US3668001A - Fibrous structure having durable elasticity and crease-resistivity and its manufacture - Google Patents

Abstract

A FIBROUS STRUCTURE SUCH AS YARNS, FABRICS, CLOTHS AND THE LIKE, HAVING DURABLE ELASTICITY AND CREASE-RESISTIVITY, PARTICULARLY LADIES HOSIERY HAVING EXCELLENT SMOOTHNESS, SOFTNESS AND STRETCHABILITY, WHICH IS MANUFACTURED BY APPLYING HOMOGENEOUSLY TO A FIBROUS STRUCTURE AT MOST 10% BY WEIGHT, BASED ON THE STRUCTURE, OF POLYORGANOSILOXANE PREPOLYMER IN THE FORM OF ITS NON-AQUEOUS SOLUTION TOGETHER WITH CATALYST FOR POLYMERIZATION THEREOF AND THEN BY HEATING THE STRUCTURE AT 50-200*C. TO POLYMERIZE PREPOLYMER THEREON INTO POLYORGANOSILOXANE HAVING AN ELONGATION AT BREAK OF AT LEAST 50%, A TENSILE STRENGTH AT BREAK OF 1-50 KG./CM.2 AND A HARDNESS OF 5-50*.

Description

United States PatentO flee I FIBROUS STRUCTURE HAVING ,DURABLE ELAS- TICITY AND CREASE-RESISTIVITY AND 'ITS MANUFACTURE Kenjiro Hosokawa, Osaka, Masao Matsui, Takatsuki, and

Noria Endo,Michio Ishikawa, and Susumu Tokura,

Osaka, Japan, assignors to Kanegafuchi Boseki Kabushiki Kaisha, Tokyo, Japan No Drawing. Filed May 29, 1969, Ser. No. 829,135

Claims priority, application Japan, Mar. 28, 1969,

Int. Cl. D06m 15/00 U.S.- or. 117-1394 7 a 29' Claims ABSTRACT OF THE DISCLOSURE. A fibrous structure such as yarns, fabrics, clothes and the like, having durable elasticity and crease-resistivity, particularly ladies hosiery having excellent smoothness, softness and stretchability, which is manufactured by ap' plying homogeneously to a fibrous structure at most 10% by weight, based 'onthe' structure, of polyorganosiloxane prepol'ymer' in the form of its non-aqueous solution together with catalyst for polymerization thereof and then byheating the structure at v50200 C. to polymerize prepolymer thereon into polyorganosiloxane having an elongation at break of at least 50%, a tensile strength at break of 1-50 kg./cm. and a hardness of -502 This invention relates to fibrous structures, such as yarns, knitted goods, woven fabrics, non-woven fabrics, made-up clothes and the like, which are provided with durable elasticity and crease-resistivity, particularly to ladies hosieries having excellent smoothness, softness and stretchability,"and also to a manufacture thereof By the term fibrous structure used in this specification and claims is meant a'structure' composed of staple fibers, continuous filaments or a mixture thereof, such'as a yarn, strand, rope, net, knitted goods, woven fabric, non-woven 3,668,001 Patented June 6, 1972 decrease-the frictional resistance of the fiber. However, the bending and abrasion resistances, the tearing'strength and tensile strength at break of the resin itself are so small that it is impossible to expect durability in elasticityaand crease-resistivity of the article treated'with such agents.

,On the other hand, a matter of great concern for imparting a shrink-proofing ability to fibrous structures, specifically Woolen structures, is a chemical finish for preventing an irreversible shrinkage of fibers (a felting effect) which is caused by interlacing of fibers in the woollen mass. Upon interpretation by Speakman, Harris and many in Water which are inherent thereto, a number of'methods,

fabric, felt, filter-cloth, substrate for synthetic leather, gar I ment and'the like. One of the most'importantfibrous structures in the present invention is a knitted fabric, especially a ladies hosiery.

In orderto improve characteristics, particularly elastic properties, 'of fibrous structures, it has so far been regarded as an appropriate method to incorporate a polyurethane elastomeric yarn in the structure, which, however, needs a complicated process and cannot be said to be the mostsuitable way for obtaining a'fabric with light Weight. Methods-for improving crease-resistivity which have been generally put. in practice are: (1) to increase resiliency of fibers in the structure (by resin-finishing with a condensation resin), (2) toimpart a sizing effect to the structure (by finishing with a polymerization resin or latex), (3) to lubricate fibers (by finishing with a silicone resin or an emulsion of polyethylene), etc; And in fact, the above method (1) is not effective for theimpro'vement of elasticity, particularly, an elastic recovery from extension of knitted or woven fabrics, though it contributes to the improvement of crease -resistivity,and the method (2) is aimed to fix the fibers to each others in the structure, so that they may 'not be slid and shifted when the structure isdeformed or folded up, but..on the contrary, it has such a "drawback that the structure, e.g. fabric is apt to be sharply creased. Such a drawback is somewhat eliminated when a soft resin is applied, but the softening alone is not enough for fully satisfyingall efi'ects originally expected from the sizing. Furthermore, the above-mentioned method (3) seems to be a good'one at a glance, for silicone type softening agents orwater-re pellents are coated over the surface of the 'fiber and auto heretofore, have been proposed and tried as the shrinkproof finish. Those methods are, for instance, (4) to modi fy the scale to decrease the DFE, (5) to cover the;scales to eliminate the DFE, (6) to introduce cross-linkages into the molecular structure of the fiber to improve itsmodu; lus in a wet state, whereby its resistance to deforming force is enhanced and (7) to bond cross-over contacts 'of fibers to hinder their relative movement. For the method (4.), use has so far been made of oxidizing agents such as an inorganic or organic chlorinated compound and a monopersulphuric acid which have ability for breaking cystine linkages, and in fact, since those agents have been put to practical use in the form of aqueous solution in which the wool fibers swell, it has been impossible to treat fibers,.attacking their scales alone without destroying their cortices/For the method (5), cellulose acetate, silicone resins, melamine resins, etc. are supposed to be applicable as the covering agent, but none but a process of interface P polymerization of nylon has been employed to add to prac- 5 tical value, though it cannot be said to be satisfactory as yet because of harsh hand of the finished structure, according to the result of the inventors investigation. The method (6) wherein diisocyanates, acrylic monomers or methacrylic monomers are used as cross-linking agents, and the method (7 such as the so-called Lanaset process in which methylol melamine is employed and the socalled Pontex process in which a rubber latex is applied, are bothjdisadvantageous for practical purposes on account of inferiority in hand and in durability of effect of the resultingproduct as well as in view of the high cost for the production in either case. As explained above, it has so far been difiicult to hinder the felting-contraction without any concern for bringing about harsh hand, degra-v b the treated fibrous structure, anyway;

7 Furthermore, stretchable ladies hosieries, for instance, stockings have heretofore been knit with a so-called torque-yarn prepared by a false-twisting or high-twisting process and however, the torque-yarn as such adds to the cost due to its low production efiiciency and further it has such a drawback that the knitting operation is difiicult owing to its intensive torques. Therefore, recently use has been made of a process for manufacturing stretchable hosieries, which process comprises knitting into hosieries a unitary composite filament ha'ving latent crimps, namely,

made from a unitary composite filament, generally have such a disadvantage that they have filament-loops on their=- own surface which are formed of the crimped filament when the stockings shrink, whereby another body in con-' tact therewith is readily caught so that a run or laddering is formed on the stockings in consequence. It may be possible to prevent the formation of run to some extent by knitting into what is called non-run stitches, while on the contrary, stockings having non-run stitches are, in general, inferior both in stretchability and in softness. Particularly, stockings main portion of which is 'knit with a unitary filament, generally exhibit less softness, because a filarnent of comparatively high denier has to be employed to impart enough strength to the stockings, and the non-run stitches further reduce the softness. The softness of the stockings may be somewhat increased by employing a multi-filament yarn of 15-30 denier of 2-5 compositefilaments to form the main'portion' of the stockings andnevertheless, stockings composed of the multi-filament yarn of composite filament generally have drawbacks such The polyorganosiloxane prepolymer to be applied to the present invention is" a-lineaFpolys'iloxane ha'ving as an enfeeblement in extensibility as well as 'inrecoverability from extension, due to a mutual frictionalresis'tance of the unitary filaments which constitute the multifilame'nt yarn, and moreover the softness is still not'entirely satisfactory.

A method for'decreasing fragility of stockings of plain I stitches knit'with a composite filament and increasing the extensibility and softness of stockings of non-run stitches knit with a composite filament as well, is for instance, to impart smoothness to the stockings by means of softening agents. However,usual softening agents which comprise oils and surface active agents as the principal components thereof provide fibrous structures with an extremely low durability for washing.

We, the inventors, have made various studies and investigations, to overcome the above-mentioned diff ficulties, on the finishing of fibrous structures to impart the afore-mentioned various favourable characteristics thereto, discovered the facts that a physical'treatmeut is more preferable to a drastic chemical treatment and that from such viewpoint, there needs a polymer for covering fibres which possesses the ability of forming thin and tough film, the ability of adhering to fibers, the durability for mechanical stresses such as compression and extension and which further does not swell in water and at last accomplished the present invention by utilizing a silicone elastomer having an excellent elastic recovery from extension, a high tensile strength at break, etc.

It is an object of the present invention to obtain fibrous structures, such as yarns, knitted goods, woven fabrics, non-woven fabrics, made-up clothes and the like, which are provided with a durable elasticity, crease-resistivity, shrink-proof ability and durability for washing.

Another object of the present invention is to furnish highly stretchable knitted fabrics, particularly ladies hosieries having a durable smoothness, increased softness and prolonged life of utility.

"Still another important object of the invention is to provide a process for manufacturing fibrous structures having a durable elasticity, crease-resistivity, shrink-proof ability and durability for washing, more particularly high 1y stretchable ladies hosieries possessing a durable smoothness, increased softness and prolonged life of utility, easily and cheaply in a commercial production.

hydroxy groups directly bonded to its silicone atoms as its end groups, which is represented by the general formula, HO-(SiR R"O) -H, wherein R and R are respectively lower alkyl groups having 1-5 carbon atoms such'as methyl, ethyl, propyl, butyl and pentyl groups; ormaybe j tCHM-CN, age, ;o.cH='. j

etc. Mention maybe made of, numerous 'c onrpounds as such. What is commonly put to'use comprises, as its principal constituent, those havinglower alkyl groups as side chains thereof, such as poly (dimethyl siloxane) diol and poly (diethyl siloxane) diol or those having aromatic groups as side chains thereof, such as poly (methylphenylx'siloxane) diol and poly-(diphenyl siloxane) diol. A polyorganosiloxane prepolymer having its principal constituentof poly (lower alkyl siloxane) diol is preferable for the objects of the present invention. When R and R are, for instance, phenyl groups instead of CH groups, the heat resistivity of the prepolymer is increased and when nitrile groupsare introduced, the oil-resistivity is improved. However, the preseut invention is not restricted by the sort of the side chain, and R and RT may be sarneor difiFerent groups. Besides, alkyl hydrogen polysiloxane e.g. methyl hydrogen polysiloxane can be eflfectively employed iucombination with those compounds as mentioned above.

