US2212369A - Synthetic oil for treating textiles - Google Patents

Description

Patented Aug. 20,1940

1 UNlTED STATES PATENT OFFICE 2,212,369 1 SYNTHETIC 011. FOR TREATING TEXTILES Alphonso. Jaegcr, Mount Lebanon, Pa., assign- :or'to American Cyanamid & Chemical Corpo- -ration,'New York, N. Y., a corporation of Delaware No Drawing. Application January 14, 1938,

1 Serial No. 184,931

g .5 Claims.

A Thisinvention relates to theoiling or lubribricants which have been used for the above purposes were 01 natural, and usually'of-animal or vegetableorigin. For the worsteds olive oil has been theprincipal lubricant while for woolens and low woolens a mixture of such oils as olive oil, teaseed oil or oleins, which are crude oleic acids containing a high percentage of free fatty acid, have been used, In many cases these oils have been mixed with mineral oils, the latter being present in amounts of 10-20% by weight or more. The many limitations of these natural oils and oil mixtures 'havelong been recognized in the textile trade, but no substitute as yet proposed has been fully satisfactory. It is true'that proposals have been made to use glycerol, or 001mprove the scouring properties by reacting triglyceridessuch as olive oil or coconut oil with suflicient' amounts "of "glycerol to produce the monoglyceride but these modified oils and fats still retain the disadvantages characteristic of the natural'oils themselves.

I have now found that lubricants for textiles oi.' the above types-are greatly improved when they containor consistof' esters of organic polycarboxylic acids or their anhydrides with a monohydric or polyhydric alcohol, or combined esters thereof. Manyof the" synthetic chemical compounds of this'class are excellent lubricants when usedsingly or in admixture with eachother as a synthetic textile oil, but it is a-characteristic property oi. all the members ofthis class of materiais that they will improve'any oi. the materials of natural origin now used as lubricating agents when mixed with them in substantial quantities.

Accordingly, my invention comprises a process of lubricating textiles or textile fibers by the applicationthereto oi lubricants consisting of or containing synthetic esters of the above defined class, either singly or in admixture. A further object of the invention resides in the improvement of the lubricating, scouring or other properties of textile lubricants by the incorporation therein of unmodified or modified esters of organic polycarboxylic acids. A still further ob- 'ject of'the invention resides in the improvement of lubricants for textiles by decreasing or eliminating their capacity for spontaneous combustion and increasing their fluidity at low temperatures, these improvements being characteristic of textile lubricants consisting of or containing substantial quantities of the unmodified or modified esters of organic polycarboxylic acids with monohydric or polyhydric alcohols of the present invention.

The polycarboxylic acids which may be employed in preparing esters for use in accordance with the present invention may be aliphatic, hydroaromatic or'aromatic, but I have also found that the esters of the aromatic and hydroaromatic polycarboxylic acids have in general better qualities than have the esters of aliphatic polycarboxylic acids. However, esters 01' allphatic dicarboxylic acids are also useful, particularly as agents for improving the scouring value of the'lubricant's, and to this extent they are also included within the scope of the-invention. For example, I have found that the class of aliphatic dicarboxylic acids consisting of malei'cacid, its isomer fumaric acid and its reduction product succinic acid will produce esters which have excellent scouring properties for textiles fibers, and

.the ester of the sulionated or phosphorylated acids of this class are even better. Moreover, esters of the aliphatic acids may be used to modify certain oi. the characteristics of the aromatic and hydroaromatic dicarboxylic acid esters of polyhydric alcohols, as will be subsequently explained, and the esters of this class are therefore also in cluded within the scope of the invention.

Among the aromatic diand polycarbox'yllc acids whose'esters form the preferred -lubricating agents of the present invention phthalic acid or anhydride and its modification products such as sulfophthalic and halogenated phthalic acids such as the chlorophthalic acids occupy an outstanding position by reasonoi. their commercial availability and relatively low price and the low vapor pressure and excellent lubricating qualities of their esters. Among the diand polycarboxylic acids of the hydroaromatic series, those obtainable by the selective hydrogenation of phthalic acid and by the "dime synthesis are of greatest interest since they produce low vapor pressure esters of excellent stability having good such as ethyl, methyl, propyl, butyl, amyl, hexyl,

heptyl or octyl alcohols such as cetyl alcohol,

ethyl hexyl alcohol, etc. as well as the corresponding higher alcohols from the saponification of waxes and the reduction of fatty acids such as lauryl alcohol, palmityl alcohol, ceryl alcohol, etc. In addition to the straight chain alcohols, isomeric or branched chain alcohols may be used, including such compounds as isopropyl alcohol, isobutyl alcohol, isobutyl carbinol or other isobutyl alcohols, capryl alcohol, pinacolyl alcohol, tetramethyl-ethyl or other isomeric hexyl alcohols and the like as well as higher alcohols of this nature. Another class of alcohols which are of value in producing esters for use in the textile lubrication are ether alcohols such as methoxy, ethoxy and butoxy ethanols, aromatic ether alcohols such as phenoxyethanols, alkyl phenoxyethanols, etc.

