US1976191A - Wrinkle resin finish - Google Patents

Description

Patented Dot. 9, 1934 UNITED STATES PATENT OFFICE 1,978,191 I WRINKLE RESIN FINISH Frank Brian Root, East Orange, N. 3., assignor to Chadeloid Chemical Company, New York, N. Y., a corporation of West Virginia No Drawing. Application December 21, 1929, Serial No. 415,778

25 Claims.

This invention relates to wrinkle finishes and more particularly to wrinkle finishes containing resins, to products utilizable in such finishes, and

4 to methods of making such products and finishes. 5 Wrinkle finishes as heretofore made in the art have generally been in the nature of varnishes and have followed the usual varnish formulas including drying oils, resins, driers and volatile thinners, the wrinkling of such compositions being particularly effected by baking. The drying oil utilized in this manner is usually one that shows a wrinkling tendency upon drying, and therefore may be said to belong to the class of oils designated as wrinkling oils" which class ineludes blown and unblown China-wood oil, the

blown forms of linseed, perilla, etc. oils. Nonwrinkling oils including the semi-drying and nondrying oils as well as their blown and boiled derivatives may be present in the composition, but the amounts of such non-wrinkling constituents should not be suificient to destroy the desired degree of wrinkle to be obtained in the finished coating. The resins utilized in such wrinkle finishes include the more common varnish gums, 2 such as Congo, kauri, damar, cumar, Amberol, copal, etc., which resins may be generally termed wrinkle finish resins to distinguish them from such substances as rosin and asphaltum which when used in large amounts, act as wrinkle in hibitors. Consequently such non-wrinkling materials should not be present in the composition to the extent where they militate against the desired wrinkle appearance. The driers utilized are the usual metallic driers employed in varnish manufacture, and the thinners, although of no special type, are chosen from those that facilitate the application of the finish and produceth'e best effect.

In general it may be said that the wrinkling oil in itself is the cause of the wrinkling phenomenon. When such an oil is applied in a thin film over a surface, and particularly when dried at an elevated temperature, oxidation occurs. There is a consequent formation of a skin over the surface of the oil and this skin expands laterally due to increase in volume through oxidation. The result is that the surface folds up into continuous ridges and creases running irregularly over the whole surface. Such explanations of the wrink ing phenomenon however are not to be taken as limiting but as merely suggestive, and the compositions and methods herein disclosed have been found in practice to give desirable results regardless of any theory of action which results in the wrinkling conformation.

(Cl. B l-36) For practical purposes, however, coatings require a number of factors and features and consequently wrinkling oils are not generally used alone to give the wrinkled finish. The general formulas therefore include other components which modify the appearance and facilitate the control of the wrinkling, and also impart desirable physical properties or aid in the'application of the-finish. Used alone in a film of suitable wrinkling thickness, a wrinkling oil gives a baked film that is relatively soft and exhibits rather poor adhesion, and also dries rather slowly. In such cases the wrinkles are quite small, close together and irregular as to size. The general appearance of the film is not as attractive as when additional substances are included in the composition.

When a suitable resin is used with the oil, the

film is harder and the adhesion improved. Also the size and appearance of the wrinkles of the baked film are desirably modified. The wrinkles are larger and moredefinable. They are more uniform in size and present a more regular pattern which is quite attractive. The function of the resin in this case appears to be, aside from its physical effects, that of diluting the oil so that its wrinkling tendency is controlled. The vigorous wrinkling of the oil when used alone and resulting in fine, often almost microscopic wrinkles is desirably modified so that the wrinkles are larger and more discernible.

These wrinkling oil compositions exhibit their best wrinkled appearances within preferred ranges of proportions of oil to resin, which are most suitable both as to utility and appearance of the finish. The resin content may be increased to the point where wrinkling is substantially eliminated, whereas increase in the oil content may result in an inferior appearance of the product.

- The driers in a wrinkling composition serve several purposes. They speed up the wrinkling by inducing rapid oxidation of the oil with the resulting formation of a surface skin. They also hasten the hardening of the interior of the applied varnish film by subsequent internal oxidation, thus shortening the baking time, when baking is used, for producing the desired hardness of film. Driers also have a modifying action on the size of the wrinkleslarger amounts of driers causing smaller wrinkles.

The primary purpose of the thinners in any coating composition of the varnish or lacquer type is to afford a solvent or dispersing medium for the other ingredients and to provide a means of applying the mixture to a surface in a thin film. The type of thinner has, in general, little effect on the appearance of the usual smooth fin-' ish. However, with a wrinkled finish, the thinner does exert an influence on the size of the wrinkles. A lower boiling solvent, such as toluol, produces coarser wrinkles than a higher boiling material like turpentine, due to the rapid evaporation and encouragement of a surface-skin formation.

These several factors referred to above indicate the many factors on which the character of a wrinkle finish produced from the varnish type of composition is dependent.

Among the objects of the present invention is the production of wrinkle finishes and wrinkle fini'sh compositions, and products utilizable for such purposes, which do not require the wrinkling oils as essential elements of the compositions, and therefore are not dependent on the usual type of varnish or lacquer formulas.

A further object of the invention is the production of synthetic resins which under suitable conditions yield a wrinkled surface.

Other and further objects and advantages will appear from the more detailed description set forth below, it being understood, however, that this more detailed description is given by way of illustration only and not by way of limitation since various changes in this disclosure may be made by those skilled in the art without departing from the scope and spirit of this invention.

In the production of wrinkle coatings in accordance with the present invention, synthetic resins are utilized which when dried under suitable conditions exhibit a wrinkled surface, and such resins may be generically referred to as rugo-resins or wrinkling resins. Such rugoresins utilized in connection with the present invention are well illustrated by the condensation complexes obtained with fatty acids of drying oils and in general monobasic acids, particularly aliphatic acids, which contain as a general rule more than 14 carbon atoms and at least two double bonds, such as linoleic acid. Such resins or condensation complexes may, therefore, be looked upon as condensation complexes or resins of the drying oil fatty acid type. Products of ,particular value in this connection are obtained by the reaction of a polyhydric alcohol, such as glycerol, polyglycerol, the glycols, polyglycols, pentaerythrite, monolinolein, mannitol, etc. on such organic acids or anhydrides as phthalic, malic, maleic, fumaric, succinic, citric, tartaric, mucic, benzoyl-benzoic, etc., and the unsaturated fatty acids obtained by hydrolyzing a drying oil, such as linseed, China-wood, perilla, chia, citicica, walnut, soya bean, poppy-seed, sunflower, candle nut, lumbang, hempseed, fish, etc. Mixtures of the acids, polyhydric alcohols and drying oil acids including two or more of the several ingredients may be employed.

