AU610554B2

AU610554B2 - A sizing composition, method of preparing same and fibrous material sized with same

Info

Publication number: AU610554B2
Application number: AU10988/88A
Authority: AU
Inventors: John C. Lark
Original assignee: Individual
Current assignee: Individual
Priority date: 1988-01-29
Filing date: 1988-01-29
Publication date: 1991-05-23
Anticipated expiration: 2008-01-29
Also published as: AU1098888A

Description

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IIi 49 3 f COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMAPLETE SPECIFICATION FOR OFFICE USE Form Short Title: Int. Ch.

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Application Number: Lodged: Complete Specification-Lodged: Accepte-d:I Lapsed: Flublished: Priority: Related Art: 00 0

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TO BE COMPLETED BY APPLICANT o o 0 0 bzi of Applicant: Address of Applicant: Actual Inventor: Address for Service: JOHN C. LARK P.O. Box 321, EDEN, NORTH CAROLINA 27288, U.S,A.

John C. Lark GRIFFITH-J 1ASSEL FRAZER 71 YORK STREET SYDNEY NSW 2000

AUSTRALIA

Complete Specification for the Invention entitled:, "A SIZING COMPOSITION, METHOD OF PREPARING SAME AND FIBROUS MATERIAL SIZED WITH SAME" The following statement is a full description of this Invention, incloding the best method of performing it known to me:- 8581A/bm s A SIZING COMPOSITION, METHOD OF PREPARING SAME, AND FIBROUS HATERIAL SIZED WITH SAME Background of Invention The use of amorphous, dense, colloidal silica materials has long been desirable to provide a frictionizing effect on fibers and to increase the strength and performance of fibrous materials, such as textile yarns during weaving. Deposition of the small, dense, amorphous particles on the surface of a fibrous material promotes friction between adjacent fibers to produce an effect with might be compared to placing two pieces of sandpaper face-to-face. Luvisi U.S. Patent No. 2,787,968 discloses in detail the effect of colloidal silica on various substrates.

However, the use of amorphous, use, colloidal silica materials as frictionizing agents in water-based process industries has not been widely accepted due to the inherent S0 chemical nature of the colloidal silica itself. When water based 0' .00: e4 0 0 colloidal silica is applied to an article in an aqueous process, the silica particles exist as small, discreet spheres. Upon 8 a removal of the process water, or the water carrier for the colloidal silica, the swall silica particles follow their water oo..0 carrier into a diminishing volume of carrier and steadily 0 increasing silica particle concentration. When enough of the °Q o 9 oo water carrier is removed, agglomeration of the colloidal 0 0 particles occurs with the formation of large, very abrasive, amorphous granules. These large agglomerated silica granules are too large to provide an efficient frictionizing effect between fibers and are so abrasive that adjacent fibers may be severely weakened or cut by their action.

ri .9r 8581A/bmi Sworn to and subscribed before me this 16th day of February, 1988.

My Commission Expires: 10-18-92 OFI LSEAL NDTAPY PUBLIC WENDY A. FARGIS 111.1 Comm VOr,.

Nota Public I. Vossos U.S. Patent No. 3,629,1398 and Kovarik U.S.

Patent No. 3,660,301 disclose a process for the production of organically coated colloidal silica solids which may be dispersed in non-polar organic solvents. The organsols produced by the cited teachings demonstrate the ability to be concentrated to yield dry, free-flowing, coated colloidal silica powders which may be redispersed in an organic media, and which retain the properties of the original colloidal silica. These teachings indicate that the drawbacks of agglomeration may be prevented when the colloidal silica particles have been modified by an organic surface coating and dispersed in an organic solvent. An attempt to exploit this technology in the textile industry was made based upon the teachings of Vossos and Kovarik in the cited patent references. This attempt was not commercially successful Re *15'8 but did prove that the organically coated silicas, applied from non-polar solvents, retained their original size and shape as discrete particles without agglomeration. The coated silica S" particles were shown to be non-abrasive toward fiber, metal, or cer-mic surfaces which came into contact with the treated yarns.

Due to the maintenance of the original size and shape of the colloidal silica particles, one of the most perplexing drawbacks 4 0 of this treatment was the frictionizing effect was so efficient 0 S that processing of treated fibrous material thrcugh subsequent steps was rendered very difficult. Equally important to the lack of acceptance of these materials was their incompatibility with existing water based process modifications. These changes would have been major capital commitments necessary for the use of these materials. These factors, coupled with an unattractive 3 economic situation with the organosol in oil, made this concept unacceptable to the industry.

