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Publication numberUS2324601 A
Publication typeGrant
Publication dateJul 20, 1943
Filing dateSep 21, 1940
Priority dateSep 21, 1940
Publication numberUS 2324601 A, US 2324601A, US-A-2324601, US2324601 A, US2324601A
InventorsEdgar W Spanagel
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Sizing
US 2324601 A
Abstract  available in
Images(9)
Previous page
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Claims  available in
Description  (OCR text may contain errors)

made.

Patented July 20, 1943 SIZING Edgar W. Spanagel, Wilmington, DeL, assignor to u Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application September 21, 1940, Serial No. 357,757

24 Claims. (01. 26032) This invention relates to new sizing compositions which are suitable for use on knitting yarns composed of synthetic linear polyamides.

For along time silk has dominated the sheer, full-fashioned hosiery field. Relatively recently, a class of synthetic yarns, prepared from a class of materials known as synthetic linear polyamides, has come to be used for sheer, full-fashioned hosiery. The preparation of this type of material and the production of yarn from the material are described in U. S. Patents Nos. 2,071,250, 2,130,523 and 2,130,948. The term synthetic linear polyamide as used throughout the specification and claims is intended to refer specifically to the material disclosed in the aboveidentified patents. The preparation of sheer, knit ladies full-fashioned stockings from this type of yarn is described in U. S. Patents Nos. 2,157,116 and 2,157,119. The knitting of ladies sheer stockings from yarns of synthetic linear polyamides created new and serious problems in the satisfactory sizing of such yarns. Without any size these yarns, when knitted into sheer, full-fashioned stockings and subsequently handled, developed an undesirably large proportion of pulled threads. For years, the art has been confronted with a similar problem in the knitting of sheer stockings from ingrain silk. The knitting of sheer stockings from ingrain silk produces stockings a very large proportion of which have pulled threads; and because this problem was never solved ingrain silk stockings are seldom There has been no sizing problem for silk in the gum because of the presence of a natural protecting coat of sericin over .the silk filaments.

When the word "sizing is used, it does not refer to the application of oils, finishes, dressings,

and the like, but is restricted to the narrower,

meaning of the word; namely, the application of an adhesive coating to protect the filaments in the knitting operation and in the course of handling the fabric subsequent to the knitting operation.

Sizes have been developed for the warp sizing of artificial silk yarns; e. g., viscose rayon, cellulose acetate, etc. It is also well known that artificial silks require no size for tricot knitting or circular knitting. Hence, the problem of sizing these yarnshas been concerned almost entirely with the preparation of the yarns for weaving. It is, therefore, evident that prior to the introduction of the synthetic linear polyamide yarns into the field of sheer hosiery knitting, there was no problem of sizing knitting yarns. It is equally true that prior to that time, no sizing composition had been developed which was satisfactory for use in knitting sheer hosiery when applied to synthetic linear polyamide yarns.

The requirements for a, good warp size for weaving yarns are much less rigorous than the requirements for a good size for yarns to be used in the knitting of sheer, full-fashioned hosiery. Furthermore, the requirements for a satisfactory size for use on yarns composed of synthetic linear polyamides are much more critical than for sizes to ,be used on previously known artificial filaments or natural fibers. Therefore, a satisfactory size for synthetic linear polyamide yarns for knitting full-fashioned hosiery must possess all of the following characteristics:

1. The size must protect the fabric from snags and pulled threads. A full-fashioned stocking fabric is sheer and delicate. It is subjected to a considerable amount of handling after the knitting operation; for it mustbe looped, seamed, stitched, inspected, and preset before it is dyed. The rough hands of operators cause entirely too many pulled threads if the size does not give good protection.

, 2. The size must adhere well and bind the filaments together during twisting, coning and other textile operations and perform well during and following the knitting operation. The action of the knitting needles and sinkers on the sized yarn is so drastic as to cause flaking 01f of the size with resultant loss of protection if the size does not adhere extremely well. Since synthetic linear polyamide filaments are spun substantially round and smooth and synthetic linear polyamides are markedly insensitive to water, the problem of size adherence is much greater than it is for relatively water-sensitive yarns such as viscose rayon, cotton, etc.

3. The sized yarn mustrun well on the knitting machine; that is, after passing through the dip trough, it must not stick to the guides and snappers following a shut-down of the machine and size must not accumulate on the needles and sinkers. Sticking on the guides and snappers causes press-offs when the machine is started up again. Accumulation on the needles and sinkers eventually causes holes and runs in the fabric if the accumulation becomes severe.

4, The size must soften sufiiciently on passing through the dip trough to enable the formation of regular stitches of uniform size and to cement the loops together when the fabric dries. If the size softens insufliciently, poor stitch formation and poor snag resistance result. on the other hand, if it softens too much, the

- edges as it comes oi! the knitting machine, the

fabric is diiiicult to seam and the cost of production increases; also theseams are likely to be bulky and crooked.

6. The size must be readily removable in an aqueous boil-oil. bath before dyeing. It is generally desirable, though not always necessary, to remove the size before dyeing the fabric. It is much more economical to remove the size with water than with some other solvent.

7. The size should be free from any tendency to cause corrosion or abrasion of the various parts of the knitting machines which the yarn contacts.

