US2305006A - Method of delustering textile material and resulting product - Google Patents

Description

Patented Dec. 15, 1942 METHOD OF DELUSTERING TEXTILE MATE- RIAL AND RESULTING PRODUCT Robert s. Holt, Bernardsville, N. J.,and Victor Charles Emile Le Gloahec, Rockland, Maine No Drawing. Application February 8, 1939,

Serial No. 255,218

18 Claims (01. 8-135) This invention relates to the treatment of yarns, either in a free state or woven, knitted or otherwise embodied into a fabric or other material, to modify the superficial characteristics thereof and to the treated product. This invention relates especially to the treatment of yarns, fabrics and the like to modify the degree of luster thereof and to modify the feel or hand thereof, including the softness of the fabric, as well as the frictional resistance afforded by the surfaces of the yarns.

It is a purpose. of this invention to accomplish the delustering of yarns and fabrics and to improve the hand thereof in a way which is superior to proposals heretofore made and which can be controlled in order to get desired effects. While this invention is applicable 'in connection with yarns of any type such as silk, wool, cotton and the like, the problem of delustering and modifying the hand ofyarns has presented certain serious aspects heretofore in connection with yarns of artificial or synthetic fibres or filaments and in connection with fabrics comprising such yarns.

There are several types of artificial fibre yarns on the market at the present time made from cellulose or cellulose derivatives as well as certain synthetic fibres not necessarily derived from natural cellulose. Such yarns which attempt to simulate the appearance of natural yarns or fibres, may be understood herein as coming under the broad term "artificial yarn. Artificial yarns were originally designed to simulate natural silk, and have only recently through extensive changes in the treatments originally proposed been made to simulate other natural fibres, such as cotton, linen, wool andthe like. The yarns intended to simulate real silk, particularly yarns made of regenerated cellulose or cellulose derivatives, e. g., cellulose acetate or cellulose nitrate, are referred to herein as artificial silk. Regardless of the type or composition of artificial yarns, the artificial yarn fibresthat :have been produced up to the present time have a smoothness of. surface and index of refraction which tend to impart to the artificial yarns a high degree of luster. Fabricsmade of artificial silk, for example, normally have an appearance of harsh metallic shine as opposed to the soft diffused luster of fabrics made of real silk. Moreover, the artificial silk yarns have such a smooth surface that fabrics made therefrom tend to have a slick or sleazy feel that differs considerably from the more agreeable hand of real silk fabrics and the smoothness of surface makes fabrics made from artificial silk yarns susceptible to pulling out of shape, especially when the fabrics are made with a rather coarse weave. The high luster and slick feel 'of artificial silk fabrics and their tendency to be pulled out of shape make them of less value for most purposes than fabrics made of real silk.

Heretofore many methods have been proposed 0 for treating artificial yarns such as artificial silk so as to delusterthe yarns and make them more nearly resemble the appearance of natural fibre. Moreover, methods heretofore; have been proposed for modifying the slick or sleazy feel of artificial silk fabrics. Up to the present time, however, no satisfactory commercial method has been devised for successfully delustering the darker shades of dyed artificial yarns. In the cheaper grades of fabric no satisfactory method has been devised for producing artificial silk fabrics, for example, of a desirable feel or hand. Even in the case of spun rayons when used, for example, as upholstery fabrics, the essential smoothness of the filament elements out of which the yarn is made tends to cause the fabrics to. pull out of shape. It is likewise true that crepe fabrics of artificial silk, even when the crepe thrown rayon ,yarns are reinforced with uncreped yarns such as those of acetate, have an undue tendency to sag and stretch, and particularly in dark shades the delustered efiect of the creped yarnsis negatived by the bright efiect of the uncreped yarns in such combination fabrics.

Heretofore attempts have been made to deluster artificial silk yarn byincorporating in the yarn titanium oxide or some other pigment in order to make the yarn more opaque. Any such method of delustering yarns has proved unsatisfactory for several reasons: In the first place,

the introduction of pigments or other inert mate-,

rials into the body of a colloidal fibre destroys the homogeneity of the fibre and tends to weak- -en the yarn. If the pigment does not penetrate into the yarn, but merely occurs on the surface one of a dark color. In the dyeing of artificial silks, the dye does not appear to penetrate deeply into the body of the fibres but seems to be adsorbed on the surface. If a dye of light color is applied toan artificial silk which has been delustered until it has a more or less opaque appearance as by a, pigmenting treatment, a film of light colored dye subsequently applied does not substantially negative the previous delustering treatment, inasmuch as the relatively opaque surface of the yarns remains visible through the light colored transparentfilm of the dye. When, however, a dye of darker color is used, the previous delustering of the yarn by methods heretofore proposed is negatived orminimized in direct proportion to the depth of color of the dye. A coating of dark colored dye onthe surface of the yarn renders the yarn itself substantially invisible through the coating of dye. Since the artificial fibres, even after delustering by pigmentation or other method heretofore proposed, retain a smooth and slick surface, the dark colored dye which adheres to the surface forms a slick-appearing opaque film with the result that the yarn has a highly lustrous appearance which is entirely different from that of real silk dyed with a dye of similar color.