The wrinkle finishes may be composed of such rugo-resins, a drier and a thinner and offer certain advantages apart from the simplicity of composition, over the wrinkling oil finishes of. the varnish type. In many cases, for example, the dried film is very pale in color and is practically odorless, whereas the wrinkling-oil type of finish is usually quite dark color and the dried film often retains a persistent odor for some time, especially when China-wood oil is utilized. On prolonged baking the rugo-resin film becomes practically insoluble.

Any process of finishing with the rugo-resin compositions may be employed, and such processes may be similar to those utilized with finishes of the wrinkling oil type. For example, the

composition may be applied to the surface of an article, as by spraying, after which the article may be baked. It has been found that a short period of air-drying produces an effect upon the sizeof the wrinkles. Thus, if the article is placed in the oven immediately after it is sprayed, the wrinkles are much finer than those obtained if the article is allowed to dry at, for example, room temperature for say an hour before it is placed in the oven.

The temperatures utilized during baking operation or drying step should be of an order sufficient to obtain the desired wrinkled effect with these rugo-resin compositions. Temperatures between about 170 F. and 400 F. may thus be employed. For rapid baking a temperature of 225 F. is quite satisfactory. Coated sheet metal placedin an oven at this temperature wrinkles in ten minutes, and in half an hour the finish is hard enough for handling. However, if a coat of lacquer is to be applied over the wrinkled surface, the article is preferably baked at least an hour at this temperature. At 180 F., baking for 1 hour produces a finish that is hard enough for handling and baking for 3 hours makes it resistant to lacquer solvents. The upper limit for suitable baking is approximately 400 F., depending on the nature of the composition and the type of article being considered. At 400 F. wrinkling occurred in about a minute and a finish of suitable hardness for handling is obtained in approximately 5 minutes; a finish that can be used as an undercoat for a pyroxylin lacquer or enamel is obtained in about 15 minutes. However, at this high temperature, darkening occurs very rapidly and the film has a tendency to become brittle. Also at the higher temperatures, large irregular ridges may sometimes form. This is particularly true when a heavy film of composition is applied to the article. The temperature, therefore, is generally not appreciably above 400 F. for this and other reasons. With some compositions at temperatures above 400 F., the film may become full of bubbles and loosened from the supporting base and also turn quite dark. In general, therefore, it is preferable to apply a fairly thin film of the composition, of sufficient thickness, however, to exhibit the desired wrinkling effect, and to bake such applied composition at the lowest practicable temperature. These temperatures which are employed may vary with the type of article being treated. Wood articles and other materials, such as paper, leather, etc., which might be susceptible to undesirable eifects at elevated temperatures will generally necessitate the employment of the lower ranges of temperatures; while on the other hand, the higher temperatures may readily be employed with metal, glass, pottery, etc., or other materials which are not affected undesirably by such higher temperatures.

Of the driers utilized with rugo-resin compositions, to encourage the wrinkling and hasten'the hardening of the film, cobalt driers have proved most satisfactory. A manganese drier can also be used, but lead compounds generally exhibit more of an effect on the hardening of the film than they do as wrinkle-inciters. Linoleate or resinate salts of these metals are generally preferable. Such driers may be dissolved in suitable solvents and added to the cold solution of rugoresin. One of the best driers that has thus been utilized in this connection is a composite one consisting of a solution of cobalt linoleate, 30% manganese linoleate and 10% lead linoleate.

-General solvents for the rugo-resins include esters, such as ethyl acetate, butyl acetate, butyl propionate, etc., ketones, such as acetone, methylethyl-ketone, alcohol-benzenoid hydrocarbon mixtures, ethylene glycol monoethyl ether. etc. The solubility of the resins may be controlled according to the constituents employed in the production of such resins, and also the proportions of such constituents. For example, in general it may be said that resins containing more linoleate than that given in rugo-resin E beloware usually soluble in benzenoid hydrocarbons, and those containing a large amount of linoleate as in rugo-resin F referred to below, are also soluble in petroleum hydrocarbons.

Insofar as an explanation of the wrinkling process of the rugo-resins or newer types of wrinkle finishes is concerned, without implying any limitation by this assertion, a similar explanation may be offered, namely, superficial oxidation and formation of a surface skin on the applied coating, which skin expands and produces folds and creases over the coated surface.

The following examples of rugo-resins may be considered as exemplary of the class of resins particularly employed in connection with the present invention. As indicated above, the term rugoresin may be used to designate any synthetic resin which when dried under suitable conditions gives a wrinkle surface. Hugo-resin of the drying oil fatty acid type may be employed to cover those particular resins in which fatty acids of drying oils are utilized in the production of the complexes; while the term rugo-resin of the phthalic type, rugo-resin of the glyceride type, and rugo-resins of the phthalic glyceride type may be variously employed to designate the particular types of constituent material present in those resins, including also the equivalents of such materials.

Raga-resin A Per cent Phthalic anhydride 44. 4 Glycerol 27.6 Linseed oil acids 28.0

These materials may be heated together to produce the desired resin.

In general, the resins are prepared by heating the ingredients to a desired reacting temperature. such as 200 C. or higher, preferably with agitation, and desirably while passing a stream of inert gas through the mixture which may serve to agitate the ingredients and prevent undue darkening, until reaction to the desired extent, as indicated by acid number, is obtained. Further examples of the exact procedure are given below.

Raga-resin B Per cent Phthalic anhydride 45. 21 Glycerol 18. 74 Monolinolein 36. 05

other inert gas serves the double purpose of keeping the batch agitated, and also of insuring a pale colored product by minimizing darkening during the reaction.

This formula represents approximately the low est amount of linoleic acid complex that may desirably be used in a modified glyceryl-phthalate, in order to obtain a satisfactory wrinkle finish. It is' interesting in this connection, without implying any limitations from such theoretical consideiations, to calculate the composition of the last resin, for example, in terms of linseed oil and glyceryl-phthalate and consider it as a mixture of resin and drying oil. The composition then becomes 19% linseed oil and 81% glyceryl-phthalate. This assumed oil-resin mixture is in the proportions of 3 gal. linseed oil to 100 lbs. glycerylphthalate. This oil-to-resin ratio is much lower than any hitherto encountered in a satisfactory wrinkle finish formula of the varnish type. The nearest approach to it is by use of blown Chinawood oil which wrinkles satisfactorily when the oil-to-resin ratio is 5 gal. of oil to 100 lbs. resin. Thus, it is apparent that the linoleic radical combined as it is in the rugo-resin is a more powerful wrinkling medium than any form of drying oil, as such, that is known. Or stated in another way without implying the presence of the materials either as drying oils or as glyceryl-phthalate combinations, it may be said that if the drying oil acids contained in this composition were combined with glycerin in the form of a drying oil, the oil content would be equivalent to a 3 gal. linseed oil varnish. Aside from any such theoretical considerations, however, which are not to be considered as limiting the nature of the present disclosure and invention, these considerations may be taken as exemplary of the powerful wrinkling action whichthe rugo-resins exhibit and which serve to distinguish them markedly over the wrinkling compositions of the varnish type.