The problem of developing a size which will fulfill these rigorous requirements is relatively new in the field of synthetic yarn production. Many different sizing compositions have been developed for use on rayon yarns, and many of these sizes have been tried with synthetic linear polyamide yarns; but all ofethemany sizing compositions tried have been found to lack one or more of the above requirements to such a great extent as to render impossible their use in sizing synthetic linear polyamide yarns for the knitting of full-fashioned hosiery. Even the recently developed polyvinyl alcohol sizes which have proven to be very useful for the sizing of rayon and other weaving yarns have failed to satisfy the rigorous requirements for a good size for synthetic linear polyamide yarns used in the knitting of full-fashioned hosiery. These sizes are, in general, toowater-sensitive. They become sticky and collect on the knitting machine parts. In an eifort to increase the viscosity alcohol-boric acid sizes, or polyvinyl alcohol de-' of polyvinyl alcohol sizes, it has been suggested degree by reason of a gelling action on the polyvinyl alcohol. The addition of borax and other agents to polyvinylalcohol sizes has failed to improve them for use on synthetic linear polyamide yarns This highly viscous, borax modifled polyvinyl alcohol composition, when applied to synthetic linear polyamide yarn, flakes off of the polyamide yarn very badly, giving very poor running properties.

It is, therefore, an object of the present invention to furnish an improved type of textile sizing composition particularly suitable for sizing synthetic linear polyamide knitting yarns to be used in the production of sheer, full-fashioned hosiery.

It'is a further object of the present invention to furnish an improved method of sizing :textile yarn, particularly synthetic linear polyamide knitting yarns to be used in the production of sheer, full-fashioned hosiery.

A specific object of the invention is to provide of being successfully knitted into full-fashioned hosiery.

Other objects of the invention willbecome apparent hereinafter.

It has now been found that excellent sizing compositions, which are. suitable for the sizing of synthetic linear polyamide yarns tobe used in knitting sheer, full-fashioned hosiery, can be prepared from polyvinyl alcohol, or a watersensitive derivative of polyvinyl alcohol, and

boric acid. These new sizing compositions, characterized by a low viscosity and consequent high degree of solubility and ease of application, adhere well to the smooth, round polyamide filaments, bind the filaments together well, impart to the yarn good running properties on full-fashioned lmitting machines, protect the full-fash ioned stocking fabric well from snags and runs, prevent serious edge rolling of the full-fashioned stocking fabric, and are readily removed byhot water.

It has been further found that these polyvinyl rivative-boric acid sizes will adhere to synthetic linear polyamide yarn better if an anchor coat (or a sub-coat) of tannic acid is applied to the yarn before applying the size. The tannic acid apparently adheres very well to the synthetic linear polyamide and also tojthe size. However, it has been found that the adherence of the size to the yarn is improved by the tannic acid only if the tannic acid coat is applied first and that a single mixture of the two applied in one step does not produce a well-sized yarn having good full-fashioned hosiery knitting properties, nor does the application of a coat of tannic acid on top of a coat of the size produce a sized yarn having good full-fashioned hosiery knitting properties. The proper ratio of tannic acid in the anchor coat to the size coat imparts astonishingly good snag resistance and running properties to yarn sized in accordance with the preferred method as hereinafter described. Moreover, it has been found that the tannic acid anchor coat decreases the water-sensitivity of the size coat sumciently to make possible conditioning of the sized polyamide yarn over water. This is very advantageous because of the practical ease of controllingsuch a conditioning process. The use of 'tannic acid under-coatings in polyethylene oxide (polyethylene glycol), which serves as a plasticizing agent. This polyethylene oxide is a polymerization product obtained from ethylene oxide and preferably has a molecfreedom from flaking on, use of the polyethylene oxide plasticitd size with or without an I anchor coat of tainic acid is particularly ada sized, synthetic linear polyamide yarn capable vantageous for yarn that is to be. twisted after the sizing operation. The use of polyethylene oxide as a plasticizing agent in a water-sensitive hydroxylated polyvinyl resin sizing composition is the invention of D. E. Strain and is described and claimed in the co-pending application, Ser. No. 357,755 died of even date herewith.

The following examples are given to illustrate preferred sizing compositions and preferred methods of applying the same. The-details set forth in the examples are not, however, to be considered as limitative of the invention. The percentages set forth in the examples designate percentages by weight.

} Examplel A skein of 30-denier, 10-filament, ISO-tum polyhexamethylene adipamide yarn is sized by soaking the skein of yarn in a solution comprising 8% of partially saponifled polyvinyl acetate having a saponification number of 140 and a viscosity of centipoises in a 4% aqueous solution at 20 C.,' 1.7% boric acid, and 90.3% water. The skein is removed from the bath-and centrifuged to remove excess solution. It is then dried, wound on to a bobbin, and finally coned, applying approximately 5% olive oil in the coning operation. The yarn knits well on a fullfashioned hosiery knitting machine. It does not stick to the knitting needles or knitting machine guides when wet in the customary silk knitting method. There is no appreciable accumulation of the size on the needles and sinkers of the knitting machine. The knitted fabric has good snag resistance and is not subject to objectionable edge roll characteristics.

Example II The size is readily removed by washing the fabric in hot water.-

acid. After drying, the yarn is sized with a solution comprising 7.5% partially saponifled polylution, then dried, and soaked in a solution of partially saponified polyvinyl acetate and boric acid such as is described in Example I. The skein is removed from the size bath, centrifuged, and dried. The yarn is wound on to a bobbin and from the bobbin to a cone, applying about 5% teaseed oil tothe yarnr. The yarn knits well on a. full-fashioned knitting machine, does not flake off, and does not stick to the parts of the knitting machine. The size is removed from the yarn by washing the fabric in hot water; the size is more easily removed from the yarn by adding a small amount of soap or a small amount of alkali to the washing water.

Example III A skem of 30-denier, lu-filament, 30-turnpolyhexamethylene sebacamide yarn is sized, dried, and coned in accordance with the method outlined in Example I. The sized yarn has good knitting and snag resisting characteristics.

