US2313727A - Compositions and method of preparing and applying same - Google Patents

Description

March 16, 1943. E.c. A'rwELL COMPOSITIONS AND METHOD OF PREPARING AND APPLYING SAME Original Filed Feb. l0, 1938 .Ewe707 Fverew new zz,

Patented Mar. 16, 1943 COMPOSITIONS Es l.PirrlazN'r AND METHOD oF PREPAR- OFFICE ING'AND APPLYING SAME Everett c. atwell, Cranston, a. I., mignon` to Atlantic Rayon Corporation, Providence, It. I., a corporation of Rhode Island Original application February 10, 1938, Serial No. 189,795. Divided and this application June 10, 1939, Serial No. 278,483 o 15 Claims. (Cl. 117-176) This inventionl relates to aV physically and chemically resistant composition for impregnating and/or coating surfaces and to a method for the preparation and application of the same.

Some surfaces to which a coating is to be applied are neither soft nor rigid, but more or less resilient. With such surfaces or materials, itis necessary that the coating compositions applied to them shall be capable of exhibiting at least the same ora greater degree `of resiliency than the surface ofthe body material, especially when `.the coated surface is to be subjected to flexing.- Y In such cases, the adhesion of the coating to the surface must'also be capable of withstanding the stressesand strains set up between them by the flexion of the composite surface coating layer. The'coating must also be strong or tough enough to withstand the lateral tensions or compressions -transmitted throughout its surface when under such strains without disruption of its structural continuity;

0n the other hand, it is desirable that the coating, after having been applied, should set to a firm, or even hard but resilient consistency,

`adapted to the coating of metal and other rigid` surfaces for protection from water and various chemicaltsolutions to which they mightbe subjected, comprising for example certain aqueous solutions of inorganic acids, alkalies and salts as well as many organic liquids, their particular 'value is further exemplified in the adhesion,

strength, resiliency and exibility which they 'impart to cellulosic materials. Y

Atypical surface whichpresents certain of the conditions above set forth and to which the present invention is particularly applicable is found on the tubes whichare employed as1 supports for the retention of natural and synthetic yarns during the process of purilcatiomrdyeing and other A'fluid treatments of the same *inY package form.

A package is comprised of yarn and a. supportto hold or retain yarn wound thereon, preparatory to subsequent treatments in the mill as well as `for inspection, shipping to and use of the/yam by the weaver, knitter or other ultimate user, directly from said package. The supports may be constituted of certain metals, of momes thermo-v setting resins, of glass or ceramics, or they may be of cellulosic materials impregnated or coated with various materials. 'Ihey may be made in various forms such as springs or in perforated hollow cylinders of either plain or congurated design and having either smooth or embossed surfaces. The spring supports are of course limited to metal construction whereas the perforated hollow cylinders or tubes may be made with other classes of materials as above mentioned.

In the fluid and other treatments of yarn in such package form the supports for the yarn are subjected to various chemical and physical conditions according tothe treatment and process employed in treating the yarn. It is therefore necessary that the tubes-and surfaces thereof be of such character that they remain substantially unchanged throughout these various treatments and steps.

In the normal succession of operations for dyeing yarn in package form, the tubes are mounted on the rotatable spindle of a winding machine and the yarn is wound thereon under controlled tension and usually in cross wind formation and to the desired size or weight. One or more of the thus formed yarn packages are then mounted on a perforated spindle having a diameter .slightly less than theinside diameter of the tube. In order to prevent the flow of liquid out at the top of the spindle or bet-Ween the annular space between'the spindlen and the tube, a tight fitting cap, having a diameter in excess o f that of 'the i outside diameter of the tube, is secured to the top of the spindle, thereby simultaneously sealing the annular opening at the top of the uppermost package as above described and at the same time causing the ends ofthe other tubes to likewise form a liquid seal between their respective end surfaces or between circular washers inserted between each of the packages. In order to make these liquid seals tight and fully effective it is necessary to apply considerable axial pressure to the column of tubes through means provided for the same in the design of the cap and of the spindle top. Itis therefore a requirement that such tubes shall be capable of withstanding such axial pressure during either dry or wet treatment of the yarn while assembled on the spindles.

The spindles, containing one or a plurality of such packages are connected at thebase to the delivery side of a pump in a circulatory dyeing in the spinale and then through those 1n the tube whence the Aiiuids enter and ow throughv maintain a high pressure on the delivery side of I the. recirculating pump. This imposes the requirement on the tubes and coating thereof that they must withstand in ,the wet state the stresses and strains accompanying such fluid pressure.

Certain types of yarn, and more particularly the viscose type of rayon yarn, swell to a considerable extent when wet with aqueous liquids.

The confinement of the yarn on the tube by the tube itself results in the development of pressure against the surface of the tube imposing a further requirement that the tubes have sufficient wet strength to with-stand deformation from this source.