Raga-resin F Per cent Phthalic anhydride a, 28.4 Glycerol 17.7 Linseed oil acids 53.9

The above given resinous-material represents perhaps the largest amount of linoleic acid material that it is possible to combine in a simple glycerylphthalate to obtain a desirable and satisfactory wrinkle finish. Based on a consideration of this resin as being made up of a mixture of linseed oil and glyceryl-phthalate as indicated above in connection with considerations of rugo-resin E, the material may be considered to be equivalent to a 22 gal. linseed oil-resin varnish. But such theoretical considerations for purposes of comparison should not be interpreted as limiting the invention herein.

Rugo-resz'n G These materials may be heated together as indicated above, and after the resinification is completed, the product may be cooled to approximately 175 F. and a vigorous stream of air blown through the molten mass for about 3 hours. Blowing with air or other methods of pre-oxidation can be carried out advantageously on any of the rugoresins. Such process results in a resin which dries faster than the unblown form, and the resin film consequently wrinkles more rapidly after being placed in the oven. A shorter baking time is' thus required with such material. For example, wrinkle compositions produced with rugo-resin H and baked for comparatively similar periods gives a similar result in approximately 10% less time than do rugo-resins F and G, although they may be looked upon as having a relatively similar composition. Rugo-resin H produces a very uniform effect consisting of fine wrinkles.

Rugo-resins B and H described above may be considered as exemplary of synthetic resinous esters derived from organic acids, particularly polybasic acid, and incompletely esterified drying oil fatty acids, such as the monoglycerides of drying oil acids. These synthetic esters or resinous materials are particularly desirable components of the wrinkle compositions, although they have much wider utility. Such synthetic resinous esters are well illustrated by the reaction products of phthalic anhydride with monoglycerides of the acids obtained by saponifying linseed or Chinawood oil. But they also include mixed resins comprising products obtained by heating a mixture of a polybasic acid, the monoglyceride of a drying oil acid and a polyhydric alcohol. The production of such synthetic complexes is particularly described below, the more specific form of these reaction products including the complexes obtained from phthalic anhydride, the monoglyceride of a drying oil acid and glycerol.

In this connection we may first consider condensation products produced from a polybasic acid and a monoglyceride of a drying oil acid. Linseed oil when saponifled yieldsa mixture of more or less unsaturated acids in which linoleic acid (C17H3lCOOI-I) is present in predominating amount. Such unsaturated acids occur as glycerides in drying oils. That is, 3 molecules of unsaturated acid are united with 1 molecule of glycerol. Moreover, the acids obtained by saponifying a drying oil may be reunited with glycerol to form a substance similar to a drying oil, that is, a triglyceride, by heating 3 molecular proportions of acid with 1 molecular amount of glycerol.

However, when a fatty acid is heated with glycerol in proportions of 1 molecule of acid to 1 molecule of glycerol, there is formed a monosubstituted glycerol or monoglyceride. And with reference to the product that is obtained when 1 molecular amount of linoleic acid is heated with 1 molecular amount of glycerol, there is formed glyceryl-monolinoleate or monolinolein. In such cases it is more economical to use the mixture of unsaturated fatty acids as obtained by the saponification of a drying oil. In such case, the product is not a pure compound since there are present in small amount in linseed oil acids, other substances than linoleic acid. Also and probably, a small amount of diand tri-substituted glycerols are formed, and even a small amount of beta-substituted glycerol, as well as the alpha-glycerol, which is the chief product. In the main, the substance obtained by heating single molecular amounts of glycerol and linseed oil acids is monolinolein, and has the formula CHaCH HOH H:OC O-GnHar Monolinolein may be considered a dihydric alcohol due to the two free hydroxyl groups contained therein as illustrated in the formula given above. Considered as such, it combines with polybasic acids, such as phthalic, maleic, succinic, malic, tartaric, citric, mucic, etc., to form esters which are of a resinous nature, and have certain properties which render them valuable for special purposes, particularly considered below.

Monolinolein may be suitably prepared in the following manner: 280 parts of linseed oil acids and 92 parts of glycerol are heated to 260 C. and while the mixture is frequently agitated, held at this temperature until the mixture is homogeneous and the reaction is almost complete. The course of the reaction is determined by ascertaining the acid number. For the purposes of this invention, the reaction is far enough advanced when the acid number has fallen below 10, as the product with this acid number is particularly useful in connection with the present invention. However, this acid number is merely given as illustrative since products with higher or lower acid numbers may also be prepared in a similar manner.

Another example of a useful drying oil is China-wood or tung oil. It is composed chiefly of the glyceride of eleostearic acid. The preparation of mono-eleostearin by the reaction of 1 mole of glycerol and 1 mole of China-wood oil acids in the same way that monolinolein is obtained as described above, may be carried out. In such instances, however, the esterification may be complicated by the fact that the acids from China-wood oil coagulate on heating and this may take place before combination with glycerol is completed. However, when one desires to avoid such coagulation, mixtures of the China-wood oil acids with other materials which prevent such coagulation prior to esterification, may be utilized. For example, China-wood oil acids may be mixed with linseed oil acids in proportions up to about equal parts of each, and heated with glycerol so as to obtain a mixture of monolinolein and mond-eleostearin. Thus, 180 parts of linseed oil acids and 100 parts of China-wood oil acids, the total being equivalent to 1 molecular amount of acid, are heated with 92 parts of glycerol to 260 C. until the reaction is nearly complete, as shown by an acid number of about 12. This gives 354 parts of a mixture consisting mainly of monolinolein and monoeleostearin, and this amount contains about 227 parts of monolinolein and 127 parts of monoeleostearin.

The use of linseed oil acids to control or reg- I 1,976,191 ulate the premature coagulation of eleo-stearic .glyceride. Such oils include perilla, soya bean,

chia, walnut, poppy-seed, candle nut, lumbang,

fish, oiticica, etc., or mixtures of these oils or acids obtained from such oils. The monoglycerides thus obtained may be combined with a polybasic acid in the same way as monolinolein is treated above. While the monoglycerides are particularly emphasized in this connection, it should be understood that any incompletely esterified drying oil fatty acids or mixtures of such acids may be reacted with the polyhydric alcohol, such as glycerol, to give products which contain at least 1 free hydroxyl group, and such reaction products containing at least 1 free hydroxyl group may then be reacted with the desired carboxylic acids, preferably polybasic acids. Mixtures of the polybasic acids with themselves or mixtures with monobasic and dibasic acids may, of course be utilized if desired.