Example. I V

Ezample V A BO-denier, 10-filament, 2-turn yarn prepared fro-m polyhexamethylene adipamide is put on' an uptwister and given 28 turns additional vinyl acetate having a saponlflcation number of approximately and a viscosity of approximately 5 centipoises in a 4% aqueous solution at 20 C., 1.6% boric acid, and approxmately 90.9% water. The size is applied on-the-run in a machine constructed much like a coning machine, but having a bobbin as the windup package. The size is applied by passing the yarnover a rotating roll dipping into a trough containing size solution. Sizing is carried out in a room having 50% relative humidity at 88 F. The size dries sumciently before being wound up to prevent sticking or wicking.- Three percent of size is applied. The yarn is coned while applying 3.5% of olive oil. The resulting yarn is found to knit well on a standard full-fashioned-knitting machine. The size is removed by washing the fabric in a hot water solution containing 0.1% hydrated trisodium phosphate, 0.1% oxalic acid, and 0.5% fatty alcohol sodium sulfate.

Example VI Fifty parts of a composition comprising 10% triethanolamine'oleate, 20% crude lauryl alcohol and 70% olive oil; are emulsified in 50 parts of a solution of 4% dipotassium phosphate in water. The eniulsification may be accomplished by slowly dropping the oil phase into the water phase while vigorously stirring with a high speed stirrer followed by several passes through a colloid mill.

The resulting oil emulsion is applied to a yarn coated first with tannic acid and then sized as in Example V. The oil emulsion is applied during the coning operation by means, of a rotating roll dipping in the oil emulsion; Approximately 4% of the oil is applied. The resulting yarn has excellent knitting properties even though conditioned at a high relative humidity. The size and the coning oil are readily removed by washing the fabric in hot water.

Example VII Yarn sized as in Example V is coned while applying 5%, of a neutral vegetable oil. This yarn is conditioned over water and knitted in the usual manner with the yarn passing through a water dip or a water wick prior to going through the carrier tube. The water dip has to 4 of dipotassium phosphate added to it. This alkaline treatment improved the knitting properties of the yarn and decreases the number of press-offs and holes in the knitted fabric. The size is readily removed from the fabric by washing in hot water.

Example VIII twist while applying a 25% boat of tannic acid fashioned knitting machine.

good.

' Example IX of a low viscosity polyvinyl alcohol (obtained by" completely saponifying polyvinyl acetate) with 170 cc. of 37% formaldehyde and 16 cc. of concentrated hydrochloric acid to 75-80 C. with stirring during 3-4. hours, neutralizing with monia (using methyl red as indicator), and mixing 200 grams of this solution with 50 grams of a 5% aqueous solution of boric acid and 125 grams of water. The sized yarn was air-dried and twist set in an oven at 160 F. wet bulb, 170 F. dry bulb. The yarn was coned and knit on a full- The size ran well on the knitting machine with very little deposit and the knitted fabric had good snag resistance. The partial formal of this example had approximately 20% of formal.

Example X Ninety-six ends of a 30-denier, l5-fllament, 30-tum polyhexamethylene adipamide yarn were taken from a magazine creel, formed into a warp with ends /4 of an inch apart, sized with a 24 inch application roll, dried in a 14 foot drier at finally wound up on individual packages on a chain quiller. The size composition contained 8% of a low viscosity partial acetate of polyvinyl alcohol, 1.6% boric acid, and approximately 90.4% water. The yarn speed was 300 feet per minute. The R. P. M. of the size application roll was 9. Approximately 6% of size was applied to the yarn. After drying, the yarn was coned while applying a teaseed coning oil. The yarn was knit on a full-fashioned hosiery knitting machine. The stitch formation, edge-rolling characteristics, and snag-resistance were Example XI Seventy parts of a 10% solution of a low viscosity partially hydrolyzed polvinyl propionate (saponification No. 132) were mixed with 1.4 parts of boric acid dissolved in 28 parts of water. Vigorous agitation and cooling was necessary to produce a clear solution. This size solution was applied to a 30-denier, lo-fllament, 30-twist polyhexamethylene adipamide yarn by means of a size roll using a yarn speed of 1,000 feet per minute. The yarn after being allowed to dry overnight at a relative humidity of 50% at 25 was found to contain 4.58% size. The sized yarn was knit on a 45 gauge full-fashioned hosiery knitting machine. No size accumulated upon the needles of the knitting machine during the knitting. The yard delivered freely from the cones and did not tend to stick to the needles. The width of the fabric was satisfactory, and the rolls at the edge were not tight. The snag resistance of the knitted fabric was good.

Example XII upon the needles of the knitting machine, and 75 of the fabric were not tight.

a size roll in the usual manner.

0 gave 3.99% size.

there was no indication of stickinesson the needles or poor delivery from the cones. The snag resistance was of thesame order as that of the knitted fabric described in Example In.

Example XIII A size solutionysimilar to that of Example :1, was prepared using 10% of boric acid basedon the partially hydrolyzed polyvinyl propionate.

10 The concentration of thepolyvinyl alcohol derivative in the solution was again 7%. A 80- denier, lo-filament, 30-twist polyhexamethylene adipamide yarn was sized with this solutionat 1,000 feet per minute, the size being applied with The yarn was found to contain 2.32% of size. The yarn was knit on a 45 gauge full-fashioned hosiery machine. The siu showed a negligible tendency to accumulate .on the needles, and the knitted fabric was of good snag resistance.