Yarns are commonly dyed with any one of several different classes of dyes each employing in their application various auxiliary chemicals. Representative of these classes are direct, diazotized and developed, acid, vat, naphthcl, and sulfur dyes. 'I'hese and auxiliary chemicals, and approximate concentrations used, together with the conditions of time and temperature at which they may be employed must also be withstood by the dye tubes.

Itis therefore a requirement that the composlv tion of this invention and more particularly paper tubes impregnated and coated with the same shall not be substantaly deteriorated by the conditions or treatments as above set forth and that they withstand the stresses and strains set up by shock from alternate hot and cold aqueous baths.

Following the dyeing operation described above, the packages are preferably subjected to centrifugal action by rotating the packages at high speed, whereby the uids held loosely in the interstices 'of the yarn are thrown off. 'I'he remaining water retained by absorption within the fibers of the yarn is afterward removed by drying in an atmosphere of air at elevated temperature and low relative humidity. 'I'hus the tubes and coating thereon must be able to withstand the tremendous unbalanced forces imposed upon them in the centrifuging in a wet state as Ywell as to resist becoming brittle and to resist the development of plastic flow and printing during the prolonged heating of the drying process; that zis to say, the tendency at the elevated temperature of the dye bath and drying chamber for the coating to soften and the yarn, which swells i during the processing, to cut into the coating and embed itself in the surface illm during dyeing and drying operations, and become adherent thereto upon cooling. Inspection and wrapping follow next in order. Practice has demonstrated that the yarn on the individual packages are least disturbed in shipping when they are packed in a horizontal position. It follows therefore` that a still further requirement is imposed on such tubes that they must withstand the transverse, pressures imposed on them in packing Vand shipping in cases without appreciable permanent distortion or collapsing. 1 For reasons of economy it is obviously desirable to provide a perforated tube for the support` of yarn in package form which will stand repeated use for the types of dye baths mentioned herein and other. fluid treatments of the yarn thereon, Y

Many metal and molded thermo-setting resins fulnll the various requirements set forth above. However, their cost is high resulting in excessive capital tied upin inventory of tubes. 'I'heir much greater weight over that of impregnated paper tubes results in much higher shipping charges per pound of yarn. l

It is thus readily seen that the much cheaper and lighter weight impregnated paper tubes are to be preferred provided they are of such characteras to withstand repeated use for dyeing and other fluid or dry treatments of yarn in package form.

Impregnated or coated, perforated paper base dye tubes heretofore available are not satisfactory for repeated'use in dyeing. Someare of low wet strength, some are brittle and shatter in handling and shipping, whilesome are not resistant to chemicals. But the predominant undesirable feature which makes these tubes'unsatis- `factory for reuse is associated with their charfor use. Attempts to avoid this trouble in other ways as by using a given tube repeatedly for one color only is impractical due to the vast numbers of shades dyed. It is likewise impractical to attempt to sort the empty tubes upon their return from the customer (weaver, knitter, et al.)'. Some manufacturers of tubes have attempted to meet this condition with a more thorough coating of i the tube with a resinous composition but in so doing have been confronted with other undesirable features imparted to the tubes which are Iassociated with the characteristics of the resin itself. That is, in so doing, the initial water absorption may be very appreciably reduced but the resin coatings are so decient in flexibility that they crack readily in normal handling and use allowing the dye lliquor to penetrate and affording a potential source of trouble from staining as well as for catching and disrupting the filaments of ne denier yarns. 'I'he coating on some are removed in certain of the dyeing and treating baths.

It is therefore a. general object of the present invention to provide a suitable composition to serve such purposes, and a method of applying it to such materials and surfaces to promote (structural strength and provide a protective coating having the properties above described.

It is a further and more particular object of the invention to provide a. coating composition and coating for cellulosic containers or supports, such as dye tubes for package dyeing or other iiuid treatments of yarn, and the like, whichA 2,313,727 l'from one dyeing operation and thereby intertering with subsequent dyeing operations.

@iis a further object to provide a coating composition which, when properly applied to a laminated,- perforated paper dye tube, will provide a satisfactory dry crushing strength and an improved wet lcrushing strength, preferably equal to the dry crushing strength of the same tube. It is also an object to provide a resilient tube for dyeing yarn in package form having a smooth, continuous surface which will withstand normal handling without cracking andV which will: not have sufllcient plastic owJto cause printing Other more particular objects with respect to such supports for yarn and the like will appear from the following disclosure.

