrylate-functional oligomers is known. The article “Coatings”, Encyclopedia of Polymer Science and Engineering, supp. vol., p. 109 and 110 (John Wiley & Sons, Inc. N.Y., N.Y., 1989) notes the most widely used vehicle systems are oligomers substituted with multiple acrylate ester groups mixed with low molecular weight monofunctional, difunctional, or trifunctional acrylate monomers.
SUMMARY OF THE INVENTION
This invention relates to a composition comprising the esterification reaction product of:
a) a polycarboxylic member selected from the group consisting of polycarboxylic acids comprised of a diacid having more than about 12 carbon atoms and reactive derivatives thereof (e.g. alkyl esters thereof wherein the alkyl group has from 1 to 4 carbon atoms),
b) an ethylenically unsaturated member selected from the group consisting of ethylenically unsaturated mono-carboxylic acids and reactive derivatives thereof, (e.g. alkyl esters thereof wherein the alkyl group thereof has from 1 to 4 carbon atoms), and
c) an ethoxylated alkanetriol having an average degree of ethoxylation per hydroxyl of less than about 2 and comprised predominantly of ethoxylated alkanetriol species having one ethoxylate group per hydroxyl.
This invention also relates to a polymerizable composition comprising a compound as set forth above and to a method of coating a substrate comprising polymerizing a composition comprised of the compound set forth above while in contact with a substrate.
Broadly speaking, these polyesters are prepared by forming a mixture of a polycarboxylic acid or reactive derivative, an ethylenically unsaturated acid or derivative thereof, and an ethoxylated alkanetriol. The equivalent ratios of the acid groups to hydroxyl groups of the reactants should be roughly unitary so that the reaction product is predominantly comprised of species which have no free acid or hydroxyl functionality (or in the case of the use of a lower alkyl ester of a polycarboxylic acid or ethylenically unsaturated acid, no residual lower alkyl ester functionality). Further, it is preferred to use an equivalent ratio of polycarboxylic acid:ethylenically unsaturated acid:ethoxylated alkanetriol of roughly 1:2:3. Thus, the predominant product of the reaction should be the product of “capping” the diacid at each end with the ethoxylated alkanetriol and reaction of the remaining hydroxyl groups of the ethoxylated alkanetriol with the ethylenically unsaturated acid. However, the reaction product will be a complex mixture which is further comprised of higher oligomers and unreacted or partially reacted acids and ethoxylated alkanetriols.
DETAILED DESCRIPTION OF THE INVENTION
The polycarboxylic acid, and particularly the diacid thereof, should have the hydrophobic character of a higher fatty acid. Thus, it preferably contains polycarboxylic species having from about 12 to about 90 carbons atoms and more preferably from about 18 to about 54 carbon atoms. The polycarboxylic acid radical may be saturated or unsaturated and straight or branched. In addition to the diacid having more than about 12 carbon atoms, it typically also contains species having from 1 to 6 and more typically from 1 to 4 carboxyl groups. Instead of the free acid, it is also possible to use functional derivatives, such as acid halides, anhydrides, esters, salts or the like. Typically at least about 80 eq. % of the acid equivalents of the polycarboxylic acid will be contributed by the diacid, more typically at least about 90 eq. %, and most typically at least about 92 eq. % to about 98 eq. %.
Preferred diacids having a higher alkylene chain are described in
Encyclopedia of Polymer Science and Technology
, vol. 11, pp. 476-489, (John Wiley & Sons, Inc. N.Y., N.Y., 1988), the disclosure of which is incorporated herein by reference. Such preferred diacids include dimer acids (produced by the polymerization of fatty acids, e.g. oleic acid that results in a diacid which is a divalent hydrocarbon having 36 carbon atoms), tridecanedioc acid (produced by the ozonolysis of erucic acid), C19 diacid (produced by the hydroformylation of oleic acid with carbon monoxide) and C21 diacid (produced by the reaction of tall oil fatty acid with acrylic acid). The preferred diacids are dimer acids. Dimer acids are also described in detail in U.S. Pat. No. 5,138,027 (Van Beek), the disclosure of which is incorporated herein by reference.
The term “polymerized fatty acid” is intended to be generic in nature and to refer to polymerized acids obtained from fatty acids, the composition including predominantly dimerized fatty acids, with minor amount of trimerized fatty acids and residual monomeric fatty acids. The term “fatty acids” refers to saturated, ethylenically unsaturated and acetylenically unsaturated, naturally occurring and synthetic monobasic aliphatic carboxylic acids which contain from about 8 to about 24 carbon atoms. While specific references are made in this application to polymerized fatty acid which are obtained from C18 fatty acids, it will be appreciated that the methods of this invention can likewise be employed with other polymerized fatty acids.
The preferred starting acids for the preparation of the polymerized fatty acids used in this invention are oleic and linoleic acids, due to their ready availability and relative ease of polymerization. Mixtures of oleic and linoleic acids are found in tall oil fatty acids, which are a convenient commercial source of these acids. Fatty acids can be polymerized using various well known catalytic and noncatalytic polymerization methods. A typical composition of the polymerized C18 tall oil fatty acids which are used as the starting materials for the polymerized acids which can be used in the present invention is:
C18 monobasic acids (monomer) 0-15% by wt.
C36 dibasic acids (dimer) 60-95% by wt.
C54 (or higher) trimer acid or polybasic acids 0.2-35% by wt.
In preparing polymerized fatty acids for use in the present invention, it is preferable that the starting polymerized fatty acid contains as high a percentage as possible of the dimer (C36 dibasic) acid, e.g. at least about 90% by wt., in order to obtain optimum physical properties in the final product.
In addition to the polymerized fatty acids, a wide variety of additional dicarboxylic acids can be used in a minor equivalent amount (e.g. from 0 to about 20 equivalent percent of the total diacid equivalents) to prepare the reaction product, including aliphatic, cycloaliphatic, and aromatic dicarboxylic acids. Representative of such acids (which may contain from about 2 to about 22 carbon atoms) are oxalic, glutaric, malonic, adipic, succinic, suberic, sebacic, azelaic, pimelic, terephthalic, isophthalic, dodecanedioic and phthalic acids, naphthalene dicarboxylic acids, and 1,4- or 1,3-cyclohexane dicarboxylic acids. The ethoxylated alkanetriol organic compound contains predominantly species having 3 hydroxyl groups in the molecule. Examples of these include glycerol, trimethylolethane, and trimethylolpropane. Adducts of alkylene oxides with alkanetriols are known substances which may be obtained by the relevant methods of preparative organic chemistry. Ethoxylation of alcohols is extensively discussed in
Encyclopedia of Polymer Science and Technology
, vol. 6, pp. 225-273, (John Wiley & Sons, Inc. N.Y., N.Y., 1986), the disclosure of which is incorporated herein by reference. On an industrial scale, they are typically produced by ethoxylation of an alkanetriol in the presence of basic catalysts, such as for example lithium hydroxide, potassium hydroxide, sodium methylate, strontium phenolate or calcined hydrotalcite, at temperatures of 120 to 180° C. and under pressures of 1 to 5 bar. After the ethoxylation, the products may be neutralized by addition of acids (phosphoric acid, acetic acid, preferably lactic acid).
In the context
Acquah Samuel A.
Drach John E.
Henkel Corporation
Millson, Jr. Henry E.
Wood John Daniel
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