The non-aqueous solution of polyorganosiloxane pre- Compoundfi,

Other objects and attending advantages will becorne ap- I parent from the following description of the invention. j The above-mentioned objects are attained by applying homogeneously a non-aqueous solution of poly-organosiloxane prepolymer, in such an amount as not exceeding 10% by weight of the polyorganosiloxane component, to-

break of at least 50%, a tensile strength at break of 1-50 kgJcm. and a hardness of 5-50 is fixed upon said structure.

polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene. alkyl amine, ,polyoxyethylene alkylphosphate and polyoxyethylene, sorbitangfatty acid ester, whichare effective for providing the treated,- strucjtures. with an anti-static property.and for=eliminatingwaxy hand of the structure. Number of moles'of, OXY? ethylene units contained in the polyoxyethylene group of the above-listedpolyetheric compounds. is preferably about 5 to-40 and-as faras polyoxyethylene fatty,.acid

: esters and polyoxyethylene.alkylphosphate concern,; it

should be confined in the rangebetween about Sand 20. An appropriatenumberof carbon atoms possessedby the alkyl groups-in the compounds isasfollows:

Number of carbon atoms Polyoxyethylenealkyl ether 10 18 Polyoxyethylene alkylphenol etherv LPolyoxyetlrylene alkyl phosphate 10-18 Polyoxyemylenesorbitan fatty'acid ester 10-13 In additionjto the above-mentioned compounds, polyethyleneglycol having its degree of polymerizationof 1-4,000, more preferably .40-2,000,ca11 also be effectivelyused.

A suitable amount of the polyetheric compounds to be added to the non-aqueous. solution is 1-50}% by weight based on the polyorganosiloxane prepolymer and preferably 320% by weight. These polyetheric com pounds may be employed either solely or in combination of more than one. a a I Generally, the degree of polymerization of the prepolymer can be properly selected according to ones purpose. For instance," a prepolymer having aldegree of polymerization of about Sil -2,000 is considerablyhigh in viscosity such, as of about 30,-10Q,0O0 cs,, so that it is convenient to employ solvent, ama on theothr hand in case that the degree of polymerization lies between about 29 and 50, since the prepolymer. has a low vis-. cosityvand high permeability, it can be readily used in the formof, an aqueous emulsion in general.

A mixture of more than-one of .prepolymerdiflering in chemical structure or in degree of polymerization can, ofcourse, be used. However, in the present. invention, since the above-mentioned prepolymer-should be polymerized upon a heat treatment into a polymer having the aforementioned physical properties, the degree of polymerization of the prepolymer is limited to an extraordinarily high order such as at least 50, preferably at least 100, whereas that of the prepolymer used for common softening agents and water-repellents is not more than 50, so that it is essential in the present invention to use a non-aqueous solvent as the solvent or thinner for the prepolymer.

A polyorganosiloxane as such can beobtained easily by hydrolyzing, for instance, organohalogen silane, organoalkoxy silane, etc. to polymerize, by polycondensing oligomers of (polyorganosiloxane) diol or :by ring-opening polymerization of cyclic polyorganosiloxane having a low molecular weight. The prepolymer conv'ertedyfith a heat-treatment and by the aid of the catalyst, to a tough elastomer having its molecular weight-of more than one hundred thousand and. more specifically of several, hundred thousands to several millions. The thus formed elastomer may. contain more or lesscross-linkages and/or branches inits molecules, or may consist of linear molecules. Y

In the process of. the presentinvention, non-aqueous solution containing generally'0.1 -l% by weight of polyorganosiloxane component israpplied to the fibrous structure by means of dipping, padding, spraying, etc.,: at a room temperature in'such an amount as not exceeding by weight of polyorganosiloxane component. The concentration of polyorganosiloxane, pick-up, etc., are appropriately controlled according to the shape of the fibrous structure, the sort of the fibers, etc., .to keep the adsorption amount of'polyorganosiloxane component not more than 10% by weight based on the structure. fl

As the catalyst to be applied in the process oflthe present invention, use maybe made of an inorganic acid, such as hydrochloric acid and sulphuric acid; an alkali, such as caustic potash and caustic soda; an-alkali silanolate derived from organosilanol; an. inorganic .salt, such as iron chloride; a metal oxide, such aslead oxide, zinc oxide and tin oxide;etc.

The most suitable is metal salts of an organic acid, such' as dibutyl tin dilaurate, dibutyl tin dioctoate, dibutyl tin snccinate, stannous octoate and chelate compounds of tin. The above-mentionedcatalysts may be used solely or combination of more thanone. 3 I 1S" The addition amount .of the above-described catalyst may be suitably determined according to the kind ofpolyorganosiloxane prepolymer applied, its concentration treating conditions and further according as the kind of catalyst employed, and it-is usually 0.0l-5.0%' by weight and preferably. 0.1l.0%; by weight, .based. on the poly-. organosiloxane component :in the prepolymer applied.

Moreover, in addition to the above-mentioned catalyst; an organic" silane compound, such' as an isocyanate of silane compound; an alkoxysilane, an acetate of silane compound, etc., may be further added, as. an accelerator of cross-linking reaction, forthe purpose of improving the adhesivity of the polyorganosiloxane to the fibrous structure. As another catalyst for effecting cross-linkingue"; action, a peroxide, such as benzoyl peroxide maybe used and a bior poly-functional compound, such as triol and a vinyl compound may be incorporated to the polymeriz-' ation materials to produce a polymer having.cross-linkages or branches in its molecules.

When fibrous structures including polyamidic fibers are treated, it is preferable to incorporate the solution of prepolymers with a small amount of compound having an afiinity for polyamide, such as that having amino groups, imino groups, carboxyl groups, amidelinkages or urea linkages; and:;compounds having a reactivity with polyamide. for instance, formaldehyde.v As a resultof the above, the adhesion between the fibrous structure and the polyorganosiloxane is improved .and particularly, durability of adhesion is highly improved. The abovementioned compound is usually added in an amount not more than 15% by'weight based on the polyorganosiloxane.

As a non-aqueous solvent to be put to use in the process of the present invention, for instance, mention may be made of toluene, xylene, benzene, perchloroethylene, trichloroethylene, gasoline for an industrial use, chloroform, methyl chloroform, methylene chloride, etc. These solvents can be'employed either solely or in combination of more than one.

A usual silicone resin for textile finishing with anonaqueou's fsolvent which was available in the market was tried, but the formed resinous filmshowed a low elongation at break, a small bending resistance and little durability for washing. 7 v vThe fibrous structure to which a polyorgano-siloxane prepolymer and a catalyst have been applied'is subjected to a heat-treatment at 50-200? C. to complete their reaction. The optimum temperature in the heat-treatment varies depending upon respective kinds of the treated fibrous structure, ofthe polyorganosiloxane and of the catalyst applied and upon the adhering amounts of the polyorganosiloxane and'of thefcatalyst, and further it is in an interrelationship with the period of treating time. The temperature lower than 50". C. is not advantageous, because a polymer possessing required physical properties is not obtained or a prolonged period of treating time is required. In case the temperature gets higher than 200 0., there appear such defects that the treated article is discoloured and degraded, and its resiliency is lowered. The preferable range of the treating temperature is l00l80 C.

The period of treating time can be in the broad range of 20 seconds to 60 minutes and however, particularly preferably in the range of 1 minute to 10 minutes.

The prepolymer is converted, with a heat-treatment and by the aid of the catalyst, into a network having its molecular weight of more than several hundred thousands to form a tough elastomerhaving an elongation at break of at,least'50%, a tensile strength at break of 1-50 kg./cm. anda hardness of 550.

Heretofore, for the purpose of obtaining cloths for umbrellas, rain-coats, etc. .which have water-proofing and water repellent abilities, finishing processes such as rollcoating, knife-coating and doctor-coating of taffeta, sailcloth of synthetic fiber, tarpaulin, etc. with an acrylic resin, a urethanic resin, etc, have been well-known, and in fact,, t hose finishing processes are similar to the so-called rubbencoating, so that it is the present situation that the merit and hand of the base cloth are lost. Since the above-mentioned coating methods have their object for providing a water-proofing ability to the coated article andaccording to these methods, resinous film is superimposed-and adhered on the surface of the fibers, then the hand of the article becomes rubber-coated tone, so that the hand of the fiber itself cannot be effectuated. We, the inventors, .have found out each of the afore-mentioned requirements, as a result of various investigations on the properties of the resin to be used, various physicalprop ertles of the -fixed polymer after a polymerization treatmentfthe 'amount of the fixed polymer, etc. Namely, "in the present invention, as described hereinbefore the "polymer Which has been polymerized after adhered onto or impregnated into a fibrous structure satisfies each condition of an elongation at break of at 1east' 50%,' :a tensile strength at break of 1-50 kg/cm. and a hardness of 5-50".

\Furthermore, the preferable polymer, when formed in a; shape ofstring or thin tape, exhibits an elongation at a modulus of at most 1 g./ d.

The elongation at break, tensile strength at break and hardness are to be determined according to JIS-C-2123 asfollows:

ELONGAT'ION AND TENSIVLE STRENGTH Y AT BREAK A "test-piece in the shape of dumb-bell is cut outof silicone rubber sheet which is formed on 'aglass'plate or' in a porcelain vessel by polymerizing the same solution of polyor'gauosiloxane prepolymer as "is applied'to a fibrous structure according to the present invention. The size of the test-piece is mm. width, mm} length and 3 mm. or less thickness, respectively for itsfstrjai'ght por tion. The test-piece is stretched-at 20 C. onIristr'On universal tension tester (manufactured by Instron Engineer ing Corp., U.S.A.) ata stretching rate of 500125 mm./ min. until it breaks, and then the maximum load and length of the straight portion are observed. The elongation and tensile strength at break are calculated by the following formulae respectively: EB=L1 'L0X where, E is percentage of elongation at break; Lo,'the original length (mm.') of the'straight portiong and le' the length (mm.) of "the straight portion at break;

where, to T is tensile strength at break (kg. crni F the maximum load (kg.); and A, cross-sectional'area (cm?) of the straight portion.