In accordance with this invention it is found that a new and unique resinous impregnating and coating composition is produced through the separate formation, development, and subsehydric alcohol they are more frequently modified by the presence of organic acid. The alkyd resins of this invention are particularly charac- .terized by being modified in the esteriiicati'on process by unsaturated fatty acids-or glycerides of drying or semi-drying oils of either natural quent mixing in a mutual solvent, of two distinct types of synthetic resins-namely, alkyd resin (which may be esteriiied and developed in the presence of a drying oil unsaturated acid),` and a reactive dialcohol phenol resin, which Will be described below.

It is also found that the alkyd resin may be prepared in part inthepresence of an already prepared, partially condensed, reactive dialcohol vphenol resin and that the resulting product while stillsoluble may be dissolved in admlxture with additional solution of a separately prepared reactive dialcohol phenol resin to produce a suitable composition to serve effectively for impregnating and coating in accordance with this invention.

It is further and more particularly discovered as a part of the present invention that compositions as thus formed, are especially adaptable as compositions for the impregnation'and coating of resilient' materials or surfaces such as cellulosic dye tubes, and present the desirable characteristics indicated above. 'I'hat is, they are highly satisfactory for application to the surfaces and the porous internal structure of iirm'but resilient substances,`to protect the same,

or synthetic origin, for example, unsaturated fatty or monobasic acids or glycerides thereof suchjas linoleic, linolenic, eleostearic. clupanodonic, and other similar unsaturated hydroxy acids. Suitable compositions of this character may be prepared inraccordance with the procedure set forth in United States Patent No. 1,800,296, dated April 14, 1931, to Herbert Hnel (see Example 1'1).rv

VWhile phenolic resins in a generic sense are the condensation products of monohydric phenols with an aldehyde, the phenolic resin of this invention is characterized more particularly as the alkaline condensation product of formaldehydel or paraldehyde with phenol substituted preferably in the reactive para position only. As substituents in such reactive positions butyl and ,amyl radicals are typical and satisfactory, as in p-tertiary butyl phenol and p-tertiary amyl phenol. Suitable compositions of this character and provide a smooth, continuous surface thereon having the combined qualifications and propertiesv which have heretofore been diilicult if i,

not impossible to secure with cellulosic dye tubes of thev prior art.

A representative example of the application of the present invention will be described with reference to the impregnation and/or coating,r of hollow, cylindrical, perforated, cellulosic tubes which are intended for use as supports for yarn in the dry 'and fluid treatment of the same in package form. 'I'he compositions herein described may be used especially satisfactorily both to impregnate and to coat such fibrous cellulosic dye tubes. On the other hand, it is to be understood that the tubes may be first impregnated withother suitable stiiening agents, so long as they impart strength to the tube without making it weak or brittle and without rendering the surfaces of the tube, as thus impregnated, repellant to or undesirably reactive upon the compositions herein described. The compositions ot this invention may then be applied to the surfaces of the impregnated dye tube, in accordance with the following disclosure, and will provide a satisfactory surface thereon.

While in general alkyd resins are prepared by the esterication of a polybasic acid with!!l polymay be prepared in .accordance with the procedure set forth in United States Patent No. 1,996,069, dated April 2, 1935, to Herbert Hnel (see Example 3). A

The composition of this invention is prepared by conducting the preparation ofthe two resin components independently part way, dissolving, and then mixing the stillv potentially reactive materials in solution. Inthis condition the res,- ins remain substantially inert over long periods of time. ,The resin mixture in solvent medium is applied to the material to be impregnated or coated, the solvent removed, and the coated materials heated for sufficient time and temperature to eii'ect the reaction of the resin mass until it is converted to the insoluble and infusible state and attains the desired physical and chemical characteristics. 'I'he time and the temperatur'eto which the mass is subjected in each case will determine the degree of reaction effected and the properties developed in it but should not be so high or so long as to impair the strength of the cellulosic materials of the tube. Increased time or temperature both act independently and collectively to increase the hardness,.water impermeability, chemical resistance, insolubility, and resistance to' plastic flow `or printing of the resin mass upon Asubsequent cooling;

It is not possible to prepare any of the mixtures coming within the scope'of this invention by mixing the ingredients of the two resin masses in the kettle and preparing it simultaneously. While'it is possible to chill back the separately and partially reacted alkyd resin with separately and partially condensed or polymerized pure di-aleoholz phenol resin and thus simultaneously produce a phenolmodied alkyd resin thereby,'there The methud f the invention, that is, the indepegdent preparation of the two resin compone ts to a certain stage (i. e., with or without addition to the alkyd component) and dissolving in solvent, mixing in the proportion required, ap-

plication of the resulting `composition to the arpregnation of cellulosic dye tubes or the like with the desired composition and properties.

It is further found that the independently prepared resins if used alone for the purposes of this invention are not satisfactory and have entirely different properties than that produced by mixtures of the two within the limits specified below.