In addition to the saturated monohydric alcohols, the corresponding alcohols of the olefin series may be used. Allyl and crotonyl alcohols are typical lower alcohols of this type which may be employed in some cases and oleyl alcohol is a typical higher alcohol. Mixed alcohols from special sources may also "be used, such as the mixture of isomeric amyl alcohols obtainable from the absorption in sulfuric acid and subsequent hydrolysis of casing head gas or other petroleum fractions and sold as "PentasoP; mixed alcohols from similar treatment of other petroleum fractions; synthetic lower and. higher alcohols from the catalytic reduction of carbon monoxide or dioxide or from the hydrogenation of coal and oils, etc.

Another important class of alcohols which may be used in preparing esters for textile lubrication are those of a cyclic nature such as the aromatic alcohols including benzyl alcohol, the tolyl carbinols, the naphthyl carbinols, dialkyl benzyl alcoholsand the like. Esters of these alcohols are particlarly valuable for admixture with lubricating oils of natural origin, such as olive oil, castor oil, teaseed oil and the like, by reason of their antioxidant properties. Another special type of compounds falling within this classification are the inner esters, the lactones, which may be produced for example by reduction ofpolybasic acids having at least two carboxyl groupsin ortho position. Phthalide, which is a reduction product of pthalic anhydride, is an example of such a lactone. I

have found that this compound may be incorporated to advantage in lubricants for textile fibers, especially in combination with esters of organic dicarboxylic acids. Other lactones 'such as those obtainable by partial reduction of hydroaromatic acids resulting from the dienesynthesis may also be used, a typical example of such acids being the condensation product of maleic or fumaric acid with rosin or with dehydrated castor oil, linseed oil or the fatty acids thereof. Corresponding ester products of such acids as contain free carboxyl groups may also be used. Hydrogenation and substitution products of the above compounds may also be used such as hydrogenated and substituted phthalides, these derivatives having physical. properties which vary with the degree of hydrogenation and substitution and offer in themselves a wide field of choice for the purposes of the present invention. Other alcohols and acids may also be used, for example monoor polyhydroxy organic acids containing one or more carboxyl groups, in which acids one or more of the hydroxy groups may be esterified with a polycarboxylic acid.

It is understood that any of the esters which may be prepared by esterification of the above alcohols, either singly or in admixture, with polycarboxylic acids may be used in the oiling of textiles. These esters are well suited for use-as the sole treating agent in these processes, but another important feature of the invention resides in their use in conjunction with the vegetable or animal oils, mineral oils, fats and fatty acids which are now used for these purposes. This is important, not only by reason of the wider field of choice which is made available by the use of a mixture of lubricants, but also because the long experience which has already been acquired in treating textiles with natural oils and fatty acids becomes available in applying the mixtures thereof with plication now in use, and this constitutes an importantadvantage of the invention.

Another advantage flowing from the use of esters of phthalic acid in conjunction with the natural oils and fats now used for technical lubrication is the resistance of these esters to ultraviolet light. The incorporation of even small quantities of any of the abovedescribed phthalic acid compounds into the oiling compositions now used for textiles will result in an increased stability against rancidity andspontaneous combustion and will produce more even dyeings in the finished textiles;

Another feature of the invention which is of great practical importance resides in'the modification of the synthetic esters of the present invention by the introduction of the inorganic or organic substituents. For example, the sulfonation of these, esters or the use of sulfonated acids or sulfonated alcohols in their preparation results in a lubricant which is more easily emulsilied and more easily removed from the finished goods by the ordinary detergents now in use, and the introduction of amino, halogen, hydroxy and similar groups also will impart special properties. The most important products of this nature are, of course, sulfonation products; and these may be prepared by any of the known sulfonation processes. A particularly useful method of applying this feature of the invention is the partial sulfonation of the completed ester, or the use of a mixture of sulfonated and unsulfonated acids in esterifying, whereby an incompletely sulfonated product is produced. This method permits the preparation oftextile oils having not only good lubricating characteristics but having exactly the right emulsification properties for proper removal after weaving of the fabrics and, in fact, the use of esters of a mixture of sulfonated and unsulfonated acids will in many cases produce a composition which requires no additional detergent for removal. For example, a mixture of 90 parts by weight of dimethyl phthalate and 10 parts of the sodium salt of dioctyl sulfosuccinate or diamyl sulfophthalate constitutes a satisfactory lubricant for woolen fibers that can easily be removed by simple agitation in hot water.