In order to overcome the slipping or stretching out of shape of artificial silk fabrics, various methods of treatment as by synthetic resins in" such adsorbed colloidal organic pectized material upon the fibres of the yarns and that the material, particularly after the drying of the yarn and after the fixing action of the dehydration on the adsorbed coagula, is not readily removable either by reagents normally encountered in treating the yarn such as aqueous detergent solutions, hot or cold, or dry cleaning materials. Moreover, the material is resistant to removal as a result of rubbing the yarn against other things. When the colloidal organic material is adsorbed on the surface of the fibres or filaments, it imparts such superficial irregularity and largely microscopic roughening effect to the yarn as to alter the direction of the rays of light refracted from the yarn so that the rays are refracted in a multiplicity of directions rather than with regularity. Moreover, in so far as the light rays penetrate the deposited coagula and emerge again, the direction of the emerging light rays is affected by the difference in refractive index bewhich the fibres are bonded more or less: irremovably to each other, and in extreme cases the yarns are practically glued to each other at every point of contact between warp and filler, have been proposed, but these methods are relatively unsatisfactory and expensive and require extensive'and costly plasticizing of the resinous matetween the material of the coagula and the material of the yarn. The coagula on the surface of the fibres also affect the direction of the reflected light rays so as to break them up. In any event, the effect of the minute coagula on the surface of the fibres is to effectively deluster the yarn and to impart to it a modified diffused brilliance more nearly resembling the appearance of real silk. The delustering effect that is produced seems to be of such a fundamental character that the delustering effect persists regardless of the type or color of dye that is used in dyeing the fabric. Moreover, in addition. the

' presence of the adsorbed coagula changes the slick feel of the'yarn so as to impart to it charrial in order to obtain a satisfactory feel or "hand in the finished fabric. i

It is a purpose of this invention to produce yarns including artificial yarns which are delustered to any desired degree regardless of whether'or not the yarns are dyed with either a light or dark'colored dye and to achieve good delustering even of normally glossy and bright yarns without impairing the strength of the yarn due to the introduction of inert material into the body of the yarn or fibre or changing its chemical characteristics. An important feature of this invention is that dyed artificial silk yarns not only of light colors, but also of navy blue or black colors can be produced which have substantially no more luster than yarns of natural fibres that have been dyedto a similar color.

The extent of delustering can be controlled as desired. Moreover, delustered yarn can be produced which, when incorporated in a fabric, results in a fabric that has a feel or hand resembling the feel or hand of real silk fabrics. These desirable results can be produced even in the cheaper grades of viscose or acetate artificial silk fabrics made from inexpensive yarns by a simple weave. It is also possible to produce fabrics which are highly resistant to slippage. The

softness and frictional resistance of the yarns can be controlled according to this invention.

It is a feature of this invention th at the sur-- acteristics of hand more nearly resembling those of real silk. This modification of the slick feel of artificial silk yarns can be varied, as desired by the operator.

As hereinabove mentioned, we have found that protein materials produce coagula having desired properties on the yarn. Experiments have been made with many different proteins and these experiments indicate that the proteins as a class may be used according to this invention. The term protein as used herein isused in a broad sense and as including sucli materials as albumins, conjugated proteins, and derived proteins, and in general as including any nitrogen-containi'ng organic matter which responds to the Biuret reaction and which can be placed in a colloidal aqueous solution. Thus the proteins which may be used according to this invention include simple proteins such as the albumins egg albumen, fresh or dried, blood albumin, etc.), the glutelins (e. g., most of the vegetable albumens, glutelin, oryzenin) and the sclero-proteins (e. g., gelatin, collagen). Examples of conjugated proteins are the chromoproteins (e. g., haemoglobin), the nucleo-proteins (e. g., nucleine), the phosphoproteins (e. g., casein). The derived proteins may also be used such as the proteoses (e. g., albumose, globulose), the peptones (e. g., soluble peptone) and the peptides.

Protein materials are colloidal in character and can be dispersed in the form of a hydrosol. A proteinous sol can be transformed to a proteinous gel by'treatment with certain substances, the action being known as pectization of the colloidal; material. A substance adapted to pectize a colloidal proteinous material is referred to herein as a pectizing agent for the protein.

In the practice of this invention the treatment of a protein with a pectizing agent, therefore, plays an important part. Many substances are pectizing agents for all proteins, while others are'pectizing agents for some only of the proteins. Many illustrations of pectizing agents can be given. The so-called alkaloidal reagents are particularly effective pectizing agents in the practice of this invention, examples of such reagents being tannic acid, picric acid, phosphotungstic acid, phosphomolybic acid, metaphosphoric acid, sulphosalicylic acid, tri-iodohydriatic acid, ferricyanic acid, etc. Other protein pectizers which may be used are the quinones such as parabenzoquinone. Aldehyde derivatives may be used, and particularly condensation products with aldehydes such as sulphonic derivatives of phenols and aldehydes, particularly when such derivatives are mixed with salts of metal such as aluminum or chromium, e. g., aluminum acetate and basic chromic acetate. Products of polymerization of primary aldehydes such as ing the yarn after the colloidal material has been adsorbed thereon. The adsorbed and pectized protein on the surface of the dehydrated .yarn not only results in a very effective delustering of the yarn, but also overcomes the slick or sleazy used care should be taken not to use such excessive quantities of the metallic salts as will result in coagulating the protein until its colloidal ac tivity is substantially destroyed. Acids may also be used as protein pectizers, although acids cannot be used in connection with all proteins. For example, acetic acid may be used as a pectizer for such proteins as casein, blood albumin, or egg albumen. While acetic acid does not pectize a protein such as gelatin, gelatin may be pectized with some other protein pectizer such as tannic acid or chromium alum. A protein such as casein can be pectized by a material such as rennet.

It is desirable that the protein material being applied to a yarn be in an active lyophilic colloidal state so that it may more readily be adsorbed on the surface of the fibres. Protein materials having characteristics of typical colloidal activity and having the property of existing in an aqueous colloidal solution appear to be more intensely and morerapidly adsorbed on the surface of the yarn as compared with material lacking, or having a low degree of colloidal activity. Ordinarily it is preferable to treat the protein with a pectizing agent as a separate step. In other words, the yarn may be first subjected to the protein material in colloidal solution and thereafter the yarn carrying adsorbed colloidal protein may be treated with a pectizing agent so as to fix the colloid with greater permanence on the surface of the yarn. Alternatively, however, the yarn can be treated with the appropriate pectizing agent and thereafter treated with a colloidal solution of protein. This results in a pectization of the protein as fast as it is adsorbed on the surface of the yarn. As will be mentioned more in detail below. a protein maprotein material.

feel of artificial silk yarns. When, however, the.