When four obtained values resulted from repeated tests with respect to B or T on four test pieces are denoted as S S S and 8,, which are in a relation of:

then E or T is determined by the following equation:

E or T =0.5S +0.3S +0.1(S +S HARDNESS A flat-surfaced test-piece having its thickness of at least 12 mm. is prepared. When its thicknessis'lesstha'n' mm., a plurality of such test-pieces are superimposed each other until total thickness reaches to 12 mm. or more. Upon the test-piece is placed a spring-type hardness tester which comprises a flat pressing surface providedwifh a hole having a diameter of at least 10 mm;, a vertical pressing needle which *is sprung forthout of said hole beyond the pressing surface and is positioned-atthe ce'nter of said hole, and-a pointer which exhibits-the amount of movement of the needle according as thehai'dneis's of the test-piece. t

' When the elongability is less than 50%*;'the formed film is so brittle that the fibrous structure having durable elasticity, crease-resistivity, shrink-proof ability-and durability for washing cannot be obtained. The preferable value of the degree of elongation at break lies in the range of ISO-800%. Tensile strength at break is 1-50 leg/cm; and preferably 3-20 kg./crn. When itis lower than: 1

' kg./cm.3, the formed film, is so brittle that the'resultant fibrous structure is not satisfactory as its mechanical strength decreases, and on the other hand, when it is higher. than 50 kg./cm. the hand and feel of the treatedgfibrous structureare considerably impaired, whereasthe hardness increases. The hardness should be 5-50 ar rd preferably. 8-30. In case that it is less than 5, the film-formability is insufficient, and on the other hand the hardness which exceeds 50 is not desirable, because the treated fibrous structure becomes rigid and the hand and feel: are marked ly deteriorated.

Furthermore, an important requirement for obtaining a fibrous structure having durable elasticity, :creaseer'esistivity, shrink-proof ability and durability foriwvashing toganosiloxane adhered to the fibrous structure. Namely, in the present invention, at most-l0% by weight of thepolyorganosiloxane having the aforesaid physical properties must be adhered or impregnated to the fibrous structure. The amount of-the adheredor impregnated polyorganosiloxane' is usually in the range of- 0.05-10% andpreferably. 0.25% by weight based on the fibrous structure; When the amount is'less than 0.05% by weight, the elfect of the treatment is insufl'icient and on the otherhand, when ittexceeds 10% by weight, it is undesirable because defectssuch as the lowering of compression degree, the decrease of bulkiness and chalk marks are brought about. Fibrous materials which constitute fibrous structures toube applied 'to' the present invention arenatural fibers, synthetic fibers, regeneratedrellulose or their blends :in the form' of staple,'-filament ortheir mixture. As the natural fibers, mention, mayv be made .of wool, silk, .cotton, hemp, etc.; as the .syntheticsfibers, vpolyesters,'polyamides, polyureas, polyacrylonitrile, polyvinyl alcohol, polyolefins, polyvinyl chloride, 'polyvinylidene chloride, polyurethanes, etc.; and as the;regenerated.celluloses,viscose rayon, cupra, cellulose acetate, cellulose triacetate,etc.

.\Although.the;fibrous. structures may be composedof staples alone, like as-a spun staple: yarn, needle-locked non-woven. fabrics'and the like,.yetthe process. of vthe present invention can bemore favourably applied to fibrous structures comprising at least 20%"of continuous filaments,.'such as yarns, knittedwgoods, woven fabrics, made-up clothes and'the like, which-"are, for instance, yarnsona skein, cloths, piece-goods, shirts, hosieries, tights, gloves andthe 'like.. Asfor the texture of the fibrous structure a coarse structure may be provided with the greatest effects. The'present invention is, of course, not confined within knitted goods, woven fabrics and non-wovenfabrics. The process of the present invention is particularly effectivefor'fibrousstructures,'espe cially for ladys hosieries, consisting of continuous filaments alone and even in' case that'continuous filaments areus'ed' along With-staple yarns, for instance, as blended yarns,-tmixed' woven; fabrics, etc-.,"durable elasticity and excellent crease-resistivity are imparted to such structures,1=as long'as-the-content ofthe continuous filaments is 20% 'or-*more.-- i

Now, a treatment of ladys hosieries e.g'.stockingswhich is one OfgthC most importanrembodimentof the present invention will be described in detail-hereunder. r For the manufctureof ladys stockings,;bo,th of a mul: ti-filament yarn and a unitaryfilamentyarn can be applied in general and however, the. multi-filamentv yarn most des'irably. applied to, the; present invention is, that of 1-0.-3O denier of 2'-.-5 filaments which .consists of composite filaments having latent erimps that. can be 'developed upon. heating. Thecompositefilamentas such can be-prepared by. the process comprising; separately melting'at' least two't fiber-forming thermoplastic synthetic polymers, extruding the molten polymers simultaneously'from-the 'same'orifice-of a spinneret :to form a unitary filament consisting 'of'at-least two components ofzsaidpolymers differing in shrinkability'uponxheating wherein said components are adherent to and disposed in an eccentric relation witheachothers throughout the entire length of the filament, and drawing the extruded ifilament.

Stockings composed of. a multi-filament yarn mean those having their 'principal' portion eg a leg portion knit with a multi-filament yarneither solely or in combination-with a unitary filament' yarn. Furthermore,='a unitary composite filamentyarn having' latent crimps can'be used with advantages; Stockings composed of a unitary -filamentryam means those having their principal portion knit with a :unita'ry filament yarn and their-toe,-

heel, solet'and welt may be-with amulti-filament yarn.

-The principalrportion of the'stockings may be knit into anysti-tches, for instance .plain" stitches, non-run gether with desirable hand, is the amount of the polyorstitches :(run-proof stitches), meshes," micromeshes, jac-1 quards and the like. By the term stockings used herein is meant ladys seamless stockings, panty-stockings and the like. Subsidiary portions of stockings, namely, toe, heel, welt, pants, etc., needless to say, may be knit in any fashion with any sort of yarn.

A process for manufacturing stretchable stockings from a composite filament yarn comprises sequential steps of knitting, crimp-developing, dyeing and boarding. In order to obtain highly stretchable stockings, it is necessary to treat the stockings with polyorganosiloxane prepolymer after the crimp-developing step, namely, the treatment according to the present invention may be conducted'before the dyeing step, or before or after the boarding step. However, since stockings treated with polyorganosiloxane have somewhat decreased dyeability, it is more desired to conduct the polyorganosiloxane treatment after the dyeing step. Particularly, it is preferable to perform the polyorganosiloxane treatment on stockings which have been boarded and then allowed to relax for a period sufficient for releasing their residual shrinkages, for in this way the stockings are provided with the most uniform and balanced appearance and with an excellent extensibility.

The dyed stockings are steeped in a non-aqueous solution of polyorganosiloxane prepolymer, squeezed to gain a suitable pick-up and dried to polymerize the prepolymer. A baking or curing step may be further added after the drying step, if required, to accelerate the polymerization reaction. It is most preferable to carry outv the polymerization reaction, i.e. the hardening treatment, as the stockings are in a sufiiciently contracted condition, so that attention should be paid to minimize the tension of the stockings to the possible extent.

The amount of the polyorganosiloxane fixed upon stockings is preferably 0.l-% by weight based on the weight of the stockings and more preferably 0.33% by weight. If it is to small, the stockings exhibit less smoothness, while it is too large, they are not only'provided with an excessively increased smoothness, but also in the worst case, the polyorganosiloxane adheres lumpily onto stitches, forming films upon meshes of the stockings, so that the appearance of the stockings is markedly impaired. Since an uneven adhesion of polyorganosiloxane readily leads to the formation of the film, care should be taken so that the solution of prepolymer adhered on the stockings may be kept in a uniform condition during the drying step.

As it is possible in most cases, to break and get rid of the film formed over meshes by applying an intensive tension of the stockings, a step as such may follow the hardening treatment. Namely, it is one of the most suitable processes, for instance, to treat stockings with polyorganosiloxane prepolymer after dyeing and then conducting the hardening treatment which is followedby boarding, because most of the afore-said films is eliminated due to the tension applied thereto when boarding.

Stretchable stockings obtained according to the process of the present invention exhibit extremely. excellent softness, smoothness, extensibleness and durability, and fit comfortably on account of the fixed polyorganosiloxane thereupon. Those eflfects can be more enhanced by knitting the principal portion i.e., leg of the stockings with a multi-filament yarn consisting of composite filaments. Moreover, the softness and smoothness of the resultant stockings are so stable that they are not substantially diminished by washing. Thesmoothness provided by the process of the present invention is far superior to that furnished by treating with a conventional softening agent comprising silicone oil (an aqueous emulsion of silicone oil, etc.). Furthermore, stockings manufactured according to the process of the present invention possesses such a smoothness that they show less probability of breakage due to scratching or yarn catching incidents. Stockings having their principal portion knit with a multi-filament yarn are more excellent in run-proofing ability, because even if some filaments of the ,multi-filament yarn be broken owing to a certain incident, yet other filaments of the yarn can sustain the stockings as unbroken.

Stocking prepared by the process of the present invention also display an excellent ability of recovering from extension.

There is seen an appreciable tendency that the appearance of the stockings having their main portion knit with a unitary filament yarn is impaired as the amount of the adhered polyorganosiloxane increases, while in case of the stockings knit from a multi-filament yarn, the abovementioned tendency is reduced.

As is apparent from the description made hereinabove, of the preferable embodiment of the present invention, the fibrous structure of the present invention exhibits excellent tensile elasticity and compressive elasticity according to the resisting force against an external force whichis due to an action of incorporated polyorganosiloxane as a member in the fibrous structure, and therefore, the obtained fibrous structure is provided with durable elasticity and crease-resistivity, and displays shrinkpro of ability and durability for Washing.

A resin finish of fibrous structure in the past has been accompanied with an action of fixing cross-over contacts in the structure, which has provided the structure, specifically fabrics, with flat hand, and it has been inevitable for the stretchability of the structure such as knitted goods to be impaired on account of the fixation of crossover contacts of yarn loops. However, in the process of the present invention, as the resin is high in tensile elasticity as well as in toughness, even if it exists on the crossover contact of fibers, the treated structure not only becomes stabe but also exhibits a satisfactory stretchability.