In addition to the esters of organic dicarboxylic acids with monohydric alcohols of the classes enumerated, there are certain classes of ,reaction products of these acids with dihydric and polyhydric alcohols "and their ether compounds which are of value in the lubrication of textiles, and

' oil, etc., animal oils and the like, either singly which are included in the invention. Many of the esters of this class, such as the phthalic glycerides, harden or polymerize to synthetic resins which in themselves have no lubricating value, but I have found that many of the esters of this class may be modified in such a manner as to produce liquids of relatively low viscosity having excellent lubricating properties. For example, the reaction products of polyhydric alcohols with organic dibasic acids, which reaction products contain substantial quantities of oils or oily materials such as higher fatty acids as modifying agents, with or without additional esterificationwith monohydric alcohols, form excellent lubricants for textiles.

Another advantage of esters of polyhydric al- .cohols with polybasic acids is the opportunity which they present for preparing compounds containinganexcess of .hydroxy groups over and above those necessary for ,esterification of the polycarboxylic acids themselves. as an important feature of the invention, that esters of polyhydric alcohols with polybasic acids, which esters contain an excess of hydroxy or ether groups as above defined have important scouring properties and are much more easily removed from the fiber by the ordinary detergent after spinning and weaving. Thesehydroxy groups may be present in uncombined form, as in the case of dlglycol phthalate, phthalate, dibenzoyl diglyceryl maleate, etc., or they may be completely esterified with monobasic acids as in the case of dioleyl diglycol monophthalate, or succinate. The results obtainable with compounds of this class are illustrated in the following examples.

Suitable oils, fats or fatty acids which may be used for modifying polyhydric alcohol esters' of polybasic acids for textile lubricants include the non-drying vegetable oils, such as cottonseed oil, palm oil, corn oil, coconut oil, olive oil, teaseed having an iodine value not greatly in excess of 100 and do not polymerize to a greater extent than does castor oil on blowing with air. A special class ofacids which are readily obtainable and are excellently suitable for this purpose are the fatty acids such as oleicandstearic acids derived from talloil or black liquor soap which is produced as by-product in the kraft process of paper pulp manufacture.

The compounds obtained upon introduction of i the above oils, fats, and fatty acids into complex esters of polybasic acids with polyhydric alcohols may be further modified by combination with any of the monohydric alcohols, suchas those previously described, or by combination with non-oil acids such as benzoic acid, acetic acid. furoic acid, propionic acid, tetrahydrobenzoic acid, etc. This class of compounds is known technically by the term long oil alkyd resins, which term is defined as a polyhydric alcohol-poly-carboxylic acid ester containing at least 50% of an oil or of a fatty acid obtained from an oil.

The lubricants of the present invention may be applied to the textiles by any of the methods now in use, and may be employed as such, in admixture with each other, in the form of emulsions, or in admixture with soaps in the form of the so-called wool creams. 'Irrespective of the I have found,

tage of the present invention that all the synthetic esters used therein are readily emulsinable with most of the emulsifying and securing agents now used in the wool industry, which greatly facilitates their removal from the fiber after weaving or knitting. A short list of surface active agents which may be used in preparing the lubricants in emulsified form or for removing them from the finished piece goods is the following.

(1) Sulfonated aromatic hydrocarbons and their homologs, such as sulfonated naphthalene, 3

propyl or isopropyl, butyl or isobutyl and amyl naphthalene sulfonic acids, or their ammonium, alkali metal or triethanol amine salts.

(2) Salts of sulfonated aromatic or aliphatic esters of mono-, diand polycarboxylic acids, such as dipropyl, diamyl, di- (methyl amyl) or dioctyl esters of sulfonated phthalic acid.

(3) 'Sulfated or sulfonated higher alcohols, such as sulfonated lauryl or other alcohols prepared from the fatty acids of vegetable oils.

(4) Sulfonated mineral, vegetable or animal oils such as the aquasols which are castor oils of varying degrees of sulfonation.

(5) Sulfonated amides and imides of aromatic or aliphatic, mono-, diand polycarboxylic acids.

(6) Salts of diene condensation products, such as the sodium, ammonium or triethanolamine salts of the condensation products of abietic and maleic or fumaric acids and their esters, salts and sulfonation products.