protein material by itself is adsorbed on the yarn, the process has to be quite carefully controlled to avoid a stiffening of the yarn. If the amount of coagula is limited, a partial, but in many instances, fully satisfactory delustering can be effected without undesirable stiffening of the yarn. However, if an excess of the coagula is adsorbed on the fibres, the coagula tend to stiffen the yarn somewhat. tendency to stiffen the yarn can be successfully overcome by incorporating an amine with the The amine is believed to react with the protein on its acid function to form a complex reaction product which is referred to herein as a protein-amine complex. The molecules or miscelles of the colloid are more complex than when the simple protein is used. The' the coagula, with the result that the light is refracted and reflected in the greatest possible number of directions, whilst at the'same time the amine tends to produce coagula on the yarn which Iionot stifien the yarn. When the protein is coagulated as a protein-amine complex, a very soft and flexible fabric can be produced which is likewise thoroughly delustered and has a desirable hand. I

In referring to an'amine, we refer generally to all substances including an amine function, inasmuch as the large number of amines tested by us indicates that all of the amines as a classare operable. The amines include primary amines such as ethyl amine and phenyl amine (aniline). The class of amines also includes secondary amines such as diphenyl amine, diethyl amine and methyl ethyl amine, and tertiary amines like trimethyl amine, methyl ethyl phenyl amine and hexamethylene amine. Amines which are referred to also include quaternary ammonium salts like the hydrate of tetra ethyl ammonium or the hydrate of triethylphenyl ammonium. Also included are the diamines such as ethylene diamine and the triamines such as rosaniline. The amino alcohols may also be used such as monoethylene amine, diethanol amine, triethanol amine, morpholine, choline and neorine. The phenyl amines are also operable such as orthoaminophenyl. The amino acids can be used such as glycocolLalarine, leucine, aspartic-acid, lysine and arinine. Acid phenol amines may likewise be used.

When an amine is used, the amine can be incorporated in the colloidal solution of protein and in such case a colloidal protein-amine complex is formed that becomes adsorbed upon the surface of the yarn. This complex like the protein alone can'be pectized by aprotein coagulant due to the action of the pectizing agent on the protein component of the complex. While it is logical We have found that this tions of the protein.

to mix the amine with the protein prior to application of the mixed materials to the yarn, the amine can be applied to the yarn either before: or after the application of the protein to'the yarn, the fixation of the amine on the protein to form a protein-amine complex taking place under such conditions. It is preferable, however, to mix the amine and the protein before the protein is pectized by a protein coagulant.

When the yarn is treated according to this invention after the fabric has been dyed or during the dyeing, the pH of the treating liquid may be important if the dye used is sensitive to acids or alkalis. This is especially important. in connection with the use of amines, inasmuch as amines which are normally basic in character may have an adverse effect on the dye used. When a dye is used which is sensitive to alkaline pH, we can use hexamethylene amine, which amine is about neutral. Hexamethylene amine has the disadvantage, however, of notbeing stable when used at about 160 F. If one wishes to operate at such temperature, then some other amine can be used which, if excessively alkaline, can have its alkalinity neutralized. In this connection, acids are usually too strong, if used to neutralize. the free alkalinity of the amine. Therefore, it is better to add to the amine some material such as formaldehyde or trioximethylene until the pH is reduced to about 7.0 to 7.5. An amino-acid may also be added to the amine, such as acid -1 amino-8-naphthol 3-6 disulfonic, to form a product of neutral pH while still retaining one or more amine functions.

According to a further feature of this invention, the adsorbed coagula can be rendered more permanent and more resistant to chemical reagents and likewise of better optical properties for effecting delustering by including in the coagula a metal other than the alkali metals, such metals all being operative as a class and being referred to hereinafter for the sake of brevity as'nonalkali metals. While alkaline earth metals may be used and are included in the above group, they are less desirable than the other nonalkali' metals, inasmuch as the alkaline earth metals tend to impair the bond between the yarn and the coagula and tend to produce a somewhat brilliant coagula, thereby counteracting the delustering effect that is desired. The preferred class of metals which are operative (all metals except the alkali metals and the alkaline earth metals) are referred to herein for the sake of brevity as non-alkaline metals. 'Examples of non-alkaline metals that may be'used are tin, zinc, lead, aluminum, copper, iron, gold, silver, platinum and the like. The metals tend to increase the opacity of the coagula and, therefore, increase the effectiveness of the coagula for the purpose of delustering the yarn. The metals, particularly the non-alkaline metals, also make the coagula more resistant to chemical agents such as solvents used in dry-cleaning operations, weak alkalis and weak acids, and impart increased stability to the coagula. The effect of metals in forming metal-protein material or complexes is referred to herein as metalizing the coagula, and refers to -the fixation of a metal on or reaction of the metal with the basic func- The phenomenon of in.- creased stability-of adsorbed materials when molecular complexity is increased has been cited hereinabove and explains one function of the metal as outlined herein.

The non-alkali metals may be used in the (particularly heavy metals which are coagulants form of soluble salts, e. g.', as the chloride, nitrate, acetate, or the like. Some of such metals for protein) tend to prematurely excessively peetize or coagulate the protein or protein-amine colloidal material, if the metal is mixed with a colloidal material prior to adsorption thereof by the yarn. In such case, the yarn can be treated with metal by means of .a separate application, either before or after the yarn is treated with the colloidal organic material. Ordinarily, it is preferable to treat the yarn with the metal after the yarn has adsorbed the colloidal organic material in order to metalize the colloidal material, although in certain cases when it is desired to obtain a preliminary etching of the fibre before it is caused to adsorb the colloidal organic material, the initial use of a metallic salt solution for this purpose may be desirable, and in such case the colloidal is metalized as it is adsorbed on the yarn carrying the metal. It should be noted that the etching or roughening of the fibre is designed solely to create a greater surface area on the fibre for colloidal adsorption of the protein and pectizing agent. It is possible to effect metalization of the protein or protein-amine complex colloidal material even with a heavy metal and prior to the adsorption of the colloidal material on the yarn, if the amount of metal is limited so as not to coagulate entirely, that is, to degrade the colloidal activity of the material. When the metal has a pectizing action on the colloidal material, the metalizing step and the pectizing step take place simultaneously. If the protein is treated with a limited amount of metallic pectizing agent prior to adsorption on a yarn, the pectized material can be rendered more stable after the metalized protein has been adsorbed on the-yarn by a further treatment with a protein pectizer and final dehydration.