The following examples will illustrate more specifically the preparation of monolinolein resin.

Resin I 354 parts of monolinolein and 148 parts of phthalic anhydride are-heated. These quantities represent 1 molecular amount, of monolinolein and 1 molecular amount of phthalic anhydride. The temperature is slowly raised to 220 C. and held at this point until foaming diminishes, and the acid number has fallen to about 15. When cooled the resinous material obtained by this process has the consistency of a heavy ,oil. It offers an interesting example since it may from one aspect be looked upon as an oil-resin because it combines the qualities of both a drying oil and a resin, that it, it may be looked upon as a varnish base. A solution of this material spread upon a surface, dries in the first place, by evaporation of the solvent. This leaves a sticky film which subsequently hardens by oxidation. drying, the solution behaves like a varnish In further amplification of its relation to a drying oil or oil-varnish it may be noted that metallic driers greatly speed up the final hardening or oxidation.

As driers for use in this connection, any of the liquid japan driers work satisfactorily. A lead drier, such as the resinate or linoleate is perhaps the most suitable especially if the coating is to be baked. Although not as active a drier as, for example, cobalt, it causes more thorough oxidation of the film, inducing hardening of the interior as well as of the surface. Manganese driers may also be used. All driers are preferably added to the solution cold rather than cooked into the resin as in ordinary varnish manufacture. In the latter case a turbidity or even precipitation may occur, especially in the case of lead driers. Such turbidity or precipitate may be due to the formation of an insoluble phthalate.

Resins of the character of resin I referred to above are soluble in hydrocarbons either of coal tar or petroleum origin, simple esters, such as ethyl acetate, butyl acetate, butyl propionate, ketones, such as acetone and methyl-ethyl-ketone, ethylene glycol monoethyl ether, turpentine, alcohol-benzol mixtures, etc. In general such resins are insoluble in alcohols and hydroxy- Thus, in'

esters. These resins, such as resin I are miscible with nitrocellulose and may be used in conjunction therewith in a pyroxylin lacquer. Used in a lacquer, they may serve two purposes: as a plasticizer to impart elasticity and durability to the film, and as a resin to increase the gloss and adhesion of the film.

Resin J The following example illustrates the use. of mono-eleostearln. 354 parts of a mixture of 127 parts mono-eleostearin and 227 parts of monolinolein as described above, are heated to 230 with 148 parts of phthalic anhydride. The mixture is held at this temperature and frequently stirred until the acid number has fallen to about 18. Resin J produced in this manner is somewhat more viscous than that of resin I, but its solubility in general is the same as that of resin I.

Resin K A modification in the preparation of such resins, as that illustrated as resin I above may be made in the following way. At the endof the heating process in the preparation of the resin, the temperature is allowed to fall to about 175 C. and a vigorousstream of air is rapidly. blown through the mixture for about 3 hours. This results in a much more viscous product than resin I. The resin thus treated shows an improvement in several ways. In'the first place, varnishes prepared therefrom dry more rapidly than do the varnishes made from the unblown resin. And second, clearer solutions are obtained after driers are added. This-may be due to expulsion of a part of the free phthalic anhydride by sublimation in the stream of air.

The condensation products represented by resins I to K above, are generally very soft and quite fluid. In appearance they may be compared with bodied drying oils rather than resins. And in. their drying properties they are quite similar to a long-oil varnish. In order to make harder and more distinctly resinous products, they may be treated in various ways, preferably with the addition of other resinous substances, and desirably such addition may take place in the process of formation of the resins or condensation products themselves. For example, a mixture of monolinolein, phthalic anhydride and glycerol may be heated until a suitable stage of resinification is reached. The amount of phthalic anhydride utilized in such instances may be such that there is sufficient phthalic anhydride to react with all the monolinolein, and in addition sufiicient phthalic anhydride is used to combine with all or a part of the glycerol. A complex condensation product is obtained which from one standpoint may be looked upon as a complex mixture of phthalic-linoleic glyceride condensation products and phthalic glyceride condensation products. Glycerine and phthalic anhydride are known to form hard, brittle resins, and the complex resins described above may be considered as harder, depending upon the amount of phthalic glyceride they contain. But such considerations are not intended as limitations, but merely as explanations of what takes place during the complex condensation reaction.

The following table shows four examples of resins containing varying proportions of-ingredients. In the order given, the percentages of monolinolein are in an increasing progression; and the percentages of glycerol and phthalic anhydride are in a decreasing series. Resin L is the reaction is carried the hardest and resin 0 the softest of these resin-= cus products given in this table.

Table 1 No. 1. M N 0 Mol. amts. mcnolinolein 1 1 2 2' Mol. amts. glycerol 4 2 3 1 Mol. nmts; hthalic anh drlde..- 7 .3 5 3 Parts by we ht oi mono inoleim. 364 364 718 7(8 Parts by weight of glycerol 308 184 276 92 Parts by weight of phthalic anhydride 1038 444 740 444 Percent mcnolinolein 1). ll 30. 0B 41. 07 60. 02 Percent glycerol i8. 74 1e. 01 7. 39 Percent phthalic anhydrid 45. 21 42.92 36. 09 10c. 00 100. no 100. 00

in a kettle provided with an air condenser to about 200 C. and to hold the mixture at this temperature while the batch is frequently agitated until resinification is sufficiently far advanced as shown by the acid number. It is often desirable to bubble a stream of carbon dioxide through the mixture as it is being heated. This serves the double purpose of keeping the batch agitated and insuring a pale colored product by minimizing darkening. As soon as the requisite acid 'number is reached in the heating process, the mixture is removed from the fire. number is a better index of the progress of the reaction than is a specific time limit, since the heating time required to produce these resins depends not only upon the materials being treated and the temperatures utilized, but also upon the size of the batch of the material being reacted. In general it may be stated, however, that for large batches, say of 100 lbs. of resin, the time would vary from approximately 5 to 6 hours at 200 C. At the end of the reaction, as indicated by acid number, the product may then be poured out into pans to cool or allowed to cool in the kettle to a determined point and a solvent then added. The latter results in a solution ready for use. For example, at the end of the preparation of resin M above, the resin is allowed to cool to about 160 C. and an equal amount of toluol is slowly added and stirred into the mixture.

We give below a more detailed description of each of the resins L to O referred to above.