(7 Soaps of various fatty acids such as oleic, stearic, palmitic, and those obtained from t'alloil or black liquor soap in wood pulp manufacture.

(8) Certain fatty acids and their monoor di-glycerides such as Wood soap fatty acids, glyc- 'erol mono-ricinoleate, di-glycerol oleate, etc. Sulfonated fatty acids may also be used.

(9) Sulfonated terpenes, and especially. their polymerization products and their condensation agents are more effective than are others for the emulsification of any given polybasic acid ester or mixture thereof, but all of the above classes of surface active agents possess emulsifying prop erties in greater or lesser degree.' In Example 2 I have pointed out a representative composition which produces a stable emulsion, and this will serve to'indicate the way in which the most suitable compositions can be'prepared.

The invention will be further described in conjunction with the following specific examples, which are intended to illustrate typical compositions-of the present invention and typical methods of applying them to the fibers. understood, however, that these specific compositions are given by way of example, and not by way of limitation, and that where a component of one class of materials is used in conjunction with a component of another class this is intended as representative of the classes themselves. In other words, variations and substitutions of materials falling within the classes may be made without departingfrom the, scope'of the invention, which is limited only by the scope of the claims appended hereto.

It should be I EXAMPLE 1 aaiasee The following table gives the time required to Lubricants used in the textile industries are ordinarily evaluated on the basis of their lubricating qualities, their scouring qualities or completeness of removal from the thread or fabric after spinning or weaving by the ordinary detergent methods their resistance to rancidity or oxidation and their physical and chemical constants. The constants of greatest importance are their viscosity, their cold ,test, their flash point and their resistance to auto-oxidation or spontaneous combustion which is determined by the so-called Mackey test.

In the following examples, the new lubricants of the present invention will be described in detall with reference to the above properties. order to exemplify the methods by which these properties are determined, the following tests will be described in detail with reference to simple esters of phthalic acid, using two natural nondrying oils, teaseed oil and olive oil, as standards of comparison.

FRICTION TESTS To establish a standard of. lubricating properties; the following tests were made:

A 200 gram weight was attached to one end of a thread of 36/3 grey cotton, this material being chosen in preference to a wool thread by reason of its greater uniformity. The thread was impregnated with the lubricant under test and the excess lubricant removed by drawing the thread through two tightly clamped pieces of rubber. The lubricated thread was then suspended over a glass rod and its free end was attached to a metal rod which was moved up and down by a, series of pulleys and an electrically driven motor.

The

friction of the thread moving over the glass rod eventually caused rupture, and the time required.

for this rupture of the thread was automatically recorded by a stop watch. Check tests showed that the results obtained with this apparatus are easily and closely reproducible.

Synthetic esters having the following physical and chemical constants were tested in the above described apparatus:

TABLE L-{hysical and chemical constants As a comparison, a vegetable oil was used having the following constants:

- Vis- Cold Acid Flash Lubnwnt cosity test No. point,

C'. C'. Teaseed oil C l 15 2.84 284 1 Cloudy. 1 Solid.

Dim ethyl phthalate.

' Diamyl phthalate rupture the thread in the above tus:

TABLE 2.-Frictton tests described appara- Lubricant tested Time required to rupture thread Distilled diamyl phthala Diethyl phthalate Teaseed oil Olive oil Min. Sec. Min. Sec. 6 9

HF-IH en mmcaceuu The tests indicated that diethyl phthalate was by far the best lubricant, and that diamyland dioctyl phthalates were next. All the synthetic esters were superior in lubricating valueto olive oil, which is a commonly used lubricant, and the majority of them were better than teaseed oil, which is one of the best textile lubricating oils. In view of the unusually high figure obtained with diethyl phthalate, the test with this material was repeated several times and the value obtained was found to be correct.

SOOURING TESTS Eighteen skein's of 36/3 grey cotton thread were prepared (allowing two for each ester tested) by the usual standard laboratory procedure. Each skein weighed approximately 5 grams. After drying the skeins for 2 hours at 0., they were weighed, tagged, and impregnated with the lubricant under test.

Oiling was accomplished by immersing the skein in the oil or ester for 5 minutes and then allowing the oil to drip off the skein for 24 hours. The skelns were againplaced into the oven for 2 hours at 70 C. and the quantity of the ester absorbed was determined from the difference in weight of each skein, before and after.