We have found that the advantage of using a non-alkali metal may be retained while avoiding the disadvantage of prematurely excessively coagulating the colloidal organic material used in the process by using a metal such as arsenic or antimony. These metals have the capacity of forming a highly stable complex with protein material or protein-amine material, which complex can be retained in a colloidal state ina colloidal solution. For example, in the practice of this invention, one can mix a protein with a The formation of protein complexes with amines and/or metals is believed to be due to the fact that proteins are capable of acting either as acids or bases to form either basic or acid salts of protein conjoined to the molecular nucleus. Thus the proteins can be reached with metals to form metal-protein complexes and can react through their acid function with amines to form protein-amine complexes and can likewise react with both to form metal-protein-amine complexes.

It has been pointed out that protein alone may be adsorbed on the yarn and that the protein is preferably adsorbed together with amine and/or metal. Any such protein or proteinous mixture or complex compound is referred to herein as organic material comprising protein.

More generally we have accomplished a satisfactory delustering by the adsorption on yarn of amorphous and non-crystalline colloidal material in a form so very finely divided that an even distribution of the coagula on the yarn is obtained and that a maximum of delustering effect is obtained while at the same time avoiding undue stiffening of the yarn. The more highly molecularly complex coagula are especially advantageous in this regard. The coagula that are obtained also of a color which does not interfere with the color of the fabric even when very light dyes are used, the oteins in particular being of a light or substantially colorless nature. The coagula that can be aflixed to the yarn are irreversible in that theyare insoluble in boiling water. Moreover, the coagula are permanently adsorbed and are resistant to chemical reagents and are also resistant to mechanical action such as rubbing. We believe that the procedure herein described results in a true colloidal adsorption. We have found that the lyophile colloids are more permanently adsorbed than are the. lyophobe colloids and that the adsorption of lyophile colloids can besubjected to better control. have also found that rate of adsorption and the adherence of the colloidal material for the yarn can be promoted by maintaining substantial oppositeness of ionic charge between the yarn and the colloidal material that is being adsorbed. The electric charge of artificial silk is normally positive, that is, cationic. The adsorption of the colloid on the yarn can be promoted when the negative charge of the colloid is increased. The

use of amines which are eitherneutral or somewhat'basic in characteris desirable, inasmuch as the presence of the amines tends to increase the anionic charge of the colloidal coagula so that the tendency of the colloid to be adsprbed by the yarn is increased. The presence of arriamine, as mentioned above, also tends to increase the complexity of the substance that is colloidally adsorbed and this also promotes the permanent adsorption of the colloid on the yarn. The tendency of a negative charged colloid to be adsorbed on the yarn can also be increased by increasing-the cationic charge on the yarn, e. g., by preliminarily passing the fabric through a dilute acid solution having a pH of around 3 so as V to insure that the yarn or fabric will carry a substantial cationic charge when it is treated with the colloidal sol. x

When a metal is used such as the metals re- .ferred to, above, the'yarn can be treated with the metal in such a way as'to preliminarily etch the surface of the yarn. The etching or disincrustation of the yarn alone has very little practical effect in delustering the yarn, inasmuch as, to substantially modify the appearance of the yarn by the etching operation alone, it would be' necessary to attackthe yarn to such an extent as to weaken the yarn so that it could not be used. The etching or disincrustation merely has some effect in roughening the surface of the yarn so that the coagula which are responsible for the delustering effect will be more firmly bonded to the yarn by creating a greater surface of the colloidal fibre for adsorption of the colloidal organic such salts are used, the yarn can be preliminarily treated with the salts so as to etch the surface thereof. Moreover, if a' small amount of the metal is left on theyarn after the preliminary treatment, this metal will combine with subse- 'quently added protein or protein-amine material to form metallic complexes with the resulting advantages hereinabove referred to. Other metallic compounds which not only are effective in forming metal-protein or metal-protein-amine complexes, but also are effective in producing a preliminary etching or disincrustation of the yarn, are antimony chloride, copper cyanate and Schwei-tzers reagent (copper oxide ammonia). If a preliminary etching or disincrustation is desired without the use of a metal, some chemical such as trichloracetic acid or caustic soda may be used; ..when a chemical .such as the ones just yarn can also be treated with a metal salt which per se does not effect an etching'or roughening of the surface of the yarn, e. g., lead acetate, copper' nitrate, potassium or sodium ferrocyanate, or the like, although when a metal is to be used and some preliminary etching effect is desired. both of these objects can be attained in the simplest manner by employing a metal salt which 'exercises an etching effect and by leaving some of this metal salt on the yarn so that it may combine with the protein.

In View of the foregoing, it is believed to be apparent that the materials and the application thereof cooperate to produce a new type of superficial treatment for yarns, which treatment we have found results in a very permanent and satisfactory modification of the luster and hand of yarns and fabrics.

In order that this invention may be more clearly understood, it will be described in connection with examples illustrating the practice thereof.