For example, the alkyd resin 'component may be prepared by esterifying together an oxidizable (unsaturated or drying ou) fatty acid g., 3 parts by weight), phthalic anhydride (e. g., 4 parts by weight) and glycerine (e. g., 2 parts by weight) by heating to about 240 C. andkeeplng the reaction'mixture at that temperature until the desired viscosity is obtained. Ihis point may be ascertained by removing from time ,to time and dissolving a sample of the mixture in a given proportion of solvent and determining the viscosity of the resulting solution.

As soon as the desired point is reached, which must of course be short of that at which the reaction product becomes insoluble or produces a solution so viscous as to impede molecular association (e. g... a viscosity of 378 centipoises at ,80 F. in a 50% solution in xylol in the above example represents a satisfactory final stage)- the temperature is promptly lowered and further development of this reaction is arrested. This may be effected in any convenient manner, as by mechanical cooling, without change in the composition, by admixture with a solvent (in a kettle l provided with a reflux condenser) by the addition of chill-back materials such as a rosin-modifled dialcohol phenol resin which has been separately prepared, as herein described under IllI, or by bodied drying oils. Substantially any proportion of these compositions may be added. (For example 2 parts of the resin-modied dialcohol phenol resin to 9 parts of the alkyd composition above described.) Pure dialcohol phenol resin may be added at this stage, but in this case the proportion of pure phenolic component which can be added to the alkyd resin is limited, and should not exceed l5 parts of the pure phenolic solids .to 85 parts of the alkyd resin, as above mentioned.

'Ihe reaction batch of the combined resin components is then pumped into an equal weight of a solvent liquid-such as xylol, hydrogenated naphtha, etc., and dissolved therein.

The unsaturated or drying fatty acid, may be perilla oil acid, which is preferred, or a mixture of linseed oil acids (2 parts) and Chinawood oil acids (1 part) may be used; also, soya bean oil fatty acid and linseed oil fatty acid alone, as well as certain oxidizable fish oil acids. The fatty acids thus used are characteristically unsaturated, oxidizable acids. While such oxidation is only slight, under conditions of procby this invention, it is of suillcient extent to initiate the fundamental reactions which are subsequently those of condensation andthe interchange of acid radicals'to form chemically lity to absorb oxygen. Hence the iodine value of the oils from which these fatty acids are derived serves as a measure of `ftheir reactivity with the dialcohol phenol resin. An iodine value of about appears to be the lower limit of the corresponding oil, in order for a fatty acid to be suitable in this respect, and fatty acids from oils of higherv iodine values are preferred.

The product as above obtained (with perilla oil fatty acid) exhibited the following properties: In 8.150% solution in xylol: Sp. gr. 0.992; acid nurnber 13 to 18, immiscible withoils and varnishes. Bakes to a hard final-condensation product in one-half to two hours at 150 to 250 F. Will tolerate the addition of petroleum solvents (that is, high boiling, aliphatic hydrocarbons), to its solutions, without causing separation, to the extent to about 60%.

vshould be oil solubility, heat hardening, and reactivity With unsaturated oil and resin acids at elevated temperatures.

For example, p-tertiary butyl phenol (e. g., 150 parts by weight) may be mixed with a formaldehyde solution (e. g. 150 parts by weight of a 40% solution) in approximately the proportions of 2 molecules of formaldehyde to 1 molecule of paratertiary butyl phenol, and caustic soda solution (e. g.f75 parts of a 3N solution in'water) and the mixture maintained at 50 to 55 C. for 24 hours. Then hydrochloric acid (10 parts) whereby the condensation product of the p-tertiary butyl phenol and formaldehyde -is precipitated. The oily condensation product, after being separated from the supernatant water, is

condensed further by heating gently for 3 to 4 hours at to 150 C.,`whereupon it resinifes.

Para-tertiary amyl phenol may be used as a satisfactory substitute for p-tertlary butyl phenol, but while some higher alkyl substituted phenols may be used such as those of octyl and phenyl alcohols, which are soluble but which are not so satisfactory because they form dark-colored products, and are not so mobile or reactive in the curing process.

Typically, the composition prepared with' p-tertiary butyl phenol as above 'described manifests the following/properties: The resin itself has .a sp. vgr. of 1.099,' an initial melting range of v140 to.175 F., either alone or `in oils and has an acid number between 12 and 60. It imparts excellent resistance to abrasion, water and weather and is lcompletely soluble in the cold in aromatic and aliphatic hydrocarbon (toluol, xylol, petroleum ,naphtha, etc.) turpentine and drying cih, but is insoluble in alcohol. On vthe other hand this pure phenolic resin alone is insuiiiciently filmforming, is brittle, of low resistance to abrasion,

vhas low crushing strength and low distensibility and` due to the fact that it forms a discontinuous is added,

nim cracks readily it will permit water to vpenetrate readily therethrough if used alone as ester gum with 30 parts of the pure phenolic resin, prepared as just described (under II) at 375 vIl'. until the resin mixture is homogeneous, and then carrying the temperature up to 525 F., until the `formation of foam subsides. The batch is then allowed to cool down to room temperature, when it is ready for use as above described under I. Upon addition to the alkyd resin it may react further to some extent to form molecular complexes.