The skeins were placed into one pint screw cap jars containing 200 cos. of water and 2 of a 10% solution of sodium dioctyl sulfosuccinate,

which is a wetting agent having good detergent The amount of wetting agent was properties.

based on the weight of lubricant taken up by the skein. "The jars were agitated for two hours at 60 C., after which'the skeins were hung up to dry for 18 hours at room temperature and then for 2 hours at 70 C. The amount of the lubricant removed by Washing was determined by the loss in weight of each skein. tests are given in Table 3.

TABLE 3.S00urmg tests The results of these Ester used for oiling Percent of cstor removed by washing Dimethyl phthalate Teaseed oil .1:

hoomqmcacn m s s w r s r$s VBFUOWUXODFO From the above it is seen that all the phthalic esters were washed out more easily and more"7 Cotton strips .of "x12" werev extracted with tested. This was accomplished by dissolving the determined amount of oil. orester in ccs. 'of' ACCELERATED OXIDATION TESTS In order to determine the degree of resistance to oxidation, thickening and rancidity upon storage of the'lubricants of the'present invention they were subjected to an accelerated aging test in the presence of ultra was as. follows:

ether to removeall the oil and each strip was impregnatedwith 2% of its weight of theoil to be ether and pouringthe ether solution over. the

vcloth in an evaporating dish, followed by evaporating the ether. The samples of treated, cloth were then placed on asbestos boards of 5x12" and covered with black masking paper, allowing 3" of the cloth to remain exposed. The samples were then exposed to the light of a mercury arc lamp in an atmosphere saturated with water vapor at 120i F. for 72 hours. 3" of masking were removed and the 'cloth was again exposed to the ultra violet rays for another 24 hours. Another 3" were removed and a further 24 hours exposure was given. The changes in color of the treated samples were then noted and recorded as follows:

TABLE 4.Accelemted aging test- Lubricant Color after exposure Dimethyl phthalate No change in color.

- Diamyl phthalate Very slight coloration.

Dioctyl phthalate Do. Dibutyl phthalate Do. Dihexyl (methyl amyli phthalate Do. Dihutyl glycol diphthalate Slight coloration. Dihexyl (ethyl butyl) phthalete. Very slight coloration. Diethyl phthalate No change in color. Teaseed oil Distinct yellow coloration.

MACKEY TEST 7 A description of this test, and of the apparatus used in performing it, is given in A llens.C ommercial Organic Analysis, Fifth Edition, volume No. 2, pages 759-761, and the values'obtairf ed' with standard vegetable oil lubricantszare stated. The

neutralesters of phthalic acid, being completely stable, showed no temperature rise even on prolonged heating for 4-5 hours. This means that, these esters present. no fire hazard upon storage of the oiled or lubricated threads or fabrics.

EXAMPLE 2 The oiling of wool is usually performed during the mixing, in which two or more grades or colors-are blended. The wool. is spread out on a floor or table and layers of the difierent grades are sprayed as the mix is made up. In the most modern mills this is done by spraying the oil in the form of an emulsion through automatic sprayers in, connection with the mixing picker.

For satisfactory results it is necessary to have a stable emulsion, and it is an advantage of the violet light. The procedureesters of the present invention thatthey can be readily emulsified with emulsifying agents that will also promote their removal from the yarn or cloth in a subsequent. scouring or washing step.

- Such an emulsion should contain, inaddition to the lubricant and water, an emulsifying agent of the sulfonic acid type and an emulsion stabilizer such as lecithin, gum arabic, casein and the like. A typical emulsion of this type will have thefol- Such a mixture can be easily emulsified with an ordinary high speed mechanical agitator and will I remain stable indefinitely.

Instead of the sodium dioctyl sulfosuccinate in the above composition, 0.5-1.0 parts of sodium 'isopropyl naphthalene sulfonate, or of pinene phenol sulfonate, or of a higher fatty alcohol sulfate, or 0.5-2.0 parts of a highly sulfonated oil such as castor oil may be used.

EXAMPLE 3 In. addition to their valuable properties when used alone, the estersof the present invention are well suited for use in'admixture with the natural vegetable oils for the lubrication of wool, cotton,

' silk and other textiles. For example, they may be used in admixture with olive oil, coconut oil, palm oil, castor oil and the like as well as with modifled, oils suchas Turkey red oil. sulfonated olive oil, sulfonated castor oil, etc. The mixture may ..also contain mine'ral oil, although this should not be present in so great a proportion as to prevent ready removal by scouring. The improvements resulting from the admixture of esters of .phthalic acid with castor oils is shown by the following tables. Castor oil is. used as a softener in the dyeing and finishing of cot ton piece goods. It is also the base of most or the oil mordants used in printing and dyeing.