A fabric composed of artificial silk, e. g., viscose such as a so-called rayon taffeta, is first dyed in the usual manner. The dyed fabric is then .passed through a 5% aqueous solution of zinc chloride at normal temperature. The solution of zinc chloride attacks the surface of the fabric and produces a slight etching or roughening of the yarns of the fabric. After a period of seconds (as in continuous passage through a conventional type of padder or soaper bath), the fabric can be removed from the solution of zinc chloride.

over a vacuum extractor so as to remove excess moisture and "insure a uniform dispersion of the material. The disincrustation or etching of the yarn can be effected by using metal salts such as zinc chloride, or stannicchloride, or both,

which affect the yarn in this manner. When 7 albumen through the interstices of the yarns of the fabric. While the fabric is in contact with the colloidal egg albumen, the egg albumen becomes adsorbed upon the surface of the yarn in the fabric. As it becomes adsorbed, it is affected by the zinc on the yarn to form a metal-protein complex. The fabric is removed from the bath of egg albumen, excess moisture eliminated by The fabric, upon removal from the solution, is squeezed between rollers or may be fabric -is treated with an albumen pectizer such as a 4% solution of tannic acid. Thereafter the fabric is passed between rollers or through a vacuum extractor in order to obtain uniform pectization and fixation of the coagula and in order to remove excess moisture. It is then dried to effect a stable coagulation of the adsorbed pectized material and can be finished according to conventional practice in any way that is desired. The finished fabric will be found to be effectively delustered even when a dye of dark color has been used. Moreover, the feel or fhand of the f-abric will be found toapproach more nearly that of natural silk.

In the foregoing processes, it, is not essential to use the zinc salt. The first bath wherein. the zinc salt is appliedto the fabric may be omitted. In such case, the protein is adsorbed bythe yarn in the fabric and is pectized by the subsequent application of the tannic acid. When the zinc chloride or other metal is omitted, the advantages which result from the presence of the metal and which have been described hereinabove are also omitted. The process above described either using or omitting the metal may be improved by including in the bath of egg albumen an amine such as triethanol amine to a concentration thereof in the bath of 4%, for example. The amine forms a protein-amine complex which is colloidally dispersed and which is adsorbed as a colloid on the yarns of the fabric as the fabric is passed through the bath containing protein and amines. When the amine is included in the bath, the'treated fabric is considerably softer than when the amine is not included.

In carrying out a process wherein a plurality ofbaths is employed, it ispreferable to avoid carrying over from one bath tothe next any excess of reagent applied in thepreceding bath. For example, it is desirable to avoid carrying over an excess of protein material into the bath of protein pectizer, inasmuch as any excess of protein carried into the bath of protein pectizer would cause a congestion of more or less agglomerated pectized material in the bath containing the pectizing agent.

The following is another example of the practice ofthis invention, the procedure being advantageous, inasmuch as it reduces the number of baths to which the fabric has to be subjected. The fabric is first passed through an aqueous colloidal solution containing about to 1% of gelatin, about of tartar emetic, and about 3% of hexamethylene amine. The antimony in the tartar emetic reacts with the gelatin to form a metal-protein complex. The hexamethylene amine also enters into the complex, with the resultant formation of a metal-proteinamine colloidal complex that is adapted to be readily adsorbed upon the yarns in a fabric.

The fabric upon being passed through a bath containing the materials above mentioned, can

be rolled or passed over a vacuum extractor to remove excess moisture and unadsorbed material and to leave a uniformly distributed residuum of adsorbed material on the yarn of the fabric. Alternatively the fabric can be subjected to a quick washing to remove any excess of the first treating bath. The fabric is then passed through a bath of protein coagulant such as a 4% solution of tannic acid to effect a pectization of the adsorbed colloidal complex. The fabric is then squeezed or passed over a vacuum extractor or is "washed with water so as to remove any excess of agglomerated unadsorbed gel on the surface of the fabric.

The process above described lends itself particularly well to a combined dyeing and delustering treatment. If desired, a dye can be included in the first bath so that the fabric is dyed at the same time that the colloid is being adsorbed. If desired, of course, the fabric can be dyed either before or after the treatment with the metalprotein-amine complex and protein pectizer. Moreover, when the protein or metal-proteinamine is introduced in the dye bath, the pectizing agent may be applied either before or after the dyeing.

The duration of the colloidal adsorption required' to obtain a desired effect depends somewhat upon the material which is being treated.

synthetic yarns or artificial silk yarns such as cellulose acetate, which are more inert or less active colloidal substances, on the other hand, require a longer exposure to the colloid, inasmuch as the adsorption proceeds more slowly. The substantivity of cellulose acetate can, however, be readily elevated by increasing the cationic disequilibrium of its charge by a preliminary acid treatment. I This is of particular use in the treatment of fabrics woven from a mixture of viscose and acetate yarns, which under normal conditions, will adsorb substantially all of the colloidal protein material on the viscose, due to the greater colloidal activity of the viscose. The acetate, however, can be treated to increase its state of cationic disequilibrium as by passing it through a dilute acid and after such treatment the colloidal protein material can be attracted more strongly to the acetate, thus rectifying the difference in adsorptive attraction based on the yarns.

In carrying out this invention, the conventional equipment such as used in textile finishing plants may be used. When two or three baths are employed, one can use equipment which is referred to in the trade as a soaper, the material being run through a series of baths with mangle rolls between the successive baths to remove excessive liquid from one bath before the fabric goes to the next. It is also possible to use equipment which is known in the trade as a padder. When a padder or soaper is used, it is desirable to either use soft rubber rolls of large diameter with good tension on the frames or rolls which have been wrapped a number of times with cheesecloth or light sheeting. In using a soaper, the fabric passes through a bath but once, so that a continuous process can be evolved. Use of a soaper or padder is best suited to the treating of fabrics such as regenerated cellulose fabrics which adsorb the colloidal organic material quite rapidly. When a material is being treated which adsorbs colloidal material rather slowly, however, equipment known as a jig is desirable. In this equipment, the fabric moves through a single bath and is re-wound on a reel-on the other side of the bath, the action being reversed when the end of the fabric is reached and since the fabric can be passed through the bath any number of times, this enables the time cycle to be lengthened to any degree that may be desired. Where two or more baths are required using a single jig-the bath can be changed; and when a pluralityof jigs are available the fabric, after treatment in one jig, can be removed to other similar equipment charged with a different bath. It is not necessarily essential to squeeze between the different baths, inasmuch as a light-washing with water may be used to eliminate excess unadpassed over a vacuum extractor between baths and at the conclusion of the operation. Alternatively, a type of equipment, namely, dye-kettles, used in the dyeing of crepe fabrics, may be used. In such case, if desired, the delustering operation can be combined with the dyeing operation, the fabric being subjected to the treat- I ments heretofore used in the dyeing of crepe fabric, except that a delustering reagent is included in the dye bath. Because of the excessive amount of-liquid at low concentration of dyestuif used in this method of dyeing as compared with jigs or padders, it is, however, desirable to utilize a separate dye-kettle or dye-box for the delustering process and to dye the fabrics afterwards. Very low concentrations of colloidal materials are so dispersed as to delay adsorption; therefore, it is more, feasible to work with normal concentrations and to save the solutions. If normal concentrations are usedin the dye-bath itself, the unadsorbed' materials which must be discarded with the exhausted dye liquor constitute a serious waste and therefore a practical objectionnot as to results but as to costs. Crepes are normally in this method of dyeing guided into rope form by pegs on the overhead reel, whereas we find some practical advantages in obtaining uniform dispersion and adsorption when we remove these pegs and keep the fabrics open or flat instead of in rope -form. The fabric may be dried in a conventional hydro-extractor and then air-dried or heat-dried on conventional equipment. Therefore, even with crepe fabrics it is possible-to obtain all of the advantages of the "delustering process herein described,