In contrast to the above results. yarn sized with partially hydrolyzed water-soluble polyvinyl propionate of .the same saponitlcation numher and the same viscosity, but without boric acid, accumulated badly upon the needles of the knittingmachine and also stuck to the needles. The width of the fabric was not nearly as satiswere tight.

100 C., oiled with a second 24 inch roll and 'Emmple XIV A size was prepared by mixing together a solution of 0.54 parts of boric acid with 36 parts of I water and 54 parts of a 10% solution of a etherified polyvinyl alcohol glycolic acid ether 35 sodium salt of medium viscosity. The boric acid 0 1,000 feet per minute. The size was applied by means of a size roll. The yarn was then coned with teaseed oil and knit. The yam delivered freely from the cones, did not stick-to the needies, and the size showed only a very slight tendency to accumulate upon the needles.

The snag resistance of the knitted fabric was very good while the width'and edge roll characteristics were satisfactory. Analysis of the sized yarn Example xv A size solution, similar to that of Example XIV, was prepared using the same quantity of the same polyvinyl alcohol glycolic ether sodium salt with 1.62 parts of boric acid dissolved in 35 of water were added to bring the viscosity down to 9, figure corresponding to that of the above polyvinyl alcohol glycolic ether sodium salt size.

A 30-denier, lo-filament, 30-twist polyhexamethylene adipamide yarn was sired with this solution at 1,000 feet per minute, the size being applied by means of a size roll. Analysis showed the yarn to contain 2.08% size. The yarn was co'ned with teaseed oil and knit on a 45 gauge fullfashioned hosiery machine. The yarn delivered 7 freely from the cones, did not stick to the needles, and exhibited a negligible tendency to accumulate upon the needles. The snag resistance of the knitted fabric was moderately good, while the width was satisfactory.

The rolls at the edge Similar yarn was also sized withdzhe sodium salt of the same polyvinyl alcohol glycolic ether sodiumsalt without modification with boric acid. The size accumulated so badly on the needles that knitting was impossible.

Example XVI A resin was prepared by-dissolving 300 grams of partially saponified polyvinyl acetate, having a saponiflcation number of to 15 and a viscosity in 4,% aqueous solution at 25 C. of to 6 centipoises, in 1,700 grams of H20 and adding 24 grams of isobutyraldehyde and 8 cc. of concentrated I-ICl to the solution. The mixture was heated for 3 hours on a steam bath with stirring and then cooled and filtered. Two hundred grams of this solution were neutralized to methyl red with KOH and then mixed with 90 grams of 5% boric acid and 85 grams oi. water. A 30- denier, 10-filament, 30-turn polyhexamethylene adipamide yarn was sized with this size on our single position bobbin-to-bobbin sizer at a windup speed of 1,500 feet per minute, and a size roll speed of 10 R. P. M. The sized yarn was twistset in a 170 F. dry bulb, 160 F. wet bulb oven for 1.5 hours and was then coned with the application of teaseed oil. Size did not accumulate on the knitting machine during knitting and the knit fabric had a. good snag resistance.

The present invention broadly contemplates the preparation of sizes from polyvinyl alcohol and water-sensitive derivatives of polyvinyl alcohol together with boric acid. Such sizes are generally suitable for sizing of synthetic linear polyamide yarn which is to be used in the knitting of sheer full-fashioned hosiery. Thus, watersensitive polyvinyl compounds in which 1% to 50%, and preferably to 50%, of the carbon atoms of the polyvinyl chain are attached to hy droxyl groups (such compounds being hereinafter referred to as hydroxylated polyvinyl resin) when treated with boric acid produce very desirabl yarn sizes.

The water-sensitive derivatives of polyvinyl alcohol which have given particularly good results are the partial esters of polyvinyl alcohol such as the partial acetates, the partial propionates, the glycolic acid esters, the partial formates, and the partial lactates; the partial ethers of polyvinyl alcohol such as the glycol ethers, the glycolic acid ethers, the methyl ethers, and the ethyl ethers, and including also. the partial acetals of polyvinyl alcohol such as the partial formal, the partial acetal, the partial glyoxal, the partial propional, and the partial butyral, and including also the partial ketals of polyvinyl alcohol such as ethyl-methyl ketal.

Likewise, water-sensitive derivatives of polyvinyl alcohol produced by interpolymerization of polyvinyl esters with small proportions of other components such as vinyl chloride, methyl methacrylate, methacrylic acid (produced by saponification), maleic anhydride, methyl vinyl ketone and unsymmetrical dichloroethylene will be suitable for use in the production of sizes in accordance with the present invention by treatment with boric acid.

In general, anyone skilled in the art can readily determine the degree of substitution on the polyvinyl alcohol and the per cent of boric acid required to produce a water-sensitive compound and to give optimum sizing properties. None of the above named derivatives, when used without boric acid, are suitable for use in the sizing of synthetic linear. polyamide knitting yarn, since they will not impart thereto asatisfactory snag resistance and good running properties on the knitting machine.

The partial acetate esters, and the partial formals, of polyvinyl alcohol, when used in 'ac-, cordance with the practice of this invention, have given outstanding results in sizing synthetic linear polyamide full fashioned hosiery. knitting yams.

Although partially saponified or hydrolyzed polyvinyl acetates having saponiflcation numbers fromv to 145 and viscoslties from 4 to 6 centipoises in 4% solutions at 20 0. modified with 20% to 22.5% boric acid (based on th weight of the polyvinyl acetate) are particularly useful for sizing synthetic linear polyamide full-fashioned hosiery knitting yarns, numerous other partially saponified polyvinyl acetates and various mixtures and combinations thereof lie within the scope of the present invention.