Resin L contains a relatively small amount of the linoleic residue. In its preparation the heating is desirably discontinued when the acid number reaches about 55, since with this particular composition there is a certain susceptibility to the formation of an irreversible gel, which results if too far. At this point the acid number corresponds to an esterification which is about complete. Practically all polybasic acid-glycerides change to an insoluble, infusible form before the esterificatlon reaction is completed. However, the inclusion of materials which postpone or delay the gel formation are desirable, and the inclusion of a radical such as linoleate in the resin molecule, as illustrated in the present invention, postpones the gel formation and produces a more nearly neutral product. Thus, phthalic glyceride, unmodified by addition of other substances, changes when heated at about 200 C. to the gel form when the reaction is less than 80% complete. The effect of the linoleic-radical in the present example is to allow the reaction to go much further. Greater proportions of mcnolinolein in the formula have a correspondingly greater effect in that they seem to act in prolonging the existence of the fusible- As a general rule, acid soluble stage during the formation of the resin and allowing a more complete reaction to take place. This is also illustrated in the further examples given. 7

Resin L is relatively hard and tough. It is soluble in esters, ketones, mixtures of an alcohol and coal tar hydrocarbon, ethylene glycol monoethyl ether, etc. The resin is miscible with nitrocellulose. A solution in 4 parts of toluol and 1 part of butanol, with or without a small amount of drier, produces a coating composition from resin L which dries quickly to give a hard, pale, smooth and glossy surface. This makes it particularly valuable as a finish for wood.

With reference to resin M, the proportions of the ingredients used in the composition of this resin are such that a product of particular value is obtained. It may be noted that in the formula of resin L, the number of hydroxyl-groups are equal to the carboxyl-groups in the molecular amounts of the reaction. In the molecular amounts of the ingredients of resin M, however, there is an excess of hydroxyl-gr'oups; the number of hydroxyl to carboxyl-groups is represented by the ratio of 8 to 6. In accordance with the general procedure outlined above, the materials are slowly heated to 200 C. and held at this temperature until an acid number of about 35 or a little lower is obtained. When cold, the resin consists of a soluble, firm elastic mass, but if the reaction is allowed to go further, a rubber-like, insoluble product is obtained. Resin M differs from resin L in being soluble in coal-tar hydrocarbons, for example, toluol, as well as in the liquids that are mentioned above as solvents for resin L. The resin solution containing resin M can be used as a coating mixture, since it dries to a smooth elastic film. However, it is preferable to add a small amount of drier to such solution, and the remarks in connection with resins I to K in regard to the type of driers that can be used, also apply to resin M. That is, a liquid cobalt or manganese drier should be added to the cold resin solution. A hard resin can also be added to the solution if it is desired to harden the film without losing the elastic properties. A pigment may also be ground in the resin solution, thus forming an enamel, as will be more fully illustrated below. Resin M exhibits very good adhesion to bare metal, and its solution can be used as a primer or undercoat for subsequent coatings. In this respect it can be used as a clear solution or may first have a pigment incorporated therewith. Resin M may also be used in a pyroxylin lacquer as a combination resin and plasticizer.

With reference to resin N, in the molecular proportion of the ingredients used in the preparation of this resin, the ratio of hydroxyl to carboxyl-groups is 13 to 10. This leaves a large excess of hydroxyl-groups. In the preparation of the resin, the reaction may be run to an acid number of 30 and the result is'a soft rubber-like resin which gives a relatively soft film, a film that is somewhat softer when dry than that obtained with resin M. The solutions of resin N are utilizable as coating compositions or-as resin plasticizers in a nitrocellulose lacquer.

Resin N is exemplary of resins produced in accordance with these disclosures which may be further utilized as a base for the preparation of harder resin products, which may be obtained for example by esterifying part of the hydroxylgroups by reaction with an acidic natural resin, such as rosin, Congo, manila, pontianak, etc. For

example 250 parts of resin N and 100 parts of ,resins may be run to substantially the same acid rosin may be heated to 260 C. for several hours until the acid number has fallen to about 18. The resulting resin is harder than resin N. It is soluble in practically all solvents except those of the alcohol-type.

In resin 0, the larger proportion of monolinolein produces a softer and more rubber-like composition than resin M, but harder in general than the resins illustrated by resins I to K above. Made according to the general procedure outlined above, the reaction may be carried to an acid number of about 20, this low acid number being possible through the large amount of monolinolein and also through the excess in the number of hydroxyl over the carboxylgroups per mole of resin. In the molecular proportions of the ingredients there are relatively 6 carboxyl to 7 hydroxyl groups. Resin 0 has the same solubility as resin M. Its solutions, preferably with a small amount of drier added, dry to give very flexible films. It may also be utilized in nitrocellulose lacquers, and in such instances may act both as a resin and as a plasticizer. In all cases, therefore, these resins which may act as both resins and plasticizers in lacquer or other composition,

do not require any addition of other resins or additional plasticizers; However, if desired, such compositions may include not only the resinplasticizers of the present invention but additional resins and additional plasticizers when desired.

In the resins designated as B and H to O inclusive,'as set forth above, such complexes were prepared with the use of monoglycerides or other hydroxyl-containing glycerides. It is interesting to compare such resins with those obtained by the simultaneous reaction of fatty oil acids, polybasic organic acids, such as phthalic anhydride, and polyhydric alcohols, such as glycerol. For purposes of such comparison the following table shows resins of the same elementary compositions as the correspcnding numbers of resins L to 0. That is, in the following table, resins P to S are comparable with resins L to 0 given in Table 1 above. The percentage composition of the ingredients is not the same in the corresponding cases, that is, resins L and P, for example, do not have the same' percentage composition of the mixture before reaction, but after reaction 1 molecular amount of resin is obtained in the production of resin L as in the production of resin P. Also, if hydrolyzed by caustic soda, resin L would give the same percentage of sodium phthalate, sodium linoleate and glycerol as would be obtained under similar conditions from resin P.

And the same analogy holds for resins M and Q respectively, N and R, and O and S.

Table 2 No P Q R S M01. amts. linseed oil acids 1 1 v 2 2 Mol. amts. glycerol 5 3 5 3 '1 Mo]. amts. phthalic anhydnde... 7 3 5 3 Parts by weight of linseed oil acids 280 E0 560 560 Parts by weight of glycerol 460 276 460 276 Parts by weight of phthalic anhydride 1038 444 740 444 Percent linseed oil acid 31. 82 43. 75 Percent glycerol .87 26.14 21. 56 Percent phthalic anhydri 42. 04 34. 69

The same general procedure can be used in preparing the resins illustrated in Table 2 as is utilized in preparing those of Table 1. Also the number-as for the corresponding resins of the L too series.

In spite of the close similarity in composition between resins L to O and P to S respectively, there are two principalpoints in which the two series of resins differ: in viscosity of solution and in hardness of film. The solutions prepared from the L to 0 series of resins have a greater viscosity than the corresponding solutions containing resins P to S. Also, films of the L to O resins are slightly harder and tougher than films prepared from the resins of the P to S series. Consequently, it may be emphasized at this point that the resins produced using monoglyceride or other hydroxy glycerides of drying oil fatty acids have in some instances markedly distinct prop- Example 1 Percent Resin 1... 45.0 Cobalt linoleate 0.5 Manganese resinate 0.2 Turpentine 10.0 Hy naphtha 44.3

This composition produces a mixture of suitable brushing consistency which dries dust-free in approximately 1 hour. After 12 hours drying the film is sufliciently hard so that it does not print and gives a very smooth, glossy, tough coating.