Mixtures of castor oil with the esters of organic dicarboxylic acids of the present invention may be substituted for straight blown or unblown castor oil in any of these applications.

- Grams Grims or Grams of Ester oi phthslic Yis- Acid of unblown blown acid used 1 on on cosity number 150 A-B 4.2 5Q A-B 6.8 .150 100 A-B 4.9 150 :so A-B 8.6 100 A-B 3.0 ,o 200 so A-B 6.8 Dilm'yl 176 60 A-B 3. 5 Do 210 I 50 A-B 6.3

Oils Castor oil U 10. 3 Blown castor oil 25 17.8 'Inmmad nil 0 2.3 Olive oil; B-0 1. 2

solidifying points, flash points, influence of ultra violet irradiation, lubricating and scouring properties, are givenin Table 2.

Tasu: 2

& I Tim r t a 1' 8 I0! 6X00! Cold F1881 111m.- quired to oil re- Lubmant used test, 0- 3 6 voilet rupture movedon irradithread scouring ation Gulfgem oil 13 is a low viscosity Dimetlyllphth1%lfltaitcast&roil. -ao 146 2 5 32 67.2 mineral oil with a flash point or c sgr oil R --i:.:-T -ao 147 2 e 12 64.8 and is frequently added to Diethyl phthalatHalstor 511--- -ao 1 151 a 9 so 66.1 textile lubricants. r gi 1. f?? ?f:?fi 1. f- -s0 I 156 a s 30 58.3 The ajbove figures that the Dibutyl nn lm-ci smr oil--. -so 174 2 6 45 58.6 properties of olive oil are definitely %il-??f.-ff?ilifffi?ii -so 111 2 5 50 54c improved by the addmm of the Igiiamy} plfiafitpcgistor oil--- -so 183 2 4 12 49.6 synthetic esters of the present in- 3? 3113 Brig 30 175 2 4 34 5 vention. They 8150 show giastor 011. -1 Z 4 30 45.1 such cheap materials as coconut 28? if 284 6 6 59 411 oil and lard can be mixed with the gigg 304 $3 4 synthetic esters to produce a lubricant having properties as good I In evaluation 01 stability to ultraviolet irradiation, 1 means best and 7 means pared with 161 experiments.

worst in the series.

From the above it will be noted that diethyl phthalate will more than double the lubricating value of castor oil when mixed with it in equal quantities and that it improves the scouring properties, the cold test, and other figures. Dimethyl and dibutyl phthalates produce the second best results, while improvements in the cold test and securing properties are shown by all the esters.

Each of the above mixtures, when subjected to the Mackey test, showed no temperature rise even after several hours heating. Accordingly, textiles lubricated with these mixtures are comor better than olive oil. This is the case even when the lubricants are diluted with substantial amounts .of mineral oil.

EXAMPLE4 Esters of organic dicarboxylic acids with poly- Tum: 1

" pletely stable upon storage and will present no spontaneous combustion hazard. W005. Acid Cold The color of cotton cloth impregnated with the ity gg' test above mixtures and exposed to ultraviolet light as in Example 1 indicated that they show much Glycol ole-ate phthalate' 2mm O m 5 25 less discoloration than castor oil, blown castor 011, Teaseed oil, 1 mol teaseed oil or olive oil. Cloth impregnated with gggggfg ffgg Ef fff Ef 'f E 5.7 -e0 castor oil alone became considerably darker after G yco p ggte oleate, G irradiation and developed a distinct odor of Dwleylpht rancidity.

The use of the esters of the present invention in admixture with other standard lubricants 0! natural origin is shown by the following.

' Tenn: 3

- Lubriea- Percent v o sitio Viscosity Add Flash o ld test Egg: lge l o 11 oznpo ll num- 0 requ move be! point ag: rupture on washthread ing on 11 333grams 22C 1 a va 0 c 011 y. gl y i l' gg F5 seo .so 171 1g i g 1 4 48 45.40 1L yo 0 ems c on y. Diamylphtha%te,66.7grams -so O.solid. 2 6 38 37-45 giliioonulili (g3 A 6.3 203 5053431212 Cd.-. 1 4 10 35.0 1

V60 grams 0011 Y. ws fgg 661mm }16 see... so 191 q Solid} 1 4 02 21.2 1L

gms. 60 gms. dibutyl glycol diphthalate. 5 C. cloudy 5o grns.dibutylphtlialate 153m" '4 --ao= C.solld 1 5 1 12.5gms. gem oi B 1.25 gms. d BOgms. dibutyl glycol dipli a 5.64 173 Solid at -25 0. 1 6 32 50.2 2 :7l(ologms. dibutyl 1113 gms. coconu o 30gms.dibuty1glylccldiphthalate. 16.8 sec.. 5.62 172 {i122 8- 1 4 2o 4 52.7 1L zaogmadibutylp thalate A-19.8 sec. B-zm sec.