Neither the' straight nor the co-condensed, kettle-prepared, phenol-modified alkyd resin nor the pure phenolic resin is suitable alone for fully carrying out the objects or purposes of this invention. However, the combination of the two resins, in solution in an appropriate solvent or solvents, such as xylol,` (and of an appropriate consistency, as when diluted to a. viscosity of not more than 160 centipoises) not only serves to combine desirable properties and to eliminate undesirable properties of each alone, but also is readily applied and imparts characteristics not given by either resin alone, nor obtained by mixtures containing extreme proportions of either.

For example, the composite phenol-modified alkyd resin alone'containing even the maximum 'phenol formaldehyde ratio which can be incorporated and handled successfully by the method of Example I will exhibit the characteristics on dye tubes of good flexibility, and good adhesion inthe dry state and freedom from printing. However, other predominant characteristicsV such as low dry and wet crushing strength, high absorption of aqueous liquors, poor alkali resistance and reduced adhesion onprolonged immersion in hot aqueous baths made them unsuitable for use alone for carrying out the objects and purposes of this invention.

The pure dialcohol phenol resin (underExample II) is totally unaffected by, dyes, water or even mild acid and alkaline baths. But due to its extreme brittleness the hardened iilm on tubes craze badly and chip or flake oil". These vcracks or craze marks are so extensive that the coating immersion. Furthermore, the alkali, water and dye resistance all decrease withincreasing proportions of drying oils. It is also diicult to completely oxidize or polymerize all of the drying oils contained within a thick, brous structure. This mobile, unoxidized oil tends to sweat to the surface of the tube during dyeing and dry- `ing of the yarn which of course spoils the yarn in contact therewith.

By combining the resins prepared as above described and in the proper proportions, in solution, a composition having the desiredsproperties and producing a coating meeting the exacting requirements above set forth is obtained. Thus', in use yas a coating on cellulosic tubes for supports in the dyeing and other fluid treatments of yarn in package form such composition is resistant to the penetration of aqueous dye baths, either hot or cold (e. g., at temperatures up to 190 F.)

whether neutral, acid or mildly alkaline, unaffected by oxidizing and reducing baths, and resistant to dyeing by the classes of dyestuifs hereinbefore set forth. Compositions containing approximately '15% to 15% of the modified alkyd resin component and 25% to 85% of the phenol formaldehyde resin component by weight, are found to be satisfactory for the purposes of this invention. Approximately equal proportionsv exemplify an especially suitable ratio of these components.

scribed phenol formaldehyde resin (II) xylol. 400 parts by Weight of xylol.

at 50% concentration in Total- 1000 parts by Weight containing 300 parts of resin solids and ,'700 parts of xylol.

'I'he amount `of solvent used may be varied to permit of obtaining a resulting solution of deis discontinuous, thereby allowing dye solution 'u and other aqueous liquors to enter the tube. The dry and wet crushing strengths of cellulosic dye tubes treated therewith are lower than those impregnated with'the composition of this invention.

'I'he phenolic resin impregnated and coated tubes are in fact so lacking in flexibility that many shatter in normal use. Thus in spite of the inertness of this resin it likewise is not suitable alone for the objects and purposes of this invention.

Attempts to produce baking varnishes by utilizing the desirable features of the phenolic resin and overcoming the brittleness and discontinuity of the resin illm by reacting the same in admixture with drying oils, particularly China-wood oil, also have not met with complete success. The presence of the oils reduces the lm strength and impart a tendency to peel upon prolonged sired consistencyl for optimum application as an impregnant or as a coating, as the case may be. 'I'he precise amount is not critical. Solvents other than xylol or mixtures of solvents may be used or diluent may be added for the purpose of controlling the volatility, cost, etc., of the solvent media. Care must, of course, be exercised in the use of diluents so as to avoid adding more diluent than the particular mixture will tolerate; otherwise, the resin is thrown out of solution by the diluent and the solution will become turbid or opaque.

In the preparation of the alkyd resin composition, under I above, instead of chilling back the batch with the rosin-modied phenolic resin as there described, and also instead of the fatty acid a partly heat-bodied oxidizable oil may be employed. For example, one part of soya bean oil, or more may be used (V, see below) or l to 2 parts'of linseed oil (VI, see below)A inthe formula there given. The iodine value of linseed oil varies from to 180 while that of soya 6 bean oil exhibits values of 130 to 165. ,If the oil is a good drying oil more can be used, if a ypoor drying oil, less. It will be observed that in such compositions' the alkyd resin component thus obtained has a zero phenolic resin content.