Partially saponified polyvinyl acetates having saponification numbers of between 10 and 300, or even somewhat lower than 10 or higher than 300, may be used to advantage in sizing synthetic linear polyamide yarns which are to be used in the knitting of sheer, full-fashioned hosiery. For better and more-consistent results, however, it is much to be preferred to use a; partially saponifled polyvinyl acetate having a saponification number between 40 and 220.

The saponification I number of the partially saponiiied polyvinyl acetate, as used herein, is defined as the number of milligrams of potassium hydroxide required to completely saponify one gram of the partially saponifled polyvinyl acetate sample.

The term "partially saponified polyvinyl acetate is intended to include polyvinyl acetate which has been partially hydrolyzed by saponification with alkali or by any other means.

Partially saponiiied polyvinyl acetates having viscosities from 1.5 to 20 centipoises in a 4% solution at 20 C. are usefulinaccordance with this invention. The viscosity should be determined on a 4% aqueous solution at 20 C.. using a Hoeppler viscosimeter (manufactured by Gebrueder Haake, Medingen, Germany).

The water-sensitive hydroxylated polyvinyl resins are preferably used in solutions containing from 3% to 12% of the resin.

As above indicated, the partial formals of polyvinyl alcohol-are also particularly useful. Formals of polyvinyl alcohol containing 10% to 30% of formal and having 5% to 20% of boric acid, based on the weight of the formal, are preferred.

Although particularly desirable results are obtained with sizes comprising a water-sensitive hydroxylated polyvinyl resin and boric acid when the boric acid used constitutes approximately 20% to 22.5% of the weight of the said polyvinyl resin, it should be understood that boric acid may be used with the Water-sensitive hydroxylated polyvinyl resins in the preparation of sizes containing other proportions of boric acid. The amount ofboric acid required to give good running properties has been found to vary with the particular hydroxylated polyvinyl resin used. To obtain the bestresults, the amount of boric acid to be used will vary between 5% and 25%, based on the weight of the said resin. One skilled in the art can formulate sizes with increasing amounts of boric acid and readily determine the optimum concentration.

Using a, polyvinyl acetate having a saponification number of and no other agent for reducing its water-sensitivity, at least 10% boric acid is generally required to give fair running properties. With a polyvinyl acetate having a saponification number of 234 only 12.5% boric acid gives desirable results, but. this is practically all the boricacid that this partially saponified polyvinyl acetate will tolerate without precipitating from solution: Likewise, with polyvinyl acetate having a saponification number of 140 and 10% aluminum acetate as an auxiliary agent. it is possible to reduce the boric acid concentration to 10% and still retain fair running properties. The use of less than boric-acid with the hydroxylated polyvinyl resin. has never given sizes with very attractive running properties except when using a tannic acid undercoating. It

is, therefore, to be understood that in practicing this invention. proportions ofboric acid up to the limit of the tolerance 01 the polyvinyl material may be used in preparing the sizing composition.

The limit of tolerance of the polyvinyl material for the boric acid is that percentage 01 boric acid based on the weight of the polyvinyl material which-can be barely tolerated by the polyvinyl material without causing the polyvinyl material to gel or precipitate. The gelling or precipitating of the polyvinyl material is an indication that the limit of tolerance oi the boric acid has been exceeded. a I

It is, of course, within the scope of this invention to apply to the yarn coats of size of various percentages other than those specifically disclosed above. It isalso within the scope or the invention to apply two or more coats of these sizes to the yarn. Furthermore. a coat of a water-sensitive hydroxylated polyvinyl resin size can be applied over a coating of another size which by itself is insufllcient for the purposes of the present invention.

As above indicated, it is desirable to provide the yarn with an anchor coat or tannic acid prior to the application of the partially saponifled polyvinyl acetate-boric acid size. It should be understood that tannic acid, gallic acid, digallic acid or any of the various tannins, when used as an anchor coat in the sizing of a yarn in accordance with the present invention, lie within the scope of this invention and are c 'onsidered to be included by the term tannic acid. as used in the specification. Good results are obtained with 0.02% to 1.5% coats of tannic acid; and particularly good results are obtained when 0.05% to 0.3% coats of tannic acid are applied to the yarn; but the anchor coat is not to be considered to be limited to these percentages. It will be apparent that numerous similar anchoring compounds may be useful as sub-coats on yarns to the end of more eflectively binding the size composition to the yarn. In view of the new and very great problem of effecting adherence of a size to a rela- 'tively water-insensitive yarn. such as synthetic linear polyamide yarn, the principle of using an anchor coat in the sizing of yarn is an outstanding improvement.

While the invention has been described with reference to the application or the water-sensitive hydroxylated polyvinyl resin coat from water solution, it is obvious that it can be applied from solutions containingother solvents; Similarly, it will be apparent that .the anchor coat and the size coat can be applied to the yarn by other means and in other waysthan' those described above;' namely, skein immersion treatment and continuous applicationbypassing the yarn over a size roll. dippi w into the soluflOn,

While these sizing compositions may be applied to the yarn in any convenient manner, it is pre-' ierred for reasons of economy and excellence of product to apply these sizes in some tom of continuous operation. When the sizes are being applied in such a manner, it is important that these size solutions be given sufiicient time to thoroughly impregnate the yarn before drying. This may be accomplished by arranging that the yarn be given suflicient air travel in an atmosphere oi high relative humidity before being wound up, or, preferably, the sizedyarn may be wound up directly on some form of bobbin while still wet and then b allowed to dry on the bobbin. This latter procedure will, insure that the yarn dries slowly enough so that thorough penetration occurs. This sizing process is further described and claimed in co-pending application Serial No. 369,951, filed December 13, 1940.