The following composition, is illustrative of erties and characteristics from those produced,

the incorporation of hard resins with the rugoresins or drying oil fatty acid resins of the present invention to modify the properties of such compositions, and to produce a harder and quicker drying varnish than is obtained ordinarily when the oil-resin is used alone. This following formula is illustrative of a rubbing varnish:

Example 2 Percent Resin I 25 Fused Congo 20.0 Cobalt linoleate .6 Manganese linoleate .4 Turpentine 15.0 Heavy naphtha 39.0

This varnish dries dust-free in about 40 minutes and can be rubbed and polished after about 12 hours. The film is glossyand hard. Other resins besides Congo can be used, for example,

kauri, pontianak. rosin, rosin ester, Amberol,

frosted film, when dry, and in this way modified effects may be obtained. However, other materials may be incorporated with such composition in order to yield clear glossy films, and for such purposes the other resins mentioned above, such as Congo, may be utilized. Using resin J in Example 2 above for a rubbing varnish, the mixture dries slightly faster than when resin I is utilized in the corresponding composition. When resin J is employed, the varnish dries dustfree in about 30 minutes and can be recoated in about 6 hours when such additional coatings are employed.

As a further example of coating compositions containing the addition of hard resins to modify the properties of the film obtained from such compositions without losing the elastic properties, the following example of an enamel which may be applied to a metal surface is given.

Example 3 Percent Resin M 27% Pigment 2 Amberol 5 Japan drier 5 Toluol 20 Xylol 20 ButanoL.

Example 4 v Percent Resin AmberoL- 20 Cobalt linolea 0.5 Toluol--- s 49.5

As indicated above, the rugo-resins and condensation complexes discussed in this application are eminently suited for the production of wrinkle and other textured finishes, and they offer marked advantages over compositions of the wrinkling oil type. Apart from the advantages of paleness of color and lack of odor which such resins and condensation complexes exhibit, there is considerable saving in the time required for the baking operation when the latter is utilized, and. even if the coated surface is allowed to air-dry for about half an hour before the article is placed in the oven, the time required to obtain a hard wrinkle finish is less with the rugo-resins than with the wrinkling oil type of finish. There has been given above a general discussion of driers, solvents, thinners and other factors which enter into the production of these wrinkle and texturing types of finishes, and there is given below a number of examples which illustrate various features of this phase of the invention. In the examples given below, as well as those set forth above, all percentages are by weight.

The mixture of rugo-resin, drier and thinner when sprayed upon a surfaceandbaked gives a very pale,'odorless finish of fairly coarse and very uniform wrinkles. The film is quite elastic, making the finish obtained therefrom suitable for metal intended for stamping and forming op- This composition gives a very uniform wrinkled effect, the wrinkles of which are very slightly coarser than those of Example 5, above, when the same thickness of baked film is utilized. The film from Example 6 is tough, pale, odorless and elastic.

Example 7 Percent Glyptal resin V 45 Japan drier 3 Toluol 52 The 'glyptal resin here used is a commercial product purchasable on the market and is known as Dux 3002. Glyptal is the name applied to con densation products of glycerol and phthalic anhydride, modified by the incorporation of an aliphatic acid, etc. The above resin solution when sprayed gives a very regular effect consisting of fairly coarse wrinkles. The film after baking is slightly soft.

Example 8 Percent Rugo-resin C 55 Japan drier 3 Toluol 32 Light naphtha 10 The resin solution and drier when spread in a film and baked gives a wrinkled effect that is fairly coarse and more or less irregular. It works best when used as a rather heavy film. The film is very elastic.

Example 9 Percent Rugo-resin D 46.0 Cobalt linoleate -L .4 Manganese resinate .1 Toluol- 43.5 Alcohol 10 A good wrinkled effect is obtained when the resin solution and drier is baked. The baked film is pale colored and flexible.

This formula gives coarse shallow wrinkles which, however, are quite regular.

Example 11 Percent Rugo-resin F 60 Cobalt linoleate 0.6 Manganese linoleate 0.2 Light naphtha 39.2

Very fine, regular wrinkles are obtained by the use of this formula.

Example 12 Percent Resin (3 50.0 Cobalt lincleate .6 Manganese linnleai'e ,3 Lead lincleate .1 Toluol 49.0

The resin-drier solution gives a regular closepattern effect which can be obtained even when the material is sprayed on the desired article in a very thin coat.

Example 13 Percent Resin H 45.0 Cobalt linoleate 1.0 Toluol 54.0.

This formula represents the use of an air-blown rugo resin, which resin dries faster than the unblown form, and the resin film consequently wrinkles more rapidly after being placed in the oven. Ashorter baking time is thus required with such materials. Example 13 bakes in approximately 10% less time than Examples 11 and 12, although they have relatively the same composition. The coating obtained with Example 13 produces a very uniform efiect consisting of fine wrinkles.

Various resins may be added to the composition in order to modify the properties thereof, and particularly natural resins such as Congo, damar,

synthetic phenol formaldehyde resins, such as Amberol, cumarone resins, such as cumar, etc. may thus be incorporated, the proportions of such materials being limited, so that the desired wrinkling effect is not completely eliminated by the proportion of material added. The following examples will illustrate the addition of such resins.

Example 14 Percent Resin A- 35.0 Amberol 15.0 Gobalt lincleate 0.8 Toluol- 39.2 Light naphtha 10.0

This composition yields a very uniform and satisfactory efiect. The wrinkles are coarser than those obtained with Example 5, which makes use of the same rugo-resin. The film is also harder than that obtained from the composition of Example 5.

' Example 15 Percent Rugo-resinA 25 Amberol 25 Cobalt lincleate 0.6 Toluol 49.4

This formula is similar to that given in Example 14 above, and is included in order to illustrate the effect of the increased proportion of the additional resin-on the wrinkling, as well as to show the extent to which this particular resin may be diluted without dastroying its wrinkling tendency. The surface effect that is obtained by this formula consists of very coarse regular wrinkles. The film has a tendency to brittleness, which, if desired, may be modified by the incorporation of fiexibilizing constituents. For purposes of calculation and considering this composition for such. purposes as a mixture of linseed oil and the resins Amberol and glyceryl phthalate, this composition is equivalent in resin content to a 3 gal. linseed oil varnish. If Amberol or other addition resin is used in amounts greater than about 3 parts to 2 parts of the rugo-resin, wrinkling may be entirely eliminated.