In addition to the astonishing improvement in elasticity and crease-resistivity of fibrous structures, the process of the present invention has outstanding features including that the crease-proof finish of silk structure can be effected Without deteriorating its hand and that the shrink-proof finish of woollen structure has been realized and particularly, woollen structure having a wash-andwear property which is durable for washing can be readily obtained, and furthermore, it is a prominent merit that since the fibers are treated with non-aqueous solution in which the fibers do not swell, so the fibers are not deformed keeping their contour in entirely natural state.

Another great advantage of the present invention is that the fibers are not degraded and the tearing strength of the structure is markedly increased. Besides, fabrics obtained by the process of the present invention have resiliency and dimensional stability, so that they are easier to cut and make up into garments with than the non-treated fabrics.

Another important merit of the present invention is that when fibrous structures are treated with a solution of polyorganosiloxane prepolymer containing the aforementioned polyetheric compound, the resultant structures possess a surpassing antistatic property, whereas most of resin-finishes provide structures which are readily statical- 1y electrified. Thus numerous troubles with which the static electrification is accompanied, such that an electrified body is readily soiled, diflicult to process and uncomfortable to wear, can be solved by the present invention. Moreover, the application of the polyetheric compound eliminates the waxy hand of the fibrous structures which may be a trouble sometimes encountered by a polyorganosiloxane finish, particularly when the adhesion amount of the prepolymer becomes in excess of the preferable limit.

Still another advantage which the fibrous structure of the present invention has is that although it is observed the dyeability of the structure of the present invention is slightly decreased as compared with that of non-treated structure, none the less it is able to be post-dyed, by which a great merit is brought about. Hitherto, a dyeing process of fibrous structures, such as fabrics and made-up clothes,

1 1 has been carried out by means of a wince or a rotary dye ing machine, during which process creases, particularly rope marks given to the structures have been concerned about. Since the fibrous structure of the present invention is excellent elasticity and crease-resistivity, it is scarcely crease-set in water, so that the above-stated difiiculty is overcome. Such a merit has never been obtained by any conventional resin-finishing process, till heat-stabilized and chemical-proofing polyorganosiloxanes are adequately put in use according to the process of the present invention.

A usual silicone resin for textile finishing having a low degree of polymerization with a. non-aqueous solvent which was available in the market was tried, but the formed resinous film showed a low elongation at break, a small bending resistance and little durability for Washing.

The present invention will be illustrated in detail=with reference to examples hereinafter. The word Part used inthe examples means part by weight. Methods for determining tensile elasticity (load for elongation,-a degree of elasticity) compressive elasticity (a degree of compression, a degree of resiliency), tearing strength, degrees of elongation, crease-resistivity and shrinkage, and conditions for washing and dry cleaning-in the examples are as follows:

TENSILE ELASTICITY (1) Load for elongation-A specimen having its effec- .tive length of cm. and its width of 2.5 cm. is stretched on Instron universal tension tester at a stretchingrateof 10 cm./min. and then the load (g.) corresponding to a certain constant elongation of the specimen is denoted as load for elongation. v

(2) A degree of elasticity.A degree of elasticity is represented by the following equation:

1 2 Z l where, 1 (cm.) is the length of specimen when a load of 500 g. is applied to in the same manner as the above,(l), l (cm.) is the length measured after standing for one minute under the load followed by further standing for. another one minute under no load and l (cm.) is the originallength of the specimen.

COMPRESSIVE ELASTICITY Four pieces of cloth are superimposed to each others, the total thickness (t mm.) after a load of 10 'g./cm. 'is applied to for one minute is measured, then the thickness (t mm.) after another load of 300 g./cm. is applied to for one minute is measured and the thickness (t mm.) after standing for another one minute under no load is determined. Then, a degree of compression'and a degree of resiliency are expressed by the following equations:

Degree of compression (percent) Degree of elasticity (percent): X 1 00 A DEGREE OF ELONGATION When a specimen having its effective length of 20 cm. and its width of cm. is stretched on Inst ron universal tension tester at a stretching rate of cm./min., the length (L cm.) of the specimen corresponding to the load of 4 kg. is measured. L cm. is the original length'of the specimen. The degree of elongation is represented by the following equation:

L ,L Degree of elongation (percent) X 100 Crease-resistivity is determined according as the method B prescribed in HS L-1079-5, 22.2 B, which corresponds to a so-called Monsantos method as prescribed in -AATCC 66-1959 T or in ASTMD 1295-60 T.

A DEGREE OF SI-[RINKAGE I Broad cloth (65% polyester staple/ 35% cotton) Measurement isconducted according as the method F-3 in I IS L-1042 as follows:

1.36 kg. of sample-cloth together with a sufiicient amount of water are put into a washing machine. Steam is supplied to the washing machine concurrently with its start of operation, to raise rapidly the temperature of water until it reaches to C.,'when the steamsupply is stopped and powderly soap is charged in an amount of 0.05% by weight. After 40 minutes soaping, the hot water is replaced with clean cold water, the temperature of which. is'rapidly raised to 60C. and washed for another 10 minutes. The washed sample-cloth is dried on a flat bed press and then the distance .between marks which have been previously marked on the sample-cloth is measured. From averaged values obtained from respective three measurements in the directions of .warp and of weft, the degree of shrinkage is calculated by the following formula:

- LL' Degree of shinkage (percent)=' L Fabrics of wool or wool/silk Measurement is conducted according as the IWS-meth od asfollows:

Upon the sample-cloth, respective three sets of'marks in the direction of warp and of weft aremarked.

One kilogramme of sample-cloth together with 25 liters of water containing 0.45% by weight of sodium dihydrophosphate, 0.80% by weight of sodium monohydrophosphate and 0.05% by-weight of a nonionic surface active agent is put into a Washing machine, soaked for 15 min utes and washed for another 5 minutes. After drying by steam pressing, the degree of shrinkage is measured and calculated in the same manner as thecase of broad-cloth.

WASHING DRY CLEANING Dry cleaning is carried out at 25 C. for 3 hours with SOtime bath of'perchloroethylene;

TEARING STRENGTH The measurement of the tearing strength is conducted according as the C-method prescribed in 118 L-1079', such as follows: 1

Respective three test-piecesin the directions of warp andof weft, having 6.5 cm. width and 10 cm. length are mounted on an Elmendorf tearing tester. i

The center of the long side of the test-piece is cut by 2 cm. wide. The maximum load (kg) shown'when the remaining width of 4.5 cm. is torn off is observed;

ExampleL-A double jersey fabric (the length extended in the wale direction was 70 mm./50 courses) knitted with a false-twist textured nylon-6 yarn of 70 denier of 18 filaments/2 ply was scoured at 70 C.'for 20 minutes in a 30 times bath containing 1 g./l.v each of ananionic surface active agent and of soda ash, dried (density, wale: 30/inch; course: 45/inch), paddedwith the solution having the below-described composition (pick-up: 100%), dried again at 80 C. and then was heat-treated at C. for 2 minutes. I

The thus obtained fabrics (density, wale: 37/inch; course: 45/inch) contained 1.5% by weight of polyorganosiloxane, displayed a favourable soft hand as well as desirable draping,-and exhibited an excellent elastic vv13 recovery from elongatiomhdesirable crease-resistivity and Trichloroethylene.solution of 15 by weightofdimethyl polysiloxane diolcontaining by mole "7, of 'y-cyanopropyl methylsiloxane unit, having a degree of polymerization (F) of about 1,200. 100

Stannous octoate p I a 1 Methyl triisocyanate silane Gasoline for an industrial use 900 Parts 5 position at Crwith a bath ratio of :1 and after the temperature was raised to 95 C. at the end of minutes heating, the heating was continued to keep its temperature for another 60 minutes.

The dyed-fabric of the present invention showed a good eflect of. uniform dyeability comparing with the untreated fabric.- Moreover, it was little creased, the elesticity of the fabric was kept satisfactory and further the dimensiohalchange of the fabric vwas negligibly small. The result is shown in Table 2 which follows. The tensile elasticity was measured when the specimen was stretched 30% in the course direction.

TABLE 2 "Contraction; I pereentage of" Compressive elasticity,

m i fahric Tensile elasticity percent Lead for Degree of I elongation elasticity .Degree of Degree of Wale "Course (g.) (percent) compression resiliency is ':.U1 1treated article 1 7. 148 78.8 17.8 70.8 ention--- as v, 0 123 92.5 21.2 93.2

'Ifreated article of th 1 For the purpose of comparison, a treatment wascarried out in the same manner as above, except that use'was made of a conventional silicone finishing'ag'ents KS 714 (a 3.0% trichloroethylenesolution of methyl hydrogen polysiloxane manufactured by Shin-etsu Kagaku Kogyo K.K., F: about. 30)- which had been used as a Waterrepelling finishing and that the bath having the following composition was used.

COMPOSITION ,oFf TREATING 's'oLUrroN FOR- 35 V CO PAR SO J 1 1 Part5 KS 714 (manufactured by Shin -etsu KagakuKogyo K.K.) v I Catalyst D7 (manufactured by' Shin-etsu Kagaku p Kogyo K.K- e

v 0 Gasoline for an industrial use 950 ""The'afore'-mentioned"polyorganosiloxane 's'olutiorrand KS-7l4 were-respectively polymerized to obtain sheets having the thickness of 0.7 mrrii Thesheet obtained from theformerzexhibited the under-mentioned physical properties,lwhile-that obtained from'KS 714 was so brittle that the elongation at -break-and tensile strength at break were unable to b'emeasur'ed.

Elongation at break;-752 g. 1 I i ensile strength-at break 6 kg./cm. f j

Hardness-10f The tensile elasticity and compressive elasticity of the treated fabrics comparingwith "those of the untreated fabrics are shown in Table 1..The tensile elasticity appearing in the Table 1 was'measure d'when th'e'specimen was stretched 30% in the course direction.

The contraction percentage of the fabric represents in percentage the ratio of the length lost by contraction after dyeing to the length before dyeing.