Although polyethylene oxide having a molecular weight 01' approximately 4,000 is preferred as a plasticizer for the hydroxylated polyvinyl resins of this invention, it is to be understood that polyethylene oxides of other molecular weights can be used and the better results are obtained with polyethylene oxides having molecular weights from approximately 282 to approximately 10,000. However, the use of other polyethylene oxides is not to be considered as excluded from the scope of this invention. It will be apparent, of course, that other concentrations Such oils as oxidized linseed oils having iodine numbers between and 105, China-wood oil, castor oil, etc., will be found to be useful in conjunction with the sizes oi! this invention. Such oils maybe applied as emulsionsin water or in solutions in various solvents, such as ethyl alcohol, isopropyl alcohol, butyl alcohol, methyl, ethyl or butyl Cellosolve," etc. It will be apparent that the drying oil may be emulsified in the size composition or that it may be applied to the yarn in a separate step.

The use of an alkaline after-treatment in connection with the sizing process of this invention has been disclosed above. The alkaline treatment tends to gel the surface 01 the size coat giving good running properties to the yarn. The alkaline after-treatment may be applied in numerousways by treating the yam-with vapors or solutions or alkaline substances. By alkaline substance is meant any substance which, when shaken with water, gives an alkaline reaction to the water.

The sizes of this invention may be modified with solutions or dispersions of various modifying agents for various purposes. For example, polymethacrylic acid or polymethacrylates may be used as modifying agents to improve the run- Various other plasticizers, suchas glycerol, the

various slycols, sorbitol, glucose, diethylene glycol, triethylene glycol, ethanol formamide, glyc erol glycollate, ethanol acetamide, tetraethylene glycol, dimethoxytetraethylene glycol, etc-., may be used with these sizes. Various lubricants, such as mineral oil, olive oil, teaseed oil, other vegetable oils, sulfonated mineral oils and sulfonated based on the weight of the yarn, affording good ethanolamine and its fatty acid ester, diglycol oleate, morpholine, pyridine, etc., may be coated over these sizes either alone or mixed with a coning oil or finishing agent. It will be apparent that many of the materials which may be added to the sizing compositions, or applied to the sized yarn, may serve more than one purpose, for example, the same material may serve as a plasticizer and also as a lubricant, or as a plasticizer and a preservative.

Although the invention has been discussed with particular reference to multifilament yarns of synthetic linear polyamides, it will be obvious that the same compositions will be applicable as sizes to other synthetic linear polyamide structures, such as monofils, films,'staple fibers, spun yarn, mixed yarn, ribbon, etc. Various structures possess to a greater or smaller extent, as the case may be, essentially the same critical sizing problems as the multifilament polyamide yarns; for the smoothness and lack of water-sensitivity of the synthetic linear polyamides prevent the close adherence of the conventional sizes to the polyamide structure.

Although the sizing compositions of this invention are unique and outstanding for the sizing of synthetic linear polyamide yarns which are to be used in the knitting of sheer hosiery, they will also be useful in the sizing of other yarns and fabrics, such as cotton, silk, Wool, linen, viscose rayon, cuprammonium rayon, cellulose acetate rayon, yarn prepared fromfsynthetic linear vinyl polymers and synthetic linear ethylene polymers, etc.; although the problem of adherence of the size to the yarn is not nearly so great in the case of these other types of yarn. These sizes will be found to be particularly useful for sizing yarns which are relatively water insensitive. It will also be obvious that these sizing compositions may be useful for sizing yarns to be used in weaving operations as Well as knitting operations.

The sizes of this invention present the distinct advantage over the prior art sizes of adhering well to synthetic linear polyamide yarn while possessing other qualities desired in a sizefor yarn to be used in the knitting of sheer hosiery.

Yarns sized with the sizes of this invention and in accordance with the process of this invention knit very well, and produce sheer, full-fashioned stocking fabrics which are relatively free of snags and pulled threads. These sizes minimize edge rolling characteristics and thus assist in the more economical production of sheer, knit, full-fashioned hosiery. The sizes of this invention cause very little wear and corrosion of the needles and sinkers of the knitting machines. In knitting yarn sized in accordance with this invention, the stitch formation is very good and may be maintained uniform over long periods of time.

comparatively small amounts of these sizes are effective in protecting the multifilament polyamide yarn, 2% to 8% by weight of the size,

protection. Since the size is easily removed from the yarn and there is not so much loss in weight of the fabric resulting from the removal of the size, polyamide yarns sized in accordance with this invention are inuch more desirable, for instance, in mixed fabrics with cellulose acetate rayon and other synthetic yarns than is natural silk. Natural silk has approximately 20% to 24% sericin; hence, the boil-off of natural silk results in a great loss in weight of the fabric and the removal of the sericin size is so diflicult that it not infrequently causes considerable damage to cellulose acetate rayon or other synthetic fibers present in a fabric mixed with naturalsilk.

Since it is obvious that many changes and modifications can be made in the above-described details without departing from the nature and spirit of the invention, it is to be understood that the invention is not to be limited to the de tails described herein except as set forth in the appended claims.

I claim:

1. A yarn sizing composition comprising a hydroxylated polyvinyl resin and 5%-25% boric acid based on the weight of the resin, said resin being sufliciently water-sensitive to be readily removable from a yarn with hot water.

2. A yarn sizing composition comprising an aqueous solution of a hydroxylated polyvinyl resin and 5%-25% boric acid based on the weight of the. resin, said resin being sufficiently watersensitive to be readily removable from a yarn with hot water.