A quite satisfactory wrinkled effect is obtained by the use of. the above soft, blown wrinkling resin, which contains a high percentage of lineleatef and a non-wrinkling resin. This formula gives a much tougher film when baked than does Example 15 due to the soft nature of the rugoresin used in this formula. A comparison of the wrinkling composition 16 with that of a satisfactory composition of the wrinkling-oil type such as is explained below in connection with Example 20 and the wrinkle varnish of Example 21, emphasizesthe comparison of the use of rugo-resins to that of wrinkling oils. Although resins of the glyceryl-phthalate type are not usually miscible with drying oils in all proportions, a certain amount of oil can be added to the resin solution here under consideration. Thus, for exampie, 1 part of blown China-wood oil to 10 or more parts of rugo-resin A gives a solution which dries to a clear film. A greaterproportion of oil gives a cloudy film but about 1 part drying oil to 2 parts rugo-resin can be used before separation of two phases in the film occurs.

The presence of a small amount of a wrinkling oil has a markedeffect upon the wrinkling of a rugo-resin composition. Even as small an amount of wrinkling oil as 1 part to 50 parts of rugo-resin has the efiect of producing smaller and finer m wrinkles than when the oil is not used. Consequently, varying amounts of wrinkling oils may be included in the composition in order to control and regulate the character of the wrinkles obtained. Some of the following examples illustrate these features.

Example 17 Percent Hugo-resin A 43.5

Blown China-wood oil 1.7

Cobalt lincleate 1.0

. Light nap 8.8

Toluol 45.0

This formula illustrates the use of a small amount of a wrinkling oil. In comparison with Example 5, the wrinkling is of a finer pattern and occurs in very thin films. The wrinkle film is quite pale and elastic.

The above is a satisfactory Wrinkle finish formula illustrating the combined use of wrinkling and non wrinkling resins and wrinkling oil.

When it is desired to give added flexibility to rugo-resin films, fiexibilizing agents may be utilized for this purpose, and for example small 10 amounts of a non-wrinkling oil, such as castor oil, soya bean, rapeseed, cotton seed, etc. and their blown and boiled derivatives can be utihead. The amount should be in general less than 1 partof non-wrinkling oil to 5 parts'of rugoresin. Or plasticizers such as. or those containing, non-volatile solvents including dibutyl This formula wrinkles satisfactorily and gives a soft flexible film.

The following example is illustrative of a mixture of a satisfactory formula of the wrinklingoil type and one of the rugo-resin type of wrinkle finish.

Example 20 Percent Wrinkle varnish 44 Rugo-resin A dissolved in 50% toluoi; 44 Japan drier 2 Alcohol 10 The wrinkle varnish utilized in Example 20 is made according to the following formula.

, Example 21 Congo 125 lbs. Rosin 6 lbs. Red lead 2 lbs. Manganese borate H lb. China-wood oil 3% gal. Blown wood oil 8% gal. Light naphtha 6 gal. Toluol 22 gal.

-The wrinkling effect of the composition given in Example 20 is of a coarse pattern.

The compositions set forth above, and particularly those illustrated in Examples 5 to 20, may

be utilized in various ways; As undercoats for pyroxylin and other lacquers, oil enamels or baking japans, the material is applied to an article and the article baked until the finish is hard. The finishing coat of suitable color is then applied over the wrinkled surface. may be pigmented or unpigmented, that is any of the above formulas may be used as given, or

from 1 to 4% for example of a pigment ground in'some of the resin sol tions may be added to tint the material to a suitable shade.

The term Amberol as used above covers rosin phenol-formaldehyde synthetic resins, that is resins of the bakelite type that have been modifled by the presence of a natural resin such as rosin. The term Hy naphtha" refers to a hightest naphtha. The term Titanox" refers to a commercially available titanium oxide.

The compositions can also be used in making enamels. From 5 to 20 per cent of a suitable pigment is ground into the resin solution. This produces a composition which yields a satisfactorilycolored finishby means of one coat. As used in wrinkling enamels the pale colored rugoresin compositions have an advantage over the dark, amber colored wrinkling oil materials in that very light colored enamels can be produced when light colored pigments are used. For example 8 percent Titanox added to the wrinkle The undercoat varnish whose formula is given in connection with Example 21, produces a cream .colored enamel, whereas the same amount of pigment as given in Example 5 yields a white enamel. The clear compositions can be used over any color of ground coat,the shade of which is afterwards visible through the baked wrinkle finish coating. In this way, it can be used over a colored design or a printed surface and the characters of the design will then show through the clear wrinkle finish. The light colored rugo-resin solutions have less effect on the color of the ground coat than the darker wrinkle varnishes. The clear material can also be applied to such materials as parchment paper and baked. There is thus produced a translucent sheet which is suitable for lamp shades, etc.

'Perhaps the most unique use for the clear, pale rugo-resin finishes is on tinned sheet metal. Applied in one coat over the bare metal and baked at a low temperature until the finishis hard enough to withstand handling, there is produced a patina effect which somewhat resembles silver or white gold.

In utilizing the compositions of the present invention for coating purposes, such compositions may be used as single coatings, or they may represent one or more coatings in a multi-layer coating. In any such cases, pigmentation may be utilized where multi-layer coatings are employed, and contrasting pigmentation may be employed as between the layers to give multi-color and contrasting color efleots.

The desired textured effectmay be obtained on any surfaces of articles of manufacture, among which there may be particularly noted metal, wood, plaster, pottery, glass, paper and leather. The desired finishes may be obtained on any structure or articles of manufacture made from such or other materials, andthe application of these compositions as finished coatings, either in single or multi-layer coatings on articles of manufacture is a particular and desirable feature of the present invention.

The light-colored compositions when applied to sheet metal, as illustrated above, yield a patinized effect which is silvery or white gold in color.

Darker colored or amber colored compositions may similarly be applied to bright reflecting surfaces, such as sheet metal, to produce a patinized eflectwhich is more or less golden or golden bronze in color. For example, the application of such compositions to sheet tin or tinned sheet iron yield a sheet supporting surface which is given a. rich patina effect at anextremely low cost. The actual depth of color may be somewhat modified by the temperature and length of heat treatment or baking operation, higher temperatures and more protracted heating tending to give darker bronze colors.

The textures of the wrinkle finishes may be modified at one or more segregated areas in the wrinkle surface so that design effects are produced in the wrinkle finish. Such modified effects may be referred to for example as sag, curtain and pine tree. These several effects may be generically referred to as accentuated rugosities or waves of wrinkle finish produced by agglomeration of heavier or thicker films of the composition at certain 'points of the surface, while at .verted V's. For the production of these wrinkle in the finish, the article may be coated with a.

relatively heavy coating of the desired composition and baked in an inclined position, which inclined position may vary from a small angle to the horizontal, to a vertical position. The extent of inclination will determine the flowing or movement of the wrinkle coating after it is applied and at or about the time when the baking commences, and in this way modified eflects are readily obtained.