By using the mixture obtained by dissolving such an alkyd resine-free from .phenolic resin content-with a pure di'alcohol phenol resin in a common solvent and impregnating a cellulosic dyeing tube or.the like therewith, evaporating The resulting product is especially characterized by presenting a continuous, 'substantially impermeable, impenetrable surface, uniformly and securely attached to the surface of the treated article to which it is applied-which is ,also

resistant to aqueous dye baths and normally active and reactive aqueous solutions such as hot,

' neutral, acid, or mildly alkaline solutionsf When the solvent and heating the resulting residual l resin mixture, a very satisfactory tube is produced. In such procedure, three reactions may v take place during the baking step. In the iirst case, the pure dialcohol phenol resin may combine to form larger molecules, by, condensation with themselves, thus imparting to the iilm the highest degree of water resistance and greater chemical resistance topalkalies and acids. Or,- the dialcohols may combine with the pure alkyd resin, so that two hydroxyl groups of one phenolic resin unit link together two of the resin molecules, thereby forming larger and more inert, chemically and water-resistant molecules. 'Ihe third reaction is the polymerization of the pure alkyd resin. The degree to which each of these reactions predominates will be determined by the relative proportion of the reagents in the composition. The water resistance, hardness, distensibility, abrasion resistance, and tensile strength will be also affected by the proportions of each of these resins present. Characteristics v of the film containing high proportions of the alkyd resin will be low water resistance, poor alkali resistance and high distensibility, as already discussed. Likewise, films containing high proportions of the pure phenolic resin are char acterized by brittleness, poor abrasion resistance,

- and high hydrolysis resistance.

The solution, as suitably prepared in accordance with the above compositions and procedures, may be applied -to some Iarticles in the usual manner as by spraying, brushing, dipping or vacuum impregnating. However, in the application to cellulosic'dye tubes or the like it is usually advisable to utilize solutions of the highest solids conthe material to be treated is permeable or porous,- as in the case of cellulosic dye tubes, the liquid composition penetrates through the surface, en-

ters the interior structure and displaces air and other gases, moisture, etc., contained in the interior of such structures. -Moreoven even lamin-ated or vporous edges or other surfaces are uniformly coated and rendered impermeable and impenetrable to the dye liquor. Furthermore, the surface of the coating and the coating .as a whole are hard and resistant lto becoming plastic or tacky and to "printing by the yarn wound thereon, even at high temperatures and yarnA pressures developed through swelling of the yarn, but is nevertheless resilient, elastic and tough 'against structural deformation of the cylinder or of the coating or outer surface and imparts a considerable degree of strength thereto. The surface of the coating is smooth and hard so that the winding and dyeing operations neither inned point of failure. The treated tubes likewise,

tent at a working viscosity and` hence to apply the solution in such a manner that it will replace as far as possible any air contained within the tube structure. This may be done by vacuum impregnation, partial vacuum impregnation or by simple immersion. It has been found that an eincient and practical method of obtaining a lpartial vacuum impregnation without the use of vacuum equipment is obtained by first heating the tubes for the dual purpose of eliminating the natural moisture in the fibers and decreasing the weight of air in the tube through expansion. The tubes while still hot are immersed in a relatively colder impregnating bath whereby .the chilling of the hot air in, the tubes causes a partial vacuum and produces the initial rapid entrance of the impregnating liquid. More than one treatment may be employed, depending upon the results desired, the condition of the material and surface of the article and the solids content resin constituents to become insoluble, infusible,

print free, hard and resilient.

upon ultimate crushing, show no clearly defined point of failure, thus indicating the flexibility and toughness ofthe coatings and of the integration of the coatings with the tubes. Results obtained with such dye/tubes by varying the compositions, proportions, and procedures followed are, indicated in the accompanying table in which the rst column gives an identifying number for each solution used; the second column the amount of a 50%- solutionof alkyd resin composition (I) dissolved in xylol and containing perilla as the fatty acid; column three, the amountof a 50% resin solution, dissolved in xylol, of resin composition (V) (like I, containing no rosin-modied phenolic resin, but bodied soya bean oil instead of it); column four, the amount of a 45% resin solution, dissolved in xylol, of resin composition VI (like No. I containing no rosin-modiiied phenolic resin but bodied linseed oil in place of it); column five,- theyamount of a 50% solution dissolved in xylol, of resin composition II; column six, the percentage of phenol aldehyde resin contained in thealkyd resin component; column seven, the total amount of phenol aldehyde resin in the coating composition used; column eight, the percentage of solids in the impregnating solution, as used; column nine, the weight of baked solids deposited upon a dye tube by three successive impregnations (and bakings); column ten, the dry crushing strength; and column eleven, the crushing strength after immersion in water forone hour at F. of the impregnated and coated dye tubes; column twelve, the amount of water absorbed by a treatfor one hour column thirteen, the effect of dyes to stain the tubes; and column fourteen, the

. effect of winding threads on the coated dye tubes to cause printing.