3. A yarn sizing composition containing from 3%-12% of a hydroxylated polyvinyl resin and 5%-25% boric acid based on the weight of the resin, said resin being sufficiently water-sensitive to be readily removable from a yarn with hot water. i

4. A yarn sizing composition comprising a hydroxylated polyvinyl resin in which 1%-50% of the carbon atoms of the polyvinyl chain are.attached to hydroxyl groups and 5%-25% boric acid based on the weight of the resin, said resin being sufficiently water-sensitive to be readily removable from a yarn with hot water.

5. A yarn sizing composition comprising boric acid and a partial ester of polyvinyl alcohol, said boric .acid being present in a quantity from 5%-25% of the weight of the resin; said resin being sufficiently water-sensitive to be readily removable from a yarn with hot water.

6. A yarn sizing composition comprising boric 'acid and 3%-12% of a partial ester of polyvinyl alcohol, said boric acid being present in a quantity of 5%25% of the weight of the resin, said resin being sufficiently water-sensitive to be readily removable from a yarn with hot water.

'7. A yarn sizing composition comprising a partially saponified polyvinyl acetate and 5%-25% boric acid based on the weight of the acetate.

8. A yarn sizing composition comprising a partial formal of polyvinyl alcohol and 5%-25% boric acid based on the weight of the formal.

9. A yarn sizing composition comprising an aqueous solution of a partially saponified polyvinyl acetate and 5%-25% boric acid based on the weight of the acetate.

10. A yarn sizing composition comprising an aqueous solution containing between 3%-12% of a partially saponifiedv polyvinyl acetate and 5%-25% boric acid based on the weight of the acetate.

11. A yarn sizing composition. comprisingfan' aqueous solution containing a partially saponie fled polyuinyl acetate and %-25% boric acid basedon the weight or the acetate, said polyvinyl acetate, having a saponiflcation number of between 40 and 220.-

12. A\ yam sizing composition comprising an aqueous solution containing a partially saponiiied' polyvinyl acetate and 5%-25% boric acid based asa'geoi tures =0: diamine with dibasic carboxylic acid. said yam suitable for use in the knitting of sheer,

from at least one of the groups consisting of (a) monoaminomonocarboxylic acids, and (b) mixtures of diamine with dibasic carboxylic acid, said yarn suitable for use in the knitting of sheer, full-fashioned hosiery, containing a coating of 'a size comprising a hydroxylated polyvinyl resin and 5%-25% boric acid, said resin being sufficiently water-sensitive to be readily removable from a yarn with hot water.

14. A yarn composed of a linear polyamide comprising the reaction product of a linear polymer-forming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting of (a) monoaminomonocarboxylic acids, and (b) mixtures of diamine with dibasic carboxylic acid, said yam suitable foruse in the knitting of sheer, full fashioned hosiery,-containing from 3%--12% of a hydroxylated polyvinyl resin and 5%-,25% boric acid based on the weight oi'the resin, said resin being sufliciently water-sensitive to be readily removable from a yarn with hot water.

15.- A yarn composed of a "linear polyamide comprising the reaction product of a linear polymet-forming composition which comprises in substantial amount reacting material selected from at least one of the groupsconsisting of (a) 'monoaminomonocarboxylic acids, and (b) mixtures "or diamine with dibasic carboxylic acid, said yarn suitable for use in the knitting of sheer full-fashioned hosiery, containing a coating oi! a size comprising a hydroxylated polyvinyl resin in which 1%50% of the carbon atoms of the polyvinyl chain are attached to the hydroxyl groups, and 5%-25% boric acid based on the weight of the resin, said resin being sufficiently water-sensitive to be readily removable from a yarn with hot water.

16. A yarn composed of a linear polyamide comprising the reaction product of a linear polymer-forming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting oil (a) monoaminomonocarboxylic acids, and (b) mixtures of diamine with dibasic carboxylic acid,

full-fashioned hosiery, containing a coating of a size comprising boric acid and 3%-12% or a partial ester of polyvinyl alcohol, said boric acid being present in a quantity of 5% -25% based on the weight of the resin, said resin being suiilciently water-sensitive to be readily removable from a yarn with hot water.

18. A yarn composed of a linear polyamide comprising the reaction'product of a linear pol mer-i'orming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting of (a) monoaminomonocarboxylic acids, and (b) mix-- tures of diamine with dibasic carboxylic acid, said yarn suitable for use in the knitting of sheer, full-fashioned hosiery, containing a coating of 'a' size comprising partially saponifled polyvinyl said yarn suitable for use in the knitting of sheer,

full-fashionedhosiery, containing a coating of a size comprising boric acid and a partial ester 01' polyvinyl alcohol, said boric acid being present in a quantity of 5%-'25% based on the weight of the. resin, said resin being sufliciently watersensitive to be readily removable from a yarn with hot water.

17. A yarn composed of a linear polyamide comprising the reaction product of a linear polymer-forming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting of (a) monoaminomonocarboxylic acids, and (b) mixacetate and 5%-25%' boric acid based on the weight of the acetate.

19. A yam composed of a linear polyamide comprising the reaction product of a linear polytrier-forming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting of (a) monoaminomonocarboxylic acids, and (b) mixtures of diamine with dibasic carboxylic acid,

,said yarn suitable for use in the knitting of sheer,

full-fashioned hosiery, containing a coating of a size comprising partially saponifled polyvinyl acetate and 5%-25% boric acid based on the weight of the acetate, said polyvinyl acetate having a saponification number between 40 and 220.