Example 3.-A fabric of double half tricot knitted with a raw silk yarn of 21 denier of 7 filaments/2 ply was scoured at 100 C. for 1 hour in a 40 times bath containing 3* g./l. of potash soap, then subjected to a beamdyeing in a bath containing 10% by weight of Direct Deep Black EAC (a trade name of direct dye manufactured' by Ciba Co.) and was dried at 100 C. on a stenter-drier (density, Wale: 42/inch; course: 46/inch). The thus dried fabric was steeped in the solution having the under-mentioned composition, squeezed at a pick-up of. dried again at C. and then heat-treated at 120 C. for Zminutes.

.The thus obtained fabric (density, Wale: 42/inch; course: 45.5/inch) exhibited excellent crease-resistivity and elasticity," so that it was suitable for ladys clothes and gloves.

' Parts Trichloroethylene solution of 15% by weight of di- 0 methyYpelysiloxane 'diol containing 5%"by mole ofmethyl hydrogen siloxane unit (F: about 900) Dibutyl tin dilaurate 3 Tetraethoxy -silane 3 Perchlorhtliyleii" 900 "TABLE'L- I (lompressive elas tieity, percent Tensile elasticity v before washing. ;l 3eferewashing A After-washing After dry cleaning 7' Load for Degree'ot' Degreefof- "'D'egreeof 7 Degree of v elongation elasticity. c0rnp1 es- Degree of compres- Degree of compres- Degree of (g.) (percent) sion resiliency s1on resiliency sion resiliency Untreatedarticle 152 80.3 18.9 11.2 .7 K r Treated articleoitheinventiontnr 94.3 20.6 94.3 19.8 92.5 20.3 92.2 87s8 19.2 82.3 .2 71.5 17.5 73.2

Comparison.--

l iixample fabrie ebtained an and was I steeped inthe dye:bath having the underrmentiojnedrom- 75 K.K.,.Erabc t.30)-.wa sed.

polysiloxan e manufactured by Shin-etsu Kagaku Kogyo 15 a COMPOSITION OF TREATING SOLUTION v (FOR COMTAR'ISON) I e Parts KS .724 (manufactured by Shin-etsu 'KagakuI- .Kogyo K.K.) 1 50 Catalyst PD (manufactured by Shin-etsu--.Kagaku- Kogyo K;K.) 1 10 Perchloroethylene .1950

The result of comparison between two fabrics shown in Table 3 Which fOllOWS: i

TABLE 3' 'Exaniple 6; -A fabric of piledtric'ot'whicli' hadbee'n knitted with a nylon-6 filament yarn of-70denief'of 1 8 filaments-was heat-set .at 170 and ;af ter.s couring at 70 C. for minutes in a 20 folded bath containing ores/inch for the wale Compressive elasticity Crease-resistivity (percent) (percent), before .was g. Afl d y:, Before washing cleaning Degree of Degreeof V f compression resiliency Wale Course Wale Course Article of the invention. .t 22.0 96.5 77.7 79.4 77.1 77.7 Comparison 19.3. 93.2 V 57.2 58.3 58.3 66.6

The afore-mentioned polyorganosiloxane solution; and The above-mentioned fabric of piled tricot was padded KS 724- were respectively polymerized and formedinto with solution'having fthe under-stated composition and sheets. The sheet obtained from the former exhibited the under-mentioned physical properties, while that obtained from KS 724 was so brittle that it was impossible to measure the elongation at break. "'1

Elongation at break650% Tensile strength at breakfikg/cm? Hardness-10 Example 4.-A skein (500 g.) of a false-twist textured nylon-6 yarn of 70 denier of 18 filaments/2 ply was steeped for one minute in the bath used in Example. 1, after which it was put into a centrifugal separator to dry up to a water content of 22% and then air-dried. The dried yarn was heat-treated at 150 C. for 10 minutes.

The amount of the polyorganosiloxane fixed onto the obtained yarn was 0.3% by weight. 1

The treated yarn exhibited an excellent elastic recovery from extension. The treated yarn and the untreated yarn were knitted into respective socks (with plain stitch, ,w'ale: 28/inch; course: 41/inch). The socks knittedwith' the treated yarn were superior in both stretchability; and-"fit, showed little variation in density of stitches causedbyr-a fluctuation of tension in the knitting process and also the knitting operation was smoothly performed. The result is shown in Table 4 which follows:

Example 5.-Piqu, both for warp and weft of which a rayon yarn of 150 denier of 32 filaments had been used (density, warp: 65/inch; weft: 84/inch), was padded with the bath used in Example 3 and squeezed with a pick-up of 85% and heat-treated at 160 C. for?) minutes. '1

The fixed amount of the polyorganosiloxane onthe fabric;

was 1.3% by weight. The result is shown;,in Table 5 which follows:

squeezed with a pick-up of 160%. Subsequently it was heat-treated at 170 C. for 45 seconds to obtain a fabric which was provided with durable elasticity and creaseresistivity.-a j

1' --The fixed, amount of .polyorganosiloxaneon the. ob tained fabric was 4.9% byiweight. I f

COMPOSITION OF TREATING S LUTION For the purposeof comparison, a treatment was carried out in the same manner as above, except that KS 714 used in Example l was used. The result is shown in Table 6.The tensile "elasticity' wa's' measured when the specimen was stretched in the Wale direction."

'TAnLEt" i111, Ten'sileelasticity" Before washing 7 I Afterlwashlng Load fort-Degree of :"Load for "5 Degreeoi elonga elasticity .elonga-,, elasticity v tron-(g1) (percent) *tion (g.') "(perce'nfl Untreated article 142 22.2, 1481 j 115 Treated article of the e invention 150 95.3 v 153 93.2 Comparison 85.8 143 '65. 2 The afore-mentioned polyorgands iloxane was ixed and formed into a sheet having a thickness of 0'.7

which exhibited the following physical properties. Elongation at break'42f1%' H f l "f. Tensile strength-,at break-;-3 leg/err]. Hardness' 7 I,

Example 7.A satin fabric that had been woven' with a cellulose acetate filament yarn of 150 denier of 60 filaments as warps and with a top-dyed woollen yarn of 60 count as 'weft's; was padded "witlr-the' treating bath usedin Examplelisand squeezed with a pick-up of 80%. fI t wa's" then heat-treated 'at 130 C. for 3 minutes to ob tain a resilient fabric which was provided with an ex- ",gcel lent" crease-resistivity: bmparison of it with the un- TABLE 5 treated fabric is" shown-imTable lwhich follows-h. Compressive elasticity 5 i 1 TABLE 7. i "f (percent .v 70

Grease-resistivity v new Crease-resisti Degree (percent (percent) Degree of of resilcompression leney Warp Weft Warp Article of the invention-.- 14.2 94.2 145 U 131 Treated arttcle of the invention..." 81Lj7 77. Untreated article 12. 8 80.2 98 3 103 75 Untreatedarticlm, p :54. 5.

Example 8.--A sports-wear" with half sleeves knitted with a st szst rciml estsr. y? .2.9t,15Q-. lea s of 48 filaments/2 ply {havingplain stitches, density,

Wale: 25/inch; coursef 40/ inch),was'steeped'for one' coMPosIrI oN 'oF TREATING soLUrroN Parts Trichloroethylene solution of 15% .by.weig ht of ,di-

methyl polysiloxane diol (1 1,300) 100 Dibutyl tin octyl maleate laurate 0.8 Phenyl triisocyanate silane 0.8 TIlChlOI'OBlIhYleHC 900 Example 9.- s '1' gentlemen-knitted with textured nylon-6 filament yarnof 70 denier of 32 filaments/ coating. minute in the solution having the'under-mentioned com- When the fixed amount "of resin exceeds 10% by w ght. thqdssraeot com re sion vis. low ed nd h hand and feel approach extremely to those of rubber- Exar'nple --11.Two hundred grammes of a raw silk 'iyarn of 21 denier of 7 filaments/2 ply in the form of a 'skein werescoured at 100 C."f0l' 1 hour with a--40 folded bathlcontaining 3 g./l. of potash soap and dried. The driedskein was steeped in the treating solution same as 10 thaf'fisedin" Example 3, put intoa centrifugal separator (to dry up to the water content of 42%), air-dried and then was heat-treated at 105 C. for 10 minutes.

The-so obtained yarn was put into a jet-type hankdyeing' machine,"whereby it was steeped in the dyeba'th with Bath ratioof 40:1 containing solution of 1.2% by weight of Kiton Fast Violet R (a trade name-of an acidic dye manufactured by Ciba Co.) and of 2% "by weight of potash soap, was boiled for minutes, dried gradually, washed with water and then dried again. The resulting 20 yarn exhibited good effect of uniform dyeing and the p'r'tflalemof the lousiness as well as the napping which had previously been arisen in silk dyeing techniques, was eliminated and the handling of the yarn was made easier. A ladys suit was knitted with three of the obtained yarn 2 p1y"'(denSity'(wa1e:lip/inch;icofirse; (plainstitch, Wale: 27/inch; course: /inch) and the soaked 'in'the solution having the under-mentioned conrposition, squeezed with}. pick-up of and then-heat H a 5 "..,C:. .i9ri. l, xed..amount-0f article having excellent crease-resistivity and elasticity was obtained. The result is shown in Table 9 which followsr polyorganoslloxane on the obtained socks was 1.1% by weight. The socks had favourable fit and excellent elas- 30 TABLEQ ticity and moreover feet felt none of stutfiness and hu- 1 it it midity inherent nylonsocks when they were worn. 7 ig e iiesit? y 1 i geige ntl y O Q 5541 UIZQ M v $55.35;. 33:55:55? W. 0......

v w w Pa -t 35 Untreatedarticle f Trichloroethylene solution of 15% by weight of dimethylpolysiloxanediobcontaining" 5% by mole false-twist nylon-6 filament yarn of denier of 18 fila- 4 ments/2 ply was scoured at 70 C. in a 30 folded bath Article of the invention...