It is normally preferable to subject the colloid to pectization by a protein pectizer after the colloid has been adsorbed upon the surface of the yarn. It is possible, however, to cause the pectization to occur before the colloid is adsorbed, provided the pectized colloid retains some of its colloidal activity. Hereinabove reference has been made to the passage of a fabric through a bath of gelatin, tartar emetic and hexamethylene amine, the fabric thereafter being treated with tannic acid in a separate bath. It is possible to add the tannic acid directly to the bath containing thegelatin, tartar emetic and hexamethylamine, provided an excess of tannic acid resulting in excessive precipitation of agglomerated-material is avoided and providedthe pectized material is kept in a state of dispersion by sufficient agitation. The metal-protein-amine,

complex, even though pectized by tannic acid, retains suflicient colloidal activity so that adsorption thereof upon the fibres of the yarns takes place. If a dye is incorporated in the bath, the yarn will be dyed at the same time that the yarns in the fabric are delustered. Similarly, other pectized proteins may be colloidally dis- 75 known as tannalbin (tannin albuminate) can be ground to a powder and colloidally dispersed and thereby placedin condition for adsorption on the yarns. Even heavy metals can be mixed with proteins or protein-amine complexes prior to adsorption if the heavy metal is added in insuflicient amounts to destroy the colloidal activity of the resulting metal-protein complex.

In practising this invention, it is apparent that concentrations of the solutions and the sequence of treatments may be varied widely. Thus it is apparent that if the concentration of a solution s increased, a'greater amount of the material will normally be deposited on the yarn unless the degree to which the fabric. is squeezed or subjected to a vacuum extractor, is correspondingly increased. Conversely, the lessening of the efiect can be controlledby using dilute solutions, although the effect of dilute solutions can be counteracted somewhat by removing a lesser amount of the solution from the yarn. It has been pointed out that the amine is particularly effective in producing a soft fabric, while the protein is particularly effective in producing a stable adsorption and heavy substantial feel. By controlling the relative proportions 'of protein and amine, it is possible to produce many. different effects as far as hand and delustering is concerned. Further in this connection, it should be borne in mind that the requirements for superficial characteristics of a fabric such as its luster or lack of luster or its hand" or softness are dependent largely upon popular fancy and the type of material which is being treated. By varying the selection of the protein that is used, or the amine that is used,-or the combination or subcombination and quantities of these materials, it is possible to vary the effects which can be produced. The choosing of reagent materials and concentrations thereof beyoncLthose set forth in the examples herein given should be made with a view to the results contemplated and readily attainable as herein described. The protein and the pectizing agent therefor and other reagents should be selected primarily with a view to obtaining to as high a degree as possible a colloidally active molecularly complex finely-divided amorphous gel and with a View to avoiding excessive agglomeration or precipitation in substantially inert crystalline form suchas tends to result from the use of excessive quantities of metallic salt as the sole pectizing agent.

In carrying out this invention, it is. usually desirable to include in the bath of colloidal mate- 'rial adsorbed on the yarn a wetting agent. Various wetting agents are known such as sodium salts of highersulphonated'alcohols. About 4% of a wetting agent may be included in the bath, thus accelerating the action of adsorption and it may be that there is thereby a certain degree of osmotic absorption by the fibre in addition to purely surface adsorption oi the colloid. The wetting agent lowers surface tension; the wetting agent also is helpful in achieving a homogeneo us distribution of the coagula on the yarn. The following is an example of theme of a wetting agent. An aqueous bath is made up containing morpholine 2%; soluble peptone'%%, and /470 of a wetting agent such as the sodium salt of sulphonatedoctyl alcohol. The fabric is first passed through this bath and is treated to re move excess solution. Thereafter the fabric is passed through a bath containing 6% of tannic acid in order to pectize the protein-amine complex on the yarns of the fabric.

While the coagula of colloidal material can be adsorbed upon the yarns as by passing a fabric through a bath of colloidal material, it is possible to apply the material by sprays or the like. It is also possible to cause the adsorption by electrophoresis. In such case the fabric, if sufficiently close-woven, may act as theseptum. Alternately, the fabric may be guided in uniform deposited on the septum by an electric current.

In a single bath process, pectized protein material can be deposited by the electric current on the septum so as to be adsorbed thereon. In this connection, since a protein such as gelatin has two isoelectric points, it is possible to vary the particle movement depending upon the polarity of the septum, by for example, using gelatihate of tannin, on the one hand, or tannate of gelatin, on the other hand. In other words, a protein such as gelatin may play the role either of an acid or a base either forming salts of gelatin or forming gelatin salts of an acid.