Summary of the Invention This invention relates to the preparation and application of strength enhancing compositions in and from aqueous media and the fibrous articles treated herewith. In its more specific aspects, this invention relates to the formation and application of a sizing composition for treating fibrous material particularly a complex of colloidal silica particles and polymeric resin in an aqueous medium with the silica particles being substantially encapsulated in the polymeric resin known collectively as organo polymeric-colloidal silica complexes produced in an aqueous medium, for application from an aqueous medium, to fibrous materials. In the course of the developments of the parameters necessary for the reduction of this invention to practice, it has been found that polymeric polyester resins are the materials of preference for use in the formation of the strength enhancing compositions. While other water soluble or dispersible polymers might find utility in the formation of the polymeric-colloidal silica complex, water soluble or dispersible polyester resins have been shown to provide additional benefits 0* such as adhesion and plasticization of other materials applied to fibrous articles. The polyester resins have demonstrated outstanding utility in providing efficient polymeric-colloidal 4 silica complexes during application of the strength enhancing materials to fibrous articles in wet processes.

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AW ,g I SPreferably, this invention relates to the application of polymeric organic-colloidal silica complexes to the sizing of textile yarns for the purpose of weaving yarns into textile materials. In this process, it is desirable before weaving to treat the warp yarn with a sizing composition or agent which adheres to and binds the fibrous components of the yarn. This treatment strengthens the textile yarns and renders them more resistant tC abrasion during subsequent weaving operations. It is especially important that the sizing process and agent impart both abrasion resistance and adds strength to the yearn due to S the abrasion and stress encountered during fabric formation.

4 a .o Failure of the yarn during weaving lowers both produce quality and the efficiency of the fabric formation process. It is also 0 P o0" importaLt that the sizing composition be easily removed from the 9°45 fabric by a conventional de-size or scouring operation.

Removability of the sizing materials allows the de-sized fabric to be processed through subsequent dyeing and finishing "S operations without interference from residual materials. Various 0000 o0 0 high molecular weight natural and synthetic materials have been 0o suggested and are currently being utilized as sizing agents for 0 0 yarns. Among such materials are starches of nearly all varieties and modifications, partially and fully hydrolyzed polyvinyl o000 alcohols and copolymers, carboxymethyl cellulose, polymers derived from acrylic monomers, polymers derived from polyvinyl acetate and those derived from vinyl acetate monomers in combination with other monomers incorporated into the polymer via vinyl polymerization. Low and intermediate molecular weight polyester resins have also shown utility in yarn sizing $1 E> 4 1 applications. Depending upon the specific requirements and desired results, nearly all sizing compositions applied to spun yarns are comprised of the aforementioned materials, or any, or all of their combinations.

The sizing composition of the present invention inclues acomplex of colloidal silica pairticles and polymeric resin in an aqueous medium, with the silica particlcs substantially encapsulated in the resin. Preferably the silica particles are in the 20-50 millimicron range anid the resin is an intermediate molecular weight 5,000 to 7,0003) polyester resin. In the preferred emhodimen: the resin is reprdfo O isophthalic acid, diethylene glycol, and trimellitic anhydride, such as disclosed in Lark Patent No. 4,268,645 neutralized *0conventionally with amine containing materials to render it Sreducible in water. Preferably the composition is soluble in water to form a size for fibrous materials which compresses a pulverized dry complex of polyester resin and colloidal silica at**particles. The ratio of resin to silica particles is sufficiently high to result in substantially encapsulation of the siiaparticles in the resin so that upon drying of the aqueous *4based composition on the sized materials in the silica particles will remain substantially discrete rather than agglomerating.

When the silica particles are of a size approximately millizuicrons, the ratio of resin to silica is at least 3 to 1.

in the preferred, embodiment the composition includes I t other conventional sizing components, such as lubricant, modified starch, a~nd polyvinyl alcohol, when the silica particles are approximately 20 or Approximately 50 millimicrons and modified 6 i r corn starch when the silica particles are approximately millimicrons.

According to the preferred method of the present invention, a composition for sizing textile materials is obtained by mixing colloidal silica particles, preferably in a size range of 20-50 millimicrons, with a polymeric resin, such as polyester resin of an intermediate molecular weight in the range of 5,000- 7,000, prepared from isophthalic acid, diethylene glycol, and trimellitic anhydride, neutralized with amine containing materials to render the resin reducible in water.

Preferably when mixing colloidal silica particles of et* a a size of approximately 20 millimicrons constituting approximately 5 parts by weight of solid with polymeric resin that is an aqueous based polyester resin which is 25% solids constituting approximately 200 parts by weight of solids, included in that mixing are approximately 300 parts by weight ethoxylated corn starch, approximately 100 parts by weight polyvinyl alcohols, approximately 50 parts by weight potato S a o, starch, and approximately 30 parts by weight lubricant.

It is further preferable that when mixing colloidal o a silica particles of a size approximately 50 millimicrons constituting approximately 2.5 parts by weight of solids with a polymeric resin which is an aqueous based polyescer resin of approximately 25% solids constituting approximately 80 parts by weight, included in the mixing are cpproximately 200 parts by weight modified cornstarch and approximately 12 parts by weight lubricant.

7 j', r* -CI- -ChPI-oa~Llr(l 4111; i-*~l~rCI l-~ S S Likewise, preferably when mixing colloidal silica particles of a size approximately 25 millimicrons constituting approximately 2.8 parts by weight solids with a polymeric resin which is an aqueous based polyester resin which is approximately 25% solids constituting approximately 72 parts by weight, included in the mixing process are approximately 180 parts by weight ethoxylated corn starch and approximately 12 parts by weight kettle wax.