Example'12.-Twil1 of 2 Woollen yarns/2' wool-silk 40 blended-yarns (warpz-worsted yarn of 2/54 count; weft: 7 worsted yarn'of 2 /54 count and silk 'yarn' of 2/21 denier;

density of warp: 42/inch; density of'weftz' worsted yarn, 38/inch and silk yarn, 38/inch) was padded with the same solution as used in Example 1-('pick'-up': 66%),

5 dried at C. and then was heat-treated at C. for

3 minutes.

containing 2 1-.QfaAQPiPHiQ.sudamaetiwagem..dyechm.-- llhefthuswobtainediabric .cqntain d.Q-9.8%..hy..w i ht with 1.2% of Hakkol BS cone. (a .tradename of anionic' v fluorescence dye manufacturedby Showa' Kagalku'KK.)

of polyorganosiloxane, displayed a favourable resilient and dried. -In order .to study of the optimum amount of m -and' durability for' washing.

the resin to be employed, treating solutiofisf sa'me as: that used in Example-6 but-"the concenlrationiof 'resirr'variedfrom 0.5 to 40% by weight, wereI-prepared. I hC a;bOV-.-

mentioned dried fabrics were padded with those solu- Forpthe purpose of comparison, a treatment was carried out in the sarne manner' a's above: except that; the'sarne bath as used at' the comparison test vin Example 1 was employed.

tions, squeezed with; a pick-up b11175 drieda'gain 411E 55... eiensile-strength elastieity;--crease-resistivity and shrinkage for washing (percentage of shrinkage and W.W., i.e. Wash-and-Wear property) of the treated fabric comparing vwith those of the untreatedwfabric as well as I g of comparison-tested oneare shown inTable 10.

ABLE 2 coneentralrion 'of'solution' 0 0.076 0.15 0:45 o-.'75-"'1.s a0 4.5 an? 7.5' Amountofsilicone'fixed..-..-l -o'- 0.13 0.26 0.78 rsr asz 5L24 7.86 0.4 15.5

Physical property z I I i V ComIpressive elasticity: r 1

' egreeof compression (percent) V 18.6 "21.1 22.4 22.4 21.9 20.8 20.3 19.6 v 18.5 16.3 Degree of resiliency (percent) 69.8 79.6 82.3 83.5 85.8 84.8 85.2' 87.5 86.2 8413 Creaseresistivity: m;-

Wale ,,;-;55,6;- 17.3 $0.6 82.2 85.0 92.2 90.6 93.4 91.7 'ssxs Cmirsa 58.9 84.4 88.4 86.6 155.6 87.8 88.9 90.6 90.0 3 88.4 H'mrl d Good Good Good Good v (10011 Good Good Slightly bad.

TABLE v v t l Durability for washing'- Compressive elasticity Crease-resistivity Tearing (percent) (crease recovery Shrinks e strength (g.) ,(percent))l l:."t(percent a? Degreeot Degreeot v Warp Welt compression resiliency Warp 'Weit Warp Weft WandW Untreatedartiele 1,472 1,230 v 18.6 89.1 86.1 .,78..8 8.2 6.5 2grade. Treated articleoftheinventio 1,888 1,600 22.2 92.5 92.5 89.8" 1.0 g 1.3 4g1'ade., Comparison 1,680 1,310 20.2 90. 81.2 2.81 4.0 2 4 Example 13.A double jersey fabric knit from worsted yarn of 1/44 count (density, wale; 39/inch; course: 34/inch) was hot-tumbled to relax. The resultant fabric having the density of wale of 38/inch and that oi course of 3 5/inch, was padded with the same bath as used in For the purpose of comparisoma treatment was carried dut'in thetsametmanner as above,.'except that the same bath as used at the comparison test in Example 1 was employed. The result of comparison of those fabrics is shown in Table 12 which follows: I

- TABLE 12" Compressive elasticity Crease-recovery (percent) Cr me-recovery (percent) (percent) (after washing) 7 -Degree of Degree of I eompressionresiliency Warp Welt I Warp Welt Untreated article 20.5. 85.1 85.5 g -87.3 81.6 83.8 Treatefd article ofthe invention I 27.0 i-89.5-- 189.8 92.3 87.9 89.9 7 86.2 84.2

" Comparison in Table'll-which follows:

f'T'iBLE 11 Compressive elasticity (a 1 (percent) (percent) The "aforementioned peiyar an'snoxane solution was p ym i to O n? s eet ha g 'thiq ne of 0-7 mm. which exhibitedan elongation at break of 424%,

a tensile strength at break of 3 kgJcm. and a hardness of8i.

Example l5,-Skiers,, socks knit .from woolen'ayarn .which had had their toes and heels reinforced gby nylon-fi Y 9 P l9 E;3.5 w o ndo y n; density, wale: 5/inch; course: ;8 inch) were soakedin t S n h v thenpqs idcsc po i worked in a centrifugal separator to reduce the water content to and then dried-at C. for' 1.5 min- Compressive elasticity Durability-for washing Tensile elasticit fter dry cleaning) (60% elongatiouyl V ,7 Degree of Degree of compression resiliency Deg'r'eeol Degreeof I Untreated article. 24. 4 89. 5 g 25. 2

Treated article of the 111- 27. 5 95. D 27.3

vention. 7

Comparison......'.'..;...'...; 7 91.5 24.8

Shrinks e (percent Degree ol' Load elasticity compression resiliency Wale Course Wand W (g.) Y (percent-)j 88.2 '12.:3' 15.4 1,5 gradea 34.8

94.0 2.2 1.3 4grade.. 15 2 95.6 89.5 10.1 153 8&7

8,5 2 grade;

Example 14.Twill which had been woven with Torelon yarn (a trade-name of polyacrylic yarn manufactured by Toyo Rayon K.K.) (warp: 1/50 count; weft: 1/32 count; density of warp: 86/inch; density of weft: BO/inch) was padded with the solution having the understated composition (pick-up: 60%), dried at 80 C. and than is 1191ct scene h sultant, fabric contained 1.62% by weight of polyorganosiloxane,

excellent crease-resistivity.

COMPOSITION OF" TREATING SOLUTION :Parts Trichloroethylene'solution of 15 by weight of dimethyl polysiloxane diol (F: about 200) 1:80 Dibutyl tin octyl maleate laurate 3.

Trichloroethylene displayed a favourable resilient hand andexhibited an" utes. The resultant socks contained 2.5% by weight of 60 polyorganosiloxane, displayed favourable elastic and warm hands, and had a suppressed felting tendency due to washing as well as wearing.

COMPOSII QN VOBTRBATING SOLUTION organosiloxane and exhibited thick hand and an excellent crease-resistant ability.

Comparison of the socks treated as above, those nontreated and those treated with conventional shrink-proof ,finish,is shown in Table 13 which follows:

TABLE 13 Durability for washing Shrinkage Shrinkage Compressive elasticity 1 (percent) Degree of Degree of l Compressive elasticity was measured with respect to two socks which were superimposed on each other. 1

1 Socks for comparison were treated with aqueous solution of 3.0% by weight of Basolan DC (a trade name of a felt-resistant agent for wool manufactured by Badische Anilin & Soda Fabrik, .A.G. in Germany).

Example 16.A skein of pure woollen yarn (500 g./ COMPOSITION OF TREATING SOLUTION skein) was soaked in the same bath as used in Example 1 for one minute worked in a centrifugal separator to Parts reduce the water content to 50% and then subjected to g i ii gi i s bysigelght of d1 50 air-drying, followed by 15 minute cure at 100 'C. The g; g i out 1 amount of polyorganosiloxane fixed upon the yarn Was i gg g g g 23 3 m e ""7 1 0.78% by weight. No appreciable shrinkage of the yarn Perchlomethylene 950 was observed and the resultant yarn has favourable hand. A sweater knit with the thus treated-yarn exhibited The comparisonbetween the fabrictreated according favourable hand and durability for washing, and had to the process of the present invention and untreated an excellent dimensional stability. Moreover, knitting 3 fabric is shOWn in Table 15 which follows:

TABLE 15 Compressive elasticity (percent) Crease-recovery (percent) Tearing strength Before dry cleaning After dry cleainng -(g.) Beforedrycleaning After dry cleaning 7 Degree of Degree of Degree of Degree of Warp Weft compression resiliency compression resiliency Warp Weft Warp Weft Untreated article 1, 920 2, 048 27. 2 78. 8 26. 5 79. 2 76.8 77. 2 75. 2 76.2

Treated article of the invention. 2, 368 2; 816 27. 0 I 89. 7 26. 2 88. 2 86. 6 89. 4 87. 6 87. 2

operation was far more smoothly performed with the treated yarn than with the untreated yarn.

Comparison between the two sweaters knitrespectively with the treated yarn and with thenuntreated yarn is shown in Table 14 which follows:

TABLE 14 Compressive elasticity Tenslle elastlcity Durability for washing (percent) Degree of Degree of Degree of Shrinkage (percent) elasticity compression resiliency Loa d(g.) (percent) Wale Course Felting 'Untreateda rticle". 38.2 svls 150 76.2 15.2 10.8 Marked.

2.5 Slight.

Treated article of the invention). 42. 5 94. 8 136 at a pick-up of and then cured for 3 minutes at 160 60 C. The resultant fabric contained 1.05% by weight of polyorganosiloxane and exhibited thick hand and creaseresistant ability.

The characteristics of the treated fabric are shown as compared with those of untreated fabric in the following Table 16.

TABLE l6 Compressive elasticity i (percent), Degree of crease recovery (percent) before washing Before washing After washing Degree of Degree of compression resiliency Warp Weft Warp Weft Untreated article; 29.5 80.0 78.8 78.8 74.4

Article of the invention 30. 5 83 85. 6 82. 7 83. 5 81. 8

polysiloxane prepolymer, whereby kinds of solution were Fabrics treated with the solution containing the polyelasticity. y

i ...TABLE.17--

pressure was'measured. v

Tetraethoxy I silane I Perehloroethylene a Amount of POYYELPI added (p'rcen't) 23,.- 'Example 19I-A double jersey fabric (the engthfextended in the Wale direction was 70 mmII/50 course) knitted with a false-twist textured nylon-6 yarn of 70 denier of 18 filaments/2 ply, was scoured at 70 C. for Properties 0 3.3 16.5 30 Gray 20 minutes in a th folded bath containing 1 g./ l ep a cl oif 5 mm A?) (4) n "(4)7v 0(4) an anionic surface active agent and of soda ash, dried, Cq pr s v as c y--- g iig gg-g g -g 38 g ;g

padded with the solution having the under-described com- Ems-tic Qwerlat 5% position (pick-up: 100%), dried again at 80 C. andthen' cured for 2 minutes at M "lgi gza itg reg e, g

a at" e yre 110% 3 v RH COMPOSITION OF TREATING SOLUTION Example 21."-Nylon-6 having its inherentvisco'sityof Pains 1.24 in m-cresol solution at 25 C. and acopolymenpf 2 polyslloxane 4 prepolymer 15 separatelynmeltedand .two: .melts .of equaljw'eight were Dibutyl gfiflg g g i conjugatedin a side by side relation which wereiextruded polyoxyethylene i gg' ggggigg g 1 x concurrently from an orifice having its diameter of 0.25 perchloroethylene w 900 mm. on a spinneret plate at 280 C. to form a unitary Amount of this polyetheric compound w'as' va ried to be 20 0%, 3.3%, 10%, 16.5% and 30 each by weight based on the prepared.