A few representative complex.

l 213,369" v 7 The results or tests outlined in Example 1- are which is then esterifled with the dior polycaras toliows: v boxylic acid. Similarly, in the case of esters or Tum: 2 I aromatic alcohols or phenols, the excess hydroxy nub c0101! ab Time w Percent groups may be attached to the aromatic nucleus 6 v Lummt I paint 1mm 'quiredto oil reas for exampleindimethoxy phenoxyethyl male- 5 9 c. diction 1 :22; 2,153 ate or fumarate. In some cases ether groups will T2mo 2&1 3- 5 4 the diethylene glycol phthalate resin described l in Eh-rample 6 as Resin B. l

meaty] mono. 4 A simpler method of improving the scouring 10 my 01m phmmb' Mm Sm serve the same purpose, an example or'this being is I Tph holate, 50% 202- 1 4 1s amlml phthmg-bii; I I value is to use the polyhydric alcohol esters in oi m 2 6 I50 I 649 admixture w1th esters or mono-hydric alcohols ififl I I v that already have goodjscouring values. Table 1 l I I Teaseodo 284 7 :0 59 I 4o.,o shows the results obtained I when the two onve 304 -7 15 methods are v I, I

' TABLE 1 i I Q i Calor Pelrcent C l Acid 1 8 er 1 1 cl reoor 1 Flash Lubrica- 1 0 it! 1 1 v l t um- Co d test ir ad 1 i moved of 011 I ompos on I I scosi y li point anon tionvalue 0? Wash A1 Q I 1 lug y '30 ts.in1oldlgl col hthalate oleate+imol diole l C. Min. Sec.

p thalic glyceri enfn 151; sec. 2.3 ms {ggggg eg 2 1 50 67.5 lL 70-pts.dibutylphtha1ate l v v Y i 20 pits-k110i diglycol phthal'ate oleatc+imol di leyl 25 p m ic glyceride 6 1w:- 172 W 2 a 12 c2 7 lL g0 pts.dibutlyl phthalatc SO(i1ig(-116"1(g s.-mono- B O ygggs Amt? 1 t f 1 l 13.1sec. 1.9 169 {g 1 3 $g 2 4 09 63.2 1L

.mon0-aury es ero co o gg z ifl yl1 g iiyfi f }l3.5 sec. 2.5 164 o 2 5 o 61.1 11. 2

5. me ox enoxye umara c wgtkdmmp 5 }i 116 Clear 0 1 1 58 2 30 N0te.-l means best color and 7 means. worst EXAMPIEIG I color. These resaultts showngie r I1I t In addition to the simple physical admixture movement in s 1 5 3 a: of the esters of the present invention with non- 85 donation that :5 fi w h 5 drying oil as illustrated in Example 3, it is pos- V organ c polycar1 xy 0 g 33 ydr c sible to u lize these materials in chemical comalcohols are adm xed 1t vegetab e 01 s as bination with each other in the form of oil moditeaseed on and Olive fied resins. This constitutes an important fea- 40 v ture of the present invention because the tend I EXAMPLE 5 ency of many of the natural oils to discolor and to ignite spontaneously upon storage of 3 the The scou in p p e of t lubricants of 1 lubricated textiles is thereby overcome. In other the p s invention can b i v d by i words a lubricant such as castor oil which dis- Dora-ting therein an excess f y y groups colors badly (see Example 3, Table 2) becomes over and above ose necessary for esterification almost completely resistant to discoloration when 01 the p ycarboxylic acid used n their used in the, form of a long oil alkyd resin. p p es excess y Q y up y For example, a castor oil modified alkyd resin be present in uncombined form as, for example, of 1000 oil length is prepared by heating together in the mono-acid esters oi glycol or glycerol, or 148 parts of phthalic anhydride, 100 parts they may be esterifiedwith moriobasic acids such .glycerol and 1000 parts of castor oil. The tem- 50 as oleic acid, ricinoleic acid, or other] acids reperature is raised over a period of two hours to sulting from the saponiflcation of coconut oil, 200 C. with continuous agitation in an at- I olive oil, palm oil, teaseed oil or other similar mosphere of carbon dioxide and held at thisfigure 5 vegetable oils. Such compounds can easily be for '7 hours or until an acidnumber of 3.6 is obprepared by reacting the natural fats or oils with tained. In Table 1 this is designated as Resin A;

excess glycerine to form the monoor diglyceride, The results obtained are as Iolows:

TABLE 1 I v Color Percent 7 Acid 6o Compmmm c s i ty it??? com ir r a ia- 3121 3? mgzl e d on gi l of v 1 I tion washing 0 m A h c. Min. Sec.