' In carrying out the process of this invention, the dyeing of the yarn or 'fabric may be accomplished at any time before, after or during the delustering treatment as previously mentioned. When the fabric is initially dyed and thereafter is treated to effect a delustering thereof, the coagulated material should be as colorless as possible and relatively thin. For this purpose a relatively colorless treating material should be used. If the treating material should be somewhat colored, this can be taken into consideration in connection with the dyeing of the yarn or fabric. Whenthe yarn is dyed before it is delustered, the delustering treatment is effective. Ayarn or fabric which has been delustered according, to this invention may, of course, be dyed after it has been treated and the dyeing will not adversely affect the delustering effect. dye may be applied before, during or after the process of this invention. It has been mentioned above that the dye may be incorporated in the bath containing protein material. In such case a compatiblemixture of dye and protein may be selected. For example, if the dye has to be applied in a heated solution, then a protein material such as gelatin or casein, which substances are not degenerated by heat, may be used. The dye may also be applied in the bath of protein pectizer. Especially when the dye is incorporated in a bath of protein or in a bath of protein pectizer, the pectization of the protein material has the effect of fixing the dye very permanently on the yarn. If the yarn is initially treated with a metallic salt or with an etching material, the dye may be incorporated in the bath of such material.

In the examples heretofore given, tannic acid has been mentioned as a specific protein pectizer which may be used according to this invention. This is because tannic acid is preferable for most purposes to other protein pectizing agents. In the first place, the tannic acid is in itself a colloid and tends to promote the colloidal The:

activity of the complex with which it is mixed and tends to promote the rapidity and permanence of the adsorption of the other colloidal material on the yarn. In the second place, the

.tannic acid has not only a pectizing effect on then the pectization of the mixture or complex can be stabilized more completely by using in addition to the protein pectizer an amine coa ulant such as a metal, e. g., lead nitrate. Most of the protein pectizers also coagulate amines, however, illustrations of such protein pectizers being lead nitrate, ferric chloride.

Other examples of the practice of this invention are as follows, it being understood that the baths are intended to be used with conventional equipment as outlined hereinabove, equipment and time cycle being adapted to the fabric or material treated:

First bath: Per cent Peptone soluble 1 Ammonium arsenate .75 Ethylene diamine 2 Water Balance Second bath:

Acid silico tungstic 3 Water Balance First bath:

Casein i 2 Triethanolamine 3 Water Balance I Second bath:

Lead nitrate 3 Water Balance Third bath:

Tannic acid 3 Formaldehyde 10 Water Balance A dye can be included, if desired, in any of the foregoing baths, or the dyeing may occur before or after the treatment or between any of the steps thereof.

A combination fabric of part acetate and part rayon yarns is treated in a dye-box as follows:

Water Balance In the foregoing example, the fabric is preferably given a light washing with clear water after the first bath and several washings after the second bam and thereafter is dyed.

'ptomaine, betaine and the like.

7 An all-acetate taifeta is treated in a "jig as follows:

First bath: Per cent Hydrochloric acid Stannic chloride 2 Waten--. Balance Run once through jig, drain and fill immediately with second bath.

.Second bath; Per cent Dried blood 2 Hexamethylene tetramin 4 'Water l Balance The fabric is run through the second bath two or three times. Then the fabric is washed once with clear water to remove any unadsorbed agglomeration of protein-amine coagulated by the stannic chloride. Then follows the third bath.

Third bath: Per cent Parabenzoquinone a 2 Water Balance Wash several times and dye, if desired, in the same jig."

Referring to the two precedingexamples, the acetic acid'and the hydrochloric acid illustrate the treatment of a fabric to increase the cationic disequilibrium thereof prior to adsorption of colloidal organic material on the yarns thereof. The use of the acid-1-amino-8-naphtho1-3-6 disulphonic with trimethylamine illustrates the lowering of the pH of an amine normally having an undesirably highpI-l. The stannic chloride not only metalizes the subsequently applied protein, but also etches or roughe'ns the surface of the yarn so as to increase the capacity of the yarn to adsorb colloidal material comprising protein.

A material such as naturally occurring latex .contains colloidally active protein. A material such as naturally occurring latexsis, therefore, useful not only because of the plastic materialscontained therein, but also because of the fact that the col'loidally active protein in the latex can be adsorbed by yarns and pectized, as mentioned herein, by protein coagulant. Thus we may proceed as described following baths:--

Per cent I. Latex a 2 Triethanolamine 2 Water .l3alance- IL-Tannic acid 3 Water Balance While this invention has been described in connection. with organic material comprising protein, there is another related nitrogen class of organic materialsthat behave similarly, namely, the alkaloids such as nicotine, morphine, opium,

' These substances are adsorbed in the mannerdescribed above in connection with protein materials and can be pectizedby an alkaloid pectizer. Most of the protein pectizers referred to above are likewise alkaloid pectizers, particularly the .so-called alkaloidal reagents, as well as parabenzoquinone,

certain aldehyde derivatives, various metallic salts, certain acids, etc. The alkaloids also form complex molecular structures with amines and with non-alkali metals as hereinabove described in connection with the employment of proteins and in other respects behave in similar manner. 7 yarn above, using the Examples of the practice of this invention using alkaloid material are as follows:-

In the example just given, the second bath can -be omitted, if no metalizing of the alkaloid is desired. a

While reference has been made to the adsorp-' tion of colloidal organic material on yarn, it is to be understood that the term yarn is to be used in a broad sense as including all types of fibres,

filaments, threads (spun or twisted) and the like Usually the organic material is adsorbed on the yarn after the yarn is incorporated in a fabric, but this is not necessarily thecase. In this connection, the process is applicable not only to woven fabrics, but also to knitted fabrics, such as hosiery and all types of other fabrics.

This invention not only is applicable to the delustering or other modification of artificial yarns,

e. g., artificial silk yarns or combinations of arother kinds of animal or vegetable yarns occurtificial yarns with other yarns of fibres, but also is applicable to all yarns or fabrics such as thosemade wholly or partly of wool, cotton and all ring either as individual yarns or in the form of fabrics. In practising this invention, the yarns or fibres are superficially modified by a blending or incrustation of the colloid material of the fibre I with the adsorbed coagula of the added material,

with the resultant production of a fibre which,

superficially at least, is a new and difierent material from the original fibre prior to treatment. The new yarn in which can be preserved homogeneity of colloidal structure throughout, is essentially a new material exhibiting different properties of light reflection and refractionand exhibiting different properties of surface rough-- ness and frictional characteristics, and exhibiting difierent properties of softness and "hand as compared with the original material.