thendrawn to 4.1 times its original length'to. obtaina unitary filament yarn Y of .15.iden ier.;A multi filament yarh .denier of '7. filaments wasobtaine d sub,- staritiirlly in tli e sarnef" 'b, ceptf thafthe draw ratio was 3.7.". I

oxye'thyle'rie Serbian monolaurate showed markedirde- E5 creased waxy hand and anti-static propertyas compared with the iab'ridtreated with the' solution not'containing l .Each of yarns -Y andY waspas I, rough a'heat ed metallic 'tlibe'having its 'i'n'side'di'ain 1" of 3"rh'n'a. and length cm., at a relaxed condition to develop slight mus. and.nounsign.a hobb in-nw entm,x mXrna 1 ocessed, the temperature of the heater tube was 140 AmoumofPOEsLlaaded (percent) ..Ci,'tlie"fecd-in speed was 280 m./min. and the delivery Untretdl -speed was 211 m/mirr, and when the yarn Y the tem- -Properties 7 0 3.3 10 16.5 30. (Gray) The comparison of those fabrics is shown in Table'l7 '30 which follows:

'p rature o'. .the heatert'ube was 180 (3., the feed-in speed a y d- 0% 6) mmwas 200 m./m1n.---andthe delivery s eed Was ISO :mL/min. Stockings jwith plain stitches wereffknit on'ja pressure (v) 4 0 2,000 700. 400 -=200. .15mi...T5.400 circular-Arnittihgmachine-:Which- WaSprovided avith 400 POESL=Po1yoxyethylenesorbitanmonolaurate. need;leS, the above Processed y 1 for the leg glistlingti. d d portion and the yarn Y for the toe, heel and welt. After are reuse. 4 r g Detennjhation of the frictional electrostaticpressure was conducted p tha knitted stockmgs were as iol1ows.Samplo clothwas rubbed with a pure cotton cloth at aspeed under a t i l s nditi fo .30 i ut .to' dev l of 1,050 rpm. at 20 9. and 65% RH. and tlicngenerated electrostatic their p Putin) a s y d in iawotary. drum 7 g 45 type'dye'ing machin'e; The dyed stockings wereb'oarded l O M k d l and steamed at 116 "C for 45 seconds; taken off'the Exanfp ens 9 5 ensl course board after drying and allowed to stand in a room of 43) a false'twst textured nylon'6 yam of 70 65% RH; at 25 C. for 1 day to shrink. The resultant qemer f 32 filaments/2 were id E ---stockingswere-denotedas stockingsS .The stockings S Hon Y g the under-melanoma fi qnr Worked, 5.0-vvere; soaked in' afsdlutidn which consisted of 1.5 parts a centnfufial Separator to reduce the water of poly-dimethyl'siloxane'diol prepolymer having its de- 1 dfled at and culled for m t gree; of polymerization "of. about 150, 98.5 parts of tri- 120 C- chloroethylene'and;0;01" part'ofibenzoyl peroxide;sub-

; jected to acentrifugal squeezing fOIIOWedbY I YiHg and COMPOSITION OF TREATING SOLUTION r *then curedin hot air"at165 C: forlS minutes; The

Parts thus treated stockings which were denoted as stockings Trichloroethylene solution of 15% by weight of dihad polyorganosnoxane a fl methyl polysiloxane diol containing 5% by mole of r .199 stockmgs' w m n t r d. sl m y 7 3 methyl ydrogen siloxane unit (F: about- .500) H.160 2 as *E QY agter d h y. Dibm-yl 3 fi he a q ""e n ,o sdfi e f s i Polyoxyethylene laurylphosphate 1 x 1A t t h 1 th 1 d d t b denoted as "stock ing sS5? n moun o t is p0 ye yer c compoun was varie 0 e 0 3.3%, 10% 10.5% and 30% each by weight based on the The stockings S and S were very smooth and soft,

polysiloxane, whereby 5 kinds of solution were prepared. whereas the stockings S exhibited a little hard hand.

us-. .lheabovmmentionedstockings S S and S were test The socks treated with the solution contain h P Y- used by 60 persons. One user wore three pairs, ench one etheric Compound Showed 3 anv adequateln} pp e s pair of those three kinds of stockings, so as to use one smooihfle flnq QXCCIICHi as y, While 36 i j fq pair every three days until all of them were broken and with solution not containing the polyetheric compbund their lives were recorded. The stockings were washed in xh it d sm ss .s mu that'their Soles w p ""hot water with nentrarisoa after wearing for a day. In pery and felt rather "dangerous when worn. this way,-th nterrelation between the life and the num- The comparison ofthose' socks'is"sho'wn'ih"Table"l8"""'15er"ofbreakags'withrespect to 60 pairs of stockings of which follows: 7 a sort was observed and it was made clear that the number of unbroken stockings decreased in inverse proportion as the time of wear and such relation was approximated by the exponential function shown in the Equation 1. I i I,

XfNumber of unbroken stockings L A: Numberof stockings tested (120) e: 2.718 (constant) 7 k: Coefficient of decrease t time When the Equation 1 is applicable, average life of 'wear is shown by the reciprocal of the coefficient k, i.e. l/k. Average life of the stockings S S and S were 75 hours, 82 hours and 77 hours respectively. Thestockings S had lost their softness after washing, whereas the stockings S did not lose their'softness' as well as smoothness.

Too much adhesion of polyroganosiloxane led to an undesirable result. In the following Table 19 ,will be shown a result of measurements of elongation and recovery of leg portion with respect to stockings which were manufactured substantially in thesame manner as that of the manufacture'of the stockings S except the amount of polyorganosiloxane adhered.

I TABLE 19.

Amount of polyorgauo- Elongation Recovery siloxane adhered (percent) (percent) (percent) -Method for determining percentages of elongation and recovery was as follows: a

. Distance (L between the welt and the heel of stockings was measured.

Next, the welt of the stocking was fixed,'from which the stocking was hung, attaching a load of 21kg. at the bottomend of its leg portion and one minute later the distance (L between the welt and the heel was measured.

Then, the load was taken off and-oneminute later-the distance (L between the welt and the heal was meas ured again. The percentage of elongation and that of recovery were calculated by the Formulae II and III -respectively. V

Percentage of elongation (Percent):

Peicentage of recovery (Percent)= X 100 V o V the same manner as that of the manufacture of, the

stockings S except that the leg portion was knit into nonrun stitches. The stockings S were extremely soft and stretchable, and further well fitted. On the contrary, non- -run stockings which had notbeenfirea'ted with poly- 26 organosiloxane were awfully poor in their stretchability as well as in their softness.

Example 22.Nylon-6 having its inherent viscosity of 1.21 in m-cresol solution at 25 C. and a copolymer of 88 parts of nylon-6 with 12 parts of polyhexamethylene isophthalamide having its inherent viscosity of 1.23 were separately melted and two melts of equal weight were conjugated in a side by side relation which were extruded concurrently from an orifice having its diameter of 0.25 mm. on a" spinneret plate at 280 C. to form a unitary filament wherein two-polyamidic components were adhered and disposed in a side by side relation with each other throughout the entire length of the filamenh/Ihe extruded filament was air-quenched, oiled, wound on a take-up tube .at a. speed of 700 meters per minute and then drawn to 4.0 times its original length to obtain a unitary filament yarn Y, of 18 denier. Multi-filament yarns Y; of 18 denier of 2 filaments and Y of 45 denier of 7 filaments were obtained substantiallyin the same manner as above except that for the latter yarn the draw ratio was 3.7.

Each of yarns Y Y and Y was passed through a heated metallic tube having its inside diameter of 3 mm. and length of 50 cm., at a relaxed condition to develop slight crimps and wound on a bobbin as respective yarn Y Y and Y When yarns Y and Y were processed,

the temperature of the heater tube was C., the feedin speed was 280 m./ min. and the delivery speed was 211 m./min., and when the yarn Y the temperature of the heater tube was 180 C., the feed-in speed was 200 m./

min. and the delivery speed was m./min. Stockings .dyeing machine. The dyed stockings were boarded and vsteamed at 114 C. for 45 seconds, taken off the board after drying and allowed to stand in a room of 65% RH.

.at 25 C. for 1 day to shrink. The resultant stockings were denoted as stockings S 3 The stockings S were soaked in a solution which consisted of 1.5 parts of polydimethyl siloxane diol prepolymer having its degree of polymerization of about 150, 98.5 parts of perchloroethylene and 0.01 part of benzoyl peroxide, subjected to a centrifugal squeezing followed by drying, and then cured in a hot air at C. for 5 minutes. The thus treated stockings which were denoted as stockings S had 0.6% of polyorganosiloxane adhered thereon. Another stockings S, were obtained substantially in the same manner as above except that the yarn Y was used for leg portion. Still another stockings were manufactured substantially in the same manner as above except that after dyeing, they were finished with an aqueous emulsion of softening agent comprising a silicone oil and a cationic surface active agent (adhesion amount of the softening agent was 1.0% by weight) andthen subjected to boarding, which were denoted as stockings S The stockings S and S; were very smooth and soft, whereas the stockings S and S7 exhibited a little hard hand 7 and a less softness.

Those stockings S S S and S were test used. They were washed in hot water with neutral soap after wearing for a day. The stockings S had lost entirely their softness after five day wearings, whereas the stockings S did not lose their softness as well as smoothness.

Too much adhesion of polyorganosiloxane led to an undesirable result. In the following Table 20 will be shown a result'of measurements of elongation and recovery of leg' portion with respect to stockings which were manufactured substantially in the same manner as that of the manufacture of the stockings S except the amount of polyorganosiloxane adhered.