The results indicated that, upon normal drying and baking of the tubes at 250 to 300 F. for three hours, as above described, those tubes having a coating containing soya bean oil and linlseed oil, instead of perilla oil (solutions 6 to 12 inclusive) showed a decided tendency to print," but this was overcome in each of these cases by prolonging the baking period of such tubes some Ahours longer than was suiilcient with tubes coated with solutions Nos. 1 to 5.

Itis possible to prepare and use solutions of the resinV components as above described, in varying concentrations. 'Ihese will also have varying viscosities accordingly. But solutions having a viscosity above 160 centipoises are not suitable for application to cellulosic dye tubes or the like, either by partial 'vacuum impregnation or by simple immersion.. On the other hand, solutions of very low viscosity usually will not contain a suiiicient amount of the resin composition and the relative efliciency of the coating or impregnation procedure 'is reduced and too many treatments are required or the tubes are not satisfactorily coated or impregnated. For example, with solutions `1 to 5, a concentration having a viscosity of 6 centipoises was used, while solutions 6 to 13i were of centipoises.

In actual practice of dyeing yarn upon cellulosic dye tubes treated in accordance with the invention, various types of dyes have been successfully employed and various procedures followed with satisfactory results in each case. These may be summarized as follows:

Direct dyes centrations up to 1.0 per cent in the bath. Dyeing may be made at temperatures varying from 60 to 192 F., and for time periods up to four and one-half hours.

After-treatment of direct colors To increase the fastness of certain direct colors, an after-treatment comprising 0.2 per cent of acetic acid and 0.2 per cent formaldehyde in the bath may be employed. This treatment may be l carried out up to 120 F. and. for up to one hour.

Diazotized and developed dyes This treatment is likewise similar to that for the application of direct dyes. Diazotization takes place in a bath containing 0.7 per cent sulfuric acid and 0.35 per cent sodium nitrite. The

treatment is usually conducted at about 75 F.

This type of dyestuff is usually applied from a boiling aqueous bath containing 0.5 per cent sulfuric acid or formic acid and 1.0 per cent Glaubers salt for approximately two to four hours duration.

Vat dyes This type of dyestuff is applied from an aqueous bath containing about 0.25 per cent sodium hydroxide and 0.25 per cent sodium` hydrosulphite or Lykapon to reduce and maintain the dye in the soluble state. This phase of the treatment may be carried out at temperatures up to about F. and for time periods up -to about one and one-half hours. After rinsing, the `,reduced dye on the yarn is oxidized from an aqueous acidied bath usually containing about 0.25 per cent acetic acid and 0.06 per cent potassium chromate. This latter treatment can be carried out at any temperature up to 180 F. and is usually complete in from ten to fifteen minutes.

Naphthol dyes This type of dyestuif (is applied from an` Sulphur dues This type of dyestui! is applied in an aqueous bath containing up to approximately 0.2 per cent of sodium carbonate (soda ash), 1.0 per cent anhydrous sodium su'lde (commercial chips or equivalent weights of other grades) and 0,'1 per cent of sulphur dyestuifs at temperatures up to F. for time periods up to three hours.

Stripping dye from yam It is frequently desirable to salvage improperly matched or dyed yarn by stripping a substantial portion of the color already on it. A suitable solution is thev aqueous bath containing 0.15 per cent commercial flake caustic soda and 0.15 per cent sodium hydrosulphite or Lykapon powder. The temperature may be as high as 180 F. and the time up to one hour. It is customary to follow any one oi the above hot dyeing .operations or any part thereof by a cold water or saline rinse to remove the dye.or chemicals from the prior treatment. p

This .application is a continuation in part of my application Serial No. 95,851, iiled Augustf13, 1936, and a division of ymy application Serial No. 189,795, filed February 10, 1938.

It should be understood that the present disclosure is for the purpose of illustration only and that this invention includes all modications and equivalents which fall within the scope of the appended claims. f

I claim:

1. A method of making supports for the dyeing or other fluid treatment of yarn in package form, comprising the steps of impregnating a ilbrous shell with a stiiening agent and coating with a solution containing a partially condensed alkyd resin, and al partially condensed phenol aldehyde resin, and drying and heating the resulting coating, thereby to develop a tough, resilient, non-plastic surface, capable of resisting dyes and chemicals.