20. A yarn composed of a linear polyamide comprising the reaction product of a linear polymar-forming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting Of (a)' monoaminomonocarboxylic acids, and (72) mixtures of diamine with dibasic carboxylic acid, said yarn suitable for use in the knitting of'sheer, full-fashioned hosiery, containing a coating of a size comprising partially saponiiied polyvinyl acetate and 5%-25% boric acid based on the weight 01 the acetate, said polyvinyl acetate having a viscosity of between 1.5 and 20, centipoises in a 4% water solution at 20 C.

21. A yarn sizing composition comprising boric acid and a partial ether of polyvinyl alcohol, said boric acid being present in a quantity from 5%25% of the weight of the resin, said resin being suflieiently water-sensitive to be readily re- 1 movable from a yarn with hot water.

22. A yarn sizing composition comprising boric acid and 3%-12% of a partial ether of polyvinyl alcohol, said boric acid,being present in a quantity of 5%-25% of the weight of the resin, said resin being sufllciently water-sensitiv to be readily removable from a yarn with hot water.

a 23. A yarn composed of a linear polyamide comprising the reaction product of a linear polymer-i'orming composition which comprises in substantial amount reacting material selected from at least one of the groups consisting of (a) monoaminomonocarboxylicacids, and (b) mixtures of diamine with dibasic carboxylic acid, said yarn suitable for use in the knitting of sheer. full-fashioned hosiery, containing a coating of a size comprising boric acid and a. partial ether of polyvinyl alcohol, said boric acid being present in a quantity of 5%-25% based on the weight of the resin, said resin being sufllciently watersensitive to be readily removable from a yarn with hot water.

24. A yarn composed of a linear polyamide comprising the reaction product of a linear polymer-iorming composition which comprises in substantial amount reacting material selected from at least one o! the groups consisting of (a) monoaminomonocarboxylic acids, and (b) mix- I tures of diamine with dibasic carboxylic acid,

said yam suitable for use the knitting of sheer,

full-fashioned hosiery, containing a coating of a size comprising boric acid. and 3%-.-12% of a partial ether of polyvinyl alcohol, said boric acid being present in a quantity of 5%-25% based on .the weight of the resin. said resin being sumciently water-sensitive to be readily removable from a yarn with hot water.

EDGAR W. SPANAGEL.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2439108 *Sep 11, 1943Apr 6, 1948Eastman Kodak CoCoating with polyvinyl alcohol
US2459052 *Mar 27, 1947Jan 11, 1949Ici LtdSized glycol terephthalate yarn, process, and composition for producing same
US2491642 *Sep 2, 1944Dec 20, 1949Du PontPolyvinyl alcohol casting solution
US2532400 *Dec 8, 1948Dec 5, 1950Celanese CorpSizing compositions
US2576915 *Apr 29, 1948Dec 4, 1951Monsanto ChemicalsMethod of sizing yarns and composition therefor
US2607765 *Dec 5, 1949Aug 19, 1952Du PontReaction of polyvinyl alcohol with boric acid
US2622044 *Aug 2, 1949Dec 16, 1952Sherwin Williams CoMethod of treating vulcanizable rubber surfaces
US2623834 *Nov 18, 1949Dec 30, 1952Ici LtdColoring process for nylon
US2630416 *Dec 6, 1949Mar 3, 1953Stein Hall & Company IncTextile size comprising an aqueous solution of a styrene-maleic anhydride copolymer and a water soluble borate
US2651587 *Jun 2, 1947Sep 8, 1953Monsanto ChemicalsTreatment of textile materials
US2663989 *Mar 19, 1949Dec 29, 1953Schlatter CarlCoated articles and textiles and emulsions for producing them
US2664409 *Oct 9, 1950Dec 29, 1953British Nylon Spinners LtdTextile treating composition and method
US2702796 *May 31, 1950Feb 22, 1955Atlas Powder CoTextile size comprising a partially neutralized polymethacrylic acid
US2826515 *Jul 30, 1956Mar 11, 1958Dow Chemical CoMethod of sizing nylon textile materials with coal acid compounds and resulting article
US2876205 *Oct 15, 1953Mar 3, 1959Nopco Chem CoTextile sizing agents plasticized with blends of water-soluble polyhydroxy alcohols, aliphatic amides and hydroxy acids
US3033808 *Jan 14, 1959May 8, 1962Crosby Forest Products CoTung oil-latex coatings
US3135648 *Jul 13, 1961Jun 2, 1964Air ReductionPolyvinyl alcohol adhesive containing a boron compound and cellulosic articles laminated therewith
US4409352 *Dec 2, 1981Oct 11, 1983International Standard Electric CorporationMethod of making a dispersion lacquer for luminescent screens
US6280849 *Jul 15, 1998Aug 28, 2001Nippon Electric Glass Co. Ltd.Glass article having surface coating of boric acid and method for producing the same
DE963550C *Mar 17, 1951May 9, 1957Phrix Werke AgVerfahren zur Verarbeitung von Faeden aus Polycaprolactam
WO2006068751A2 *Nov 18, 2005Jun 29, 2006Celanese Int CorpCorrosion-resistant ply bond adhesives and products and processes incorporating such adhesives
Classifications
U.S. Classification428/375, 528/288, 528/369, 528/367, 252/8.81, 525/56, 528/310, 8/DIG.100, 528/394, 528/328, 252/8.84, 524/405, 8/DIG.210
International ClassificationD06M11/82, D06M15/333
Cooperative ClassificationD06M11/82, Y10S8/21, D06M15/333, Y10S8/10
European ClassificationD06M11/82, D06M15/333