Other'modifled effects in the finish may be obtained by variations in the manner of application. Brushing, stippling, and modified spraying operations may be utilized to effect particular textured elfects. For example, when gang sprays are used to apply the composition, at certain points, the atomization may be made coarser to produce heavier or thicker layers at these points resulting in coarser wrinkles in such thicker layers. Accentuated rugosities distributed in the more uniformly wrinkled finishes may be produced in this way.

In the production of multi-layer coatings of various types in accordance with this invention, the textured or wrinkled or otherwise modified coatings produced with the particular compositions set forth above, may constitute either the exposed or outer layer or the inner or undercoat. Various effects may be obtained in this manner, particularly by contrasting pigmentation in the several layers. When the textured or wrinkled coating is the outer layer, such textured coating is shown against the other background, particularly when contrasting pigmentation is utilized. On the other hand, when the wrinkled or otherwise textured coating forms one of the undercoats, a substantially smooth outer coating-may be obtained thereover which exhibits the wrinkled or otherwise textured efiect through the upper layers, particularly when the outer layers are transparent. Transparent or translucent outer layers may be utilized, and may be variously pigmented or dyed, particularly when such pigmentation or dyeing is contrastingly utilized with the pigments or dyes of the undercoat.

Baked or dried finishes produced with compositions of the present invention are particularly resistant to softening by lacquer compositions, and particularly the solvents used in lacquers produced with cellulose derivatives, such as nitrocellulose. Consequently, although the rugose surface of the wrinkle finish affords a very extensive area for the action of such solvents or lacquers, the baking creates a resistance to such softening action. It follows, therefore, that the wrinkle finishes in compositions used for producing such coatings are particularly desirable as undercoats where a wrinkle or otherwise textured finish is desired, and such finishes may then be given one or more coats of pyroxylin enamels, oil enamels or baking japans. Particularly when pigments are used in the wrinkle or otherwise textured finishes which have a tendency to change ordarken under the action of elevated temperatures or due to other influences, these finishes may be coated with pyroxylin lacquer compositions.

Having thus set forth my invention, I claim:

1. A wrinkle finish composition consisting of a rugo resin having an oil fatty acids content of from approximately 15.7% to 53.9% in solution in a hydrocarbon solvent.

2. A wrinkle finish composition consisting of a rugo resin having an oil fatty acids content of from approximately 15.7% to 53.9% in solution in a hydrocarbon solvent, and a drier.

3. An article carrying a wrinkled finish containing a rugo resin having an oil fatty acids con tent of from approximately 15.7% to 53.9%.

4. The process of producing a wrinkled finish coating which comprises applying to an article, a coating composition containing a substantial proportion of a highly volatile solvent and as the essential base-forming ingredient, a resinous ester of polyhydric alcohol, a polybasic acid and fatty acids of a drying oil, and then drying the coating to produce rapid evaporation of the highly volatile solvent with consequent wrinkling of.

the coating.

5. The process of claim 4 in which the ester forms 25-75% of the composition.

6. The process of claim 4 in which the ester forms 40-50% of the composition.

7. The process of claim 4 in which the composition contains a drier.

10. The process of producing a wrinkled finish coating which comprises applying to an article, a-coating composition containing a substantial proportion of a highly volatile solvent and as the essential base-forming ingredient, a resinous ester of a polyhydric alcohol, phthalic acid and fatty acids of a drying oil, and then drying the coating to produce rapid evaporation of the highly volatile solvent with consequent wrinkling of the coating.

11. The process of producing a wrinkled finish Y coating which comprises applying to an article, a coating composition containing a substantial proportion of a highly volatile solvent and as the essential base-forming ingredient, a resinous ester of glycerol, phthalic acid and fatty acids of a drying oil, and then drying the coating to produce rapid evaporation of the highly volatile solvent with consequent wrinkling of the coating.

12. The process of producing a wrinkled finish coating which comprises applying to an article, a coating composition containing a substantial proportion of a highly volatile solvent and as the essential base -for ning ingredient, a resinous ester of glycerol, phthalic acid, and fatty acids of linseed oil, and then'drying the coating to produce rapid evaporation of the highly volatile solvent with consequent wrinkling of the coating.

13. The process of producing a wrinkled fini'sh coating which comprises applying to an article,

a coating composition containing a substantial 15. A wrinkle coating composition substantially dependent upon and containing a rugo-resin oi the drying oil fatty acids type having the effect of producing a wrinkled coating on drying.

16. A wrinkle coating composition substantially dependent upon and containing a rugo-resin of the phthalic glyceride drying oil acids type having the eiIect of producing a wrinkled coating on.

drying, said composition also containing a-drier and a vehicle.

17. A wrinkle coating composition substantially dependent upon and containing a rugoresin of the phthalic glyceride drying oil acids type having the effect of producing a wrinkled coating on drying, said composition also containing a drying oil, -a drier and a vehicle.

18. A wrinkle coating composition substantially dependent upon and containing a rugoresin of the monoglyceride-polybasic acid type having the effect of producing a wrinkled coating on drying.

19. A wrinkle coating composition substan tially dependent upon and containing a rugoresin of, the monoglyceride, polybasic acid, polyhydric alcohol type having the effect of producing a wrinkled coating on drying.

20. An article of manufacture carrying a wrinkled finish substantially dependent upon and containing a rugo-resin for producing the wrinkles.

21. An article of manufacture carrying a wrinkled coatingsubstantially dependent upon and containing a rugo-resin o! the monoglyceridepoiybasic acid type for producing the wrinkles. V 22. The process of producing coated articles which comprises applying a composition substantially dependent upon and containing a rugoresin having the effect of producing a wrinkled coating, to an article of manufacture, and drying the composition at a temperature at which a wrinkled finish is obtained.

23. The process of producing a wrinkled finish coating which comprises, applying to an article,.

a coating composition containing a substantial proportion of a highly volatile solvent and as the essential base-forming ingredient, a rugo resin, and then drying the coating to produce rapid evaporation of the highly volatile solvent with consequent wrinkling oi the coating.

24. A wrinkle coating composition substantially dependent upon and containing a rugo resin having the efiect of producing a wrinkle coating on drying, said composition also containing a drying oil, a drier and a vehicle.

25. -A wrinkle coating composition substantially dependent upon 'and containing a rugo resin having the efiect' of producing a wrinkle coating on drying, said composition also containing blown China-wood oil, a drier and a vehicle.

FRANK BRIAN ROOT.