- mam -s 0 05 152 pts.-dibutyl phthalate A 2.4 173 a a 12 73.0 1L

10 pts.-di-stearyl di-glycery Wm M 0 i ts 'u a'ii t l hth l te u I v viscous t 5 C t uy p as a 10 p t .s.-di-(glyoeryl monosteamte) mono-phthal- A 173 Waxy at l0 0 3 7 15 oo ater-resin A 150 pts.dibutyl phthulateu I A 2. 3 173 Clear liquid at 15 0.. 4 6 52 68. 5 1L 7 1x8 ptisr-crzsts lolfixanol stearate- I s.- n 140 pts.'dibutyl phthaiatc B 1. 5 173 Waxy at 15 C .2 7 12 84. 6 1L linptstrsodirnkdioctyl suliosuccinate.

.re: 11 lw ptn-dibutyl mnuuteu B I 3 1 e" at v 1 6 51 t IL Norm-Sodium dioctyi suliosuccinnte combines th e properties (ii a lubricant and a wetting agent 15 The last two columns of Table 1 illustrate another feature of the invention, namely, the use of esters of suifonated dicarboxylic acids. A

comparison of the figures will show that the ad- Instead of castor oil, other lubricants of natural origin may be employed in the form of oil modified resins. A coconut oil modified alkyd resin giving good results may be prepared as follows: 3

A mixture of 203 parts phthalic anhydride, 154 parts diethylene glycol and 1375 parts coconut oil. are heated during 1 hours to 220 C. in an atmosphere of CO2 and held for an acid number of 30. 90 parts of N-butyl carbinol are added and the temperature maintained at 180-210 C. for 13 hours after which time a resin having an acid number of 17 is obtained. In Table 2 this is designated as Resin B.

The use of resins containing less oil is illustrated by the following formulation:

148 parts phthalic anhydride, 80 parts glycerol and 200 parts castor oil are reacted over the same cooking schedule as Resin A in an atmosphere of C02. The product has an acid number of 8 and a viscosity of V-V in 50% xylol solution; they have no tendency toward spontaneous combustion and present no fire hazard when textiles lubricated with them are stored.

What I claim is: v

1. A method of lubricating textiles which comprises contacting them with a lubricant comprising an ester of phthalic acid with a monohydric alcohol and a member of the class consisting of non-drying higher fatty acids and glycerides of non-drying higher fatty acids. v

2. A method of lubricating textiles which com,- prises contacting them with a lubricant comprising an ester of an aromatic polycarboxylic acid selected from the group consisting of phthalic acid, phthalic anhydrida'substituted phthalic acid and substituted phthalic anhydride with a monohydric alcohol. r

3. A method of lubricating textile filaments which comprises contacting them with a lubricant containing a resin comprising the reaction product of phthalic anhydride, a polyhydri'c alcohol, and a quantity of a non-drying oil greater than the amount of the other two constituents.

4. A method of lubricating textile filaments,

which comprises contacting them with a lubricant'containing a polyhydric alcohol ester 01' an organic polycarboxylic acid together with a monohydric alcohol ester of a phthalic acid.

.5. A method of lubricating textiles which comtion. In Table 2 it is designated Resin C. prises contacting them with a lubricant contain- TABLE 2 Percent vColor Acid oil re- Flash after Lnbrica- Color Composition Viscosity n31.311- pomt Cold test mud on value 03187:? on 7 tion I mg 30 ta 1 B 01 d 15 0 p .--reSn ou yg8 tg ggg }14.2 sec. Ford cup N0. 4 5. 7 170 i lg oo C 2 s as 50.1 2L p n ou y- I 53 gt g g g o phthame }14.5 sec. Ford cup No. 4 as 170 u -3o C 2 a s7 7 cu 1L e V. V 500118 7 ggMg-dibgzy phthalata 3 173 Semi-solid --25 0. 3 22 p .res ggpsamg phthalm }I 2.9 178 do 2 14 03 55.6 1L

p .resm 200 tgts-dibutyl phthal- }A 2. 9 174 Clear and viscous 30 O 1 7 51 42.1 1L

No Mackey test figures are shown in the above tables because none of the materials showed any temperature rise, even after prolonged heating. This is true of all the esters of the present inven- ALPHONS O. JAEGER.