While this invention has been described in connection withspecific examples, it is to be understood that this has been done merely for the purpose of illustrating the practice of this invention and that the scope of this invention is to be limited only by the language ofthe following claims.

We claim:

-1. A method of delustering yarn which com-.

prises affixing to the yarn by adsorption an amino-protein colloid, the protein in said colloid being treated with a pectizing agent for the protein prior to the completion of'the process and said colloid being adsorbed on said yarn in the form of amorphous coagula, in minute individual particles that in the resulting product are pec- 'tized and impart a delustered appearance to the *2. A method ordelustering a yarn which comprises the aflixing to said yarn of an organic material comprising a protein, said method including the adsorption of said material on said yarn in an amorphous colloidal state in minute individual particles from a colloidal solution of material comprising protein to impart a delustered effect to the yarn, the reaction of said protein with an amine, and the reaction product including both the protein and amin components thereof being produced in a pectized condition by a pectizing agent prior to the completion of the process.

3. The method according to claim 1 wherein the protein and the amine are first adsorbed on the yarn in an amorphous colloidal state from a colloidal solution, and then are treated with a pectizing agent for the protein.

4. A method of ,delustering a yarn which comprises the aflixing to said yarn of an organic material comprising a protein, said method including th adsorption on said yarn in an amorphous protein colloid together with pectizing agent therefor carried thereby constituting the major proportion of the material adsorbed by said yarn.

9. A method of delustering yam which comprises the adsorption on said yarn from a colloidal solution of an organic nitrogen-containing colloidal state from a colloidal solution of material comprising protein, the reaction of said protein with an amine, and the metalizing of said protein with a non-alkali metalby reacting the protein with a soluble salt of a non-alkali metal,

and the metallized protein-amine complex being produced ina pectized condition by a pectizing agent prior to completion of the process and being produced in the form of minute independent particles that impart a delustered appearance to the yarn.

5. The process according to claim 1 wherein the amine is reacted with a material adapted to lower the normal pH of the amine to thereby lower the pH of the amine to about 7 to 7.5.

' '6. The process according to claim lwherein the amine is hexamethylene tetramine. 1

7. A methodof delustering yarn'which comprises the aifixing to said yarn of an organic material comprising a nitrogen-containing organic substance selected from the group consisting of proteins and alkaloids, said method including the adsorption on said yarn in an amorphous colloidal state in minute individual particles from a colloidal solution ofmaterial comprising said substance, the reaction of said substance with an amine, and the treating of said substance with a pectizing agent therefor.

8. A method of delustering yarn which comprises the adsorption on said yarnfrom a colloidal solution of a material comprising protein,

the reaction of the protein with a soluble 'nonalkaline metal compound to form an amorphous metal protein; colloid and the reaction of both the emetal and the protein c ,mponents of the colloid with an organic'pectizing agent to form apectized amorphous colloid complex, said complex being affixed to said yarn in the form of adsorbed minute independent particles that impart a delustered appearance to the yarn, and said metalsubstance selected from the group consisting of proteins and alkaloids, the reaction of said substance with a soluble non-alkali metal compound to form an amorphous metallized unpectized colloid and the subsequent pectization of said colloid including both the substance component and the metal component thereof by reaction with an organic pectizing agent to produce the metallized colloid in a pectized amorphous state, said amorphous metallized colloid in said pectized state being afiix'ed to said yarn in the form of adsorbed. minute independent particles that impart a delustered appearance to the yarn.

10. A method according to claim 9 wherein non-alkali metal is a heavy metal.

11. A method according to claim 9, wherein the non-alkali metal, is selected from the group consisting of arsenic and antimony.

12. A method according to claim 9 wherein the metalized colloid in unpectized condition is first adsorbed by the yarn and thereafter is pectized while adsorbed by the yarn.

13. An article of manufacture comprising delustered yarn .having adsorbed on the surface thereof in the form of minute independent particles amorphous colloidal organic material comprising a protein-amine, the protein in said material being in the presence of a pectizing agent for said protein.

14. An article according to claim 13 wherein the said material adsorbed on the yarn includes a pectizing agent for the amine.

.15. An article of manufacture comprising delustered yarn haying adsorbed on the surface thereof in the form of minute independent particles of amorphous coagulacolloidal organic material comprising a non-alkali metal complex compound of protein, an organic pectizing agent for the protein and an amine.

16-. A method according to claim 4 wherein said the pectizing agent is an organic pectizing agent.

17. A method according to claim 4 wherein the protein that is reacted with an amine is metallized with a non-alkaline metal to form a colloidal solution of metallized protein-amine complex, the metallized protein amine complex is adsorbed by the yarn from colloidal solution, and

the metallized protein amine complex thereafter 1 is pectized by a pectizing agent to form on the yarn amorphous pectized coagula in the form of minute independent particles.

18. An article according to claim 15'wherein the said material adsorbed in the yarn includes a pectizing agent for the amine.

ROBERT S. HOLT. VICTOR CHARLES EMILE LE GLOAHEC.

. CERTIFICATE OF GORR ECTION Patent No. 2,505,006. December 1 19h2.*

ROBERT s. new, ET. AL.

It is hereby certified that error appears in. the printed specification of the above numbered 'patent requiring correcticn as follows! Page 14., s'ec 0nd column, line 20, for "colloidal" read colloid; line 67; for the word "reached" rad --reacted--; page 9, second column, line 59, fdr "of fibrestread "pr fibres; and that the said Letters" Patent should be read with this cdrrection therein that the same may conform to the record of the case in the Patent Office;

Signed and sealed this 26th day of January, A. Do 1911.50

Henry Van-Arsda'le, (Seal) Acting Commissioner of Patents,