2. A method of rmaking supports ,for the dyeing or other uid treatment of yarn in package form, comprising the steps of impregnating` a fibrous shell with a. stiffening agent, and coating .with a solution containing a phenol aldehyde modiiled alkyd resin, and a partially condensed phenol aldehyde resin, and drying and heatingthe resulting coating, thereby to. develop the same to -form a surface capable of. resisting dyes and chemicals.

. 3. A method of making supports for the dyeing or other uid treatment of yarn in package form, comprising the steps of impregnating a' ilbrous shell with a stiiening agent and coating with a solution containing a phenol aldehyde modied alkyd resin, a drying oil fatty acid,and a partially condensed phenol aldehyde resin, drying and heating the resulting coating, thereby to develop the same to form a. surface capable of resisting dyes and chemicals.

4. A support for the dyeing or other fluid `treatment of yarn in package form, having a coating thereon comprising the reaction product of a partially condensed alkydresin with a partially condensed phenol aldehyde resin, charac terized by being `sulzbstantially unaffected by water and non-plastic at elevated temperatures up to approximately 200` F.

` 5. A' support for the dyeing or other fluid treatment ofyarn in package form, having a coating thereon comprising the reaction product of a partially condensed phenol' aldehyde modiiied alkyd resin and a partially condensed phenol aldehyde resin, characterized by being substantially unaiected by water and non-plastic at elevated temperatures up to approximately 200 F. f

6. A support for the dyeing or other uid treatment of yarn in package form, having a coating thereon comprising the reaction product of a partially condensed alkyd resin, a drying oil fatty acid, and a partially condensed phenol aldehyde resin, characterized by being substantially unaiected by water and non-plastic at elevated temperatures up to'approximately ,200 F.

acid. in the proportions of 25% to 85% of the phenol aldehyde resin and 75% to 15% of thel alkyd resin, respectively.

`11. A support for the dyeing or otherI iiuid treatment of yarn in package form, comprising a perforated hollow cylinder of fibrous material, coated .with a.v tough, resilient non-plastic resinous mass comprising the reaction products of a partially condensed alkyd resin and a partially condensed phenol aldehyderesin, in the proportions of'75% to 15% of the alkyd resin and- 25% to 85% of the phenol aldehyde resin, respectively, capable of resisting dyesand chemicals. 1

12. A support for the dyeing or other iluidl treatment of yarn in package form,;comprising a perforated hollow cylinder of fibrous material, having a tough, resilient, non-plastic coating containing the reaction products of a partially condensed phenol aldehyde resin material and apartially condensed alkyd resin in the presence of a drying oil fatty acid, in the proportions of ,ed by water and non-plastic at elevated temperatures up to approximately 200'F.

14.. A support. for the dyeing orl other uid treatment of yarn in package form, having a coating thereon comprising the reaction'products of a phenol aldehyde modied alkyd `resin par- 7. A support for the dyeing or other'uid 40 `tially condensed in the presenceof a drying oil treatment of yarn in package form, having a. coating thereon comprising the reaction products of a phenol aldehyde modied alkyd resin, partially condensed in the presence of a drying oil fatty acid, and a partially condensed phenol a1- dehyde resin characterized by being substantially unaffected by water and non-plastic at elevated temperatures up to `approximately 200 F.

8. A support for the dyeing or other uid treatment of yarn in package form, being impregnated and "having an outer coating compris- Y ing the reaction products of a partially condensed phenol aldehyde resin and a partially condensed alkyd resin, in the proportions of 25% to 85% of the phenol aldehyde resin and 75% to 15% of the alkyd resin, respectively.

9. A supportvfor the dyeing or other iluid treatment of yarn in package form, being im'- pregnated and having a nouter coating comprising the reaction products of a partially condensed phenol aldehyde resin and a partially condensed phenol aldehyde modiiled alkyd Iresin, in the proportions of 25% to 85% ofthe phenol aldehyde resin and 75% to 15% of the 'alkydv resin, respectively. l

10. A support for'the dyeing vor other uid treatmenzl o1' yarn in package form, being impregnated and having an outer coating comprising the reaction products of a partially condensed.

phenol aldehyde resin and a partially condensed 70 l alkyd resin in the presence or a drying oil fatty a member of the group consisting of unsaturated fatty acids and glycerides ,of drying. and semidrying oils, and by a separately formed resin obtained by reacting and partially condensing, in the presence oi an alkaline catalyst, formaldehyde and a phenol containing a substituent of the group consisting o1 amyl and butyl radicals and having not more than two nor lessthan one oi the reactive positions which are ortho and para tothe hydroxyl in lfree condition, and by a portion of said pure phenol laldehyde resin which has been reacted with Aan ester gum and then added to said alkyd resin while hot; and an additional amount of said unmodified pure phenolic resin, in a,- common solvent, and drying and heating the resulting coating, thereby to develop a tough, resilient, non-plastic surface, capable of resisting dyes and chemicals.

EVERETT C. ATWELL.

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