C. for minutes to develop their crimps. The c taken off the board after drying and allowed Stockings 5-, showed an elongation of 135% and a recoveryof 91.5%.. p

Method for determining percentages of elongation and As is apparent from Table 20, when the amount of polyorganosiloxane adhered is in excess of 4%, the percentage recovery is small. From the viewpoint of smoothness,

even an amount of less than "1%" gives good results and; more amount seems to be unnecessaryI""-"" A Example 23.Stockings S S and- S obtained in**Example 22 were test used by 80 persons. Que user Wore three -pairs,feach-one paii'Iof-tho's'e three kinds of 'st6ckin'gs", so

as to use one-paireverythree days' until all of them were recovery a same as t, in 'the foregoing Example '21'." 7 I broken aha their lives were recorded. In this"--way, the

interrelation b'etweentheflife and the numberofbreakag'es with respect'to' 80 pairs'of stockings ofa sort "was'ob- "served and it was made clear that the number of unbroken stockingsdecreased in inverse proportion as the" time of tial function shown in the Equation 1 hereinbeforeQAVefage life of the stockings S S S and S were 85hours, 92 hours, 82 hours and 87 hours respectively. Thus, "the stockings manufactured according to the present invention 'Wearan'd such relation was approximated bythe exponenhad an. average life longer than that of stockings which were finished with a conventional softening agenti Example 24.-Nylon-66 having its inherent viscosity of 1.15 in m-cresol solution at 25 C. anda copolymer of 4 parts of nylon-66 with 6 parts of nylorf-610having its inherent viscosity of 1.16 were separately' melted and two melts of equal weight were conjugated ina'side by side relation which were extruded concurrently {from an orifice having its diameter of 0.25 mm. on "a spinneret plate at 290 C. to form 'a unitary filament wherein two polyamidic components were adhered andTdi sposedin a side by'side'relation with'each other throughout the entirelengthof the filament. The extruded filam'entiwas air-quenched, oiled-,- wound on a take-up tube' atj a speed of 600 meters per minutes and then drawn1to3I'9ftimes its original length on a 'snubbing'pirr'at 80"C.--toobtain a filament yarn Y of 20 denier of 3 filaments. A multi- 'filament yarn Y, of denier of 71fi1arnnts was obtained substantially in the same manner as abovefexcept that the draw ratio was 3.6. The yarn \{gwas given twists of 120 turns per meter and passed .th'rodghfa heated metallic tube at'l60 C. having its' inf'side' diameter of 3 mm; andlength of '50 cm. with a gfeed-infspeed of 600' meters per minute and a delivery s' eed ofiQSSO meters per minute. The thus heatetreated yarn Ym was then woundon a-pirn. The yarn Y was treated to obtain a yarn Y in substantially the same manner as above except that the feed-in speed was ZSOmetersper minute, the delivery speed" was 222 meters per miniit e and the temperature of the, heater tube was 180 Stockings withtrun-resistant stitches were knit 'on a seamlesslknitting machine which'was provided with 401 he I the above processed ,ya'rn Y for the leg portion yarn Y for the toe, heel and welt. Afterflooping, knitted stockings were heated Witha satin Jedi, at 100 C. under a tensionless condition 'folr'iiiband were further heated with a saturated steam stockings were put into a sack and dyed then boarded and steamed at 119 'C. for. ,45 z

a room of RH. at 25 c. for 1 dayio" shrink. 7 5

'posit filament yarn-1 in a hot air at 150 C. $01 13 minutes ln the following Table 21 will be shown a' result fof,n1easur'ement of elongation and recovery of leg. pontion'sfwith respect to those stockings difiering in the'adhe'sion'ar'nount of the polyorganosiloxane, which measurement was performed in. thesameamanner as that,, in the;.-foregoing Example I I ..'TABL 'E 21- siloxaneadhered (percent) .(percent) (percent) 1 All of stockings on which polyor ganosilo'itane' had been adhered exhibited more excellent softnesas compared with those which had not been treated with polyorganosiloxane.

Another-stockings Sm which. had 0.5% by weight of polyoi'ganosiloxane-j adhered thereupon were obtained in the same mannera sQthat.inLthe manufacture of the above n'ientioned stockings except that a unitary filament of 20 denier was-employed for the leg portion. The stockings S had fa degree of elongation of 1 81% and a recovery of 86.2%, and exhibited arather hard hand that wasnnt irablenwwa ,.1 19 .stqgkinssiin had been manufactured according to the process of the present invention displayed an excellent hand.

Generally, in. case. thathosieries' or. stockings knit with a multi-filament yam are treatediiwitha.:polyorganosiloxane prepolymer according to theprooess oi the present invention, they can be given largeramountzof poly- :org'anosiloxaneas compared with-those knitwith aunitary filament .yarnand, moreov'erythemore adhesioneof the prepolymer not only effects; the better appearance of the stockings, .but also-intensifies, inmost cases,a..their stretchability mores-thaneffects. r .Whatis claimed-is? a. i121; v .I'.:.A2;pr0cess for. manufacturing a fibrousstructure composed of. at least 20% by=weightofcontinuousfilaments and at most by weight of staple fibers havingudurable elasticity, crease-resistivity and shrink-proof ability, which comprises applying homogeneously to said fibrous structure a non-aqueous solution comprising polyorganosiloxanediol .prepolymer having anaverage degree of polymerization of at least '50 selected fromthe' group consisting of poly(dimethylsiloxane)diol, poly(diethylsiloxane)diol, poly(methylphenylsiloxane)diol, and poly (diphenylsiloxane)diol and a catalyst for polymerization thereof, said solution being applied an amount such that the polyorgananosilox'ane component is---fixed"o'n said fibrous structure in an amount of not exceeding 10% by weight based on said structure and then subjecting the aple'fibers v J1 3 53p; ces's claiml; thefibroiis tur omposed'fofcontinuousfilament i A cess as claiinedih 1, where p la he-fibrous structifir'e ijsknitted goods co osedfofgcrimpable com- Q5. Apr ocessj as cla me ini clai m goods ar'ladies hosieries.

6. A process as claimed in claim 4, wherein said yarn is a multi-filament yarn.

7. A process as claimed in claim 6, wherein the knitted goods are ladies hosieries.

8. A process as claimed in claim 1, wherein the polyorganosiloxane prepolymer comprises poly (dimethyl siloxane) diol as its principal component and methyl hydrogen polysiloxane as its subsidiary component.

9. A process as claimed in claim 1, wherein said prepolymer has an average degree of polymerization of at least 100.

10. A process as claimed in claim 1, wherein the nonaqueous solution of polyorganosiloxane prepolymer is a solution in an organic solvent comprising at least one organic compound selected from the group consisting of toluene, xylene, benzene, perchloroethylene, polychloroethylene, gasoline for an industrial use, chloroform, methyl chloroform and methylene chloride.

11. A process as claimed in claim 1, wherein said catalyst is at least one organic tin compound selected from the group consisting of dibutyl tin dilaurate, dibutyl tin dioctoate, dibutyl tin succinate, stannous octoate and chelate compounds of tin.

12. A process as claimed in claim 1, wherein said catalyst is contained in an amount of 0.01-% by weight based on the polyorganosiloxane component.

13. A process as claimed in claim 1, wherein said catalyst is contained in an amount of 0.1-1.0% by Weight based on the polyorganosiloxane component.

14. A process as claimed in claim 1, wherein said catalyst comprises at least one accelerator of cross-linking reaction selected from the group consisting of isocyanates of silane compound, alkoxy silane, acetates of silane compound, and benzoyl peroxide.

15. A process as claimed in claim 14, wherein said accelerator is contained in an amount of not exceeding 15% by weight based on the polyorganosiloxane component.

16. A process as claimed in claim 1, wherein said nonaqueous solution further contains at least one polyetheric compound selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkylamine, polyoxyethylene alkylphosphate, polyoxyethylene sorbitan fatty acid ester and polyethylene glycol.

17. A process as claimed in claim 15, wherein the amount of said polyetheric compound contained is 1-50% by weight based on the polyorganosiloxane prepolymer.

18. A process as claimed in claim 15, wherein the amount of said polyetheric compound contained is 3-20% by weight based on the polyorganosiloxane prepolymer.

19. A process as claimed in claim 1, wherein the heattreatment temperature is of 100-180 C.

20. A process as claimed in claim 1, wherein the structure is subjected to said heat-treatment for 20 seconds to 60 minutes.

21. A process as claimed in claim 1, wherein the structure is subjected to said heat-treatment for 1 minute to 10 minutes.

22. A process as claimed in claim 1, in which said polyorganosiloxanediol prepolymer is selected from the group consisting of poly(dimethylsiloxane)diol, poly(diethy1- siloxane)diol and poly(diphenylsiloxane) diol.

23. A fibrous structure composed of at least 20% by weight of continuous filaments and up to by weight of staple fibers said filaments having impregnated therein not more than 10% by weight of a polyorganosiloxanediol prepolymer having an average degree of polymerization of at least 50, wherein the prepolymer is selected from the group consisting of poly(dimethylsiloxane)diol, poly(diethylsiloxane)diol, poly(methylphenylsiloxa'ne)- diol and poly(diphenylsiloxane)diol.

24. A fibrous structure as claimed in claim 23, wherein the elongation at break is ISO-800%.

25. A fibrous structure as claimed in claim 23, wherein the tensile strength at break is 3-20 kg./cm.

26. A fibrous structure as claimed in claim 23, wherein the hardness is 8-30".

27. A fibrous structure as claimed in claim 23, wherein the fixed amount of polyorganosiloxane is 0.2-5% by weight based on the fibrous structure.

28. A fibrous structure as claimed in claim 23, wherein the fixed amount of polyorganosiloxane is 0.3-3% by weight based on the fibrous structure.

29. A durable elastic crease resistant fibrous structure having an elongation at break of at least 50%, a tensile strength at break of 1-50 kg./cm. and a hardness of 550 which has a heat cured polymer formed by heat treatment of the prepolymer wherein the prepolymer is selected from the group consisting of po1y(dimethylsiloxane)diol, poly(diethylsiloxane)diol, poly(methylphenylsiloxane)diol and poly(diphenylsiloxane)diol, bonded thereon.

References Cited UNITED STATES PATENTS 2,684,379 7/ 1954 Guillissen et al. 260-448.2 2,717,258 9/1955 Kantor 26046.5 X 2,902,468 9/ 1959 Fianu 260-465 2,732,320 1/1956 Guillissen et al. 117-161 2,832,518 4/1958 Doyle et a1 1l7138.8 X 2,876,209 3/1959 deBenneville et al. 1l7-138.8 X 3,065,111 11/1962 Reeves et al. 1l7161 3,268,465 8/1966 Gilkey et a1 117135.5 X 3,385,812 5/1968 Brachman 1l7161 X 3,445,276 5/ 1969 Pikula 117161 X 3,476,581 11/1969 Weitzel et al 117-62 WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner U.S. Cl. X.R.

117-138.8 N, 139.5 A, 141, 145, 161 ZA