The present invention includes a fibrous product that has been sized with the aforesaid sizing composition.

As a result of the presence invention, enhanced strength and performance are obtained for fibrous materials that have been treated with the sizing composition. For example, textile yarns composed of short or staple fibers exhibit enhanced strength and abrasion resistance during weaving as well as being easily cleansed of the composition during conventional de-sizing or scouring. Also, the sizing composition can be applied to Sweakened yarns to restore a measure of tensile strength to aid 5444 in the more efficient processing of these yarns into fabric.

z;0 Further advantages and applications of this invention should be come obvious to those skilled in the art.

Detailed Description of the Preferred Embodiment The following are examples of preferred embodiments of the present invention as applied to fibrous textile materials and the resulting effects upon the strength and efficiency of the treated materials during subsequent processing steps. These examples are merely illustrative and should not be construed as 8 0f i /f^ s 3 r W ^C~ uSW< t-

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I Ll"oa~-pp~nrs~p limiting the scope of the invention. It must be noted that no laboratory procedure has been widely accepted to predict the effect of a size or size additive in the weaving operation. For this reason, the examples involving the effect upon weaving efficiency were performed under mill scale conditions.

In each example, the polyester resin utilized was Pioneer Chemicals, Inc. resin PL 725 or PL401, which is of intermediate molecular weight (5,000-7,000) prepared from isophthalic acid, diethylene glycol, and trimellitic anhydride as disclosed in Lark U.S. Patent No. 4,268,645 and conventionally neutralized with an amine containing material 0 f, (monoisopropylamiine) having an acid number of at least 35 to render it reducible into water. Several different particle size colloidal silicas were utilized in the separate examples, the o000 tlhao particle sizes being specified in the examples cited.

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1 EXAMPLE 1 A control sizing composition not incorporating the present invention was prepared by mixing 380 gallons of water, 300 Ibs. of ethoxylated corn starch, 50 lbs. of modified potato starch, 100 lbs. of polyvinyl alcohol, 200 lbs. of aqueous based polyester resin at 25% solids, and 30 Ibs. of was. This mixture was cooked under standard conditions and finished to a level of 505 gallons containing 11% total solids. 50/50 polyester/cotton yarn of 35's cotton count was sized through a commercial slasher with this composition. A single end of warp yarn sized with this formulation was collected on a winder located on the front end of the slasher. This yarn was submitted for laboratory strength and elongation testing, the results of which are set out in Table I below under the heading Example 1 Control. Sized warps based upon this formulation were used in weaving on a shuttle loom and exhibited on overall weaving performance of 93.20% over the life of the warps in the looms.

EXAMPLE 2 i The size formulation detailed in Example 1 was 3O"~ utilized according to the present invention by the addition of lbs. of 20 millimicron colloidal silica solids in water.

So This mixture was processed under standard conditions and finished to 507 gallons of size. A single end of yarn sized with this composition was collected on a 'inder and submitted for laboratory strength and elongation testing, the results of which are set out in Table I below under the heading Example 2. Two full warps were sized with this composition and used in weaving on a shuttle loom to be compared to the warps from the same yarn ~iii I c I *1 i 26. A fibrous product according to claim 25 and set size~d with the composition of Example 1 and exhibited overall weavirng performance of 97.45% over the life of the warps in the looms.

A com~parison of the results of Example 2 and Example 1 are set out under the heading Percent Difference in Table I.

TABLE 1 SINGLE SIZED YARN COMPARISONS EXHIBIT 1 EXHIBIT 2 PERCEN~T CONTROL TEST DIEFIffO2E 0 Elongation 4.64 4.9392 5,431 Std. Deviation 0.70 0.6 6 4.86 Coeff. of Variation 15.065 13.664 9.30 1 Elong~ation Rancig High 3.5.04. Low 0 Range Avg. gm to Break Std. Deviation S:Coeff. of Variation Q00 Streng~th Ranare 6.115 2.83 3.285 281.98 32. 62 11.57 6.342 3.308 3 .034 303.61 30.208 9.97 3.29 16.89 7.64 7.67 7.394 13.83 Hih367.67 365.876 0.469 0Low 205.47 234.332 14.047 Range 162.14 131.554 18.864 Number of Breaks 100 250 EXAMPLE 3- The mixture utilized in Example 2 was employed with the following modification. The 200 lbs. of polyester resin in water was mixed with 5 lbs. of 20 millimicron colloidal silica solids and additional water to maintain the mixed product system at a 0O~ level of 25% solids. This mixture was stored for a period of fiJVe days and then cooked with the other ingredients as desc ribed in Examples 1 anld 2. Two warps were seized with the composition containing the precompiexed poly ester-colloidal silica material and use in weaving on a shuttle loom in comparison with warps from the same yarn sized with the composition of Example 1. in I I this ,example, the warps sized with the composition of Example 1 provided a weaving performance of 93.31% in comparison with a performance of 97.42% for the test warps,, EXAMPLE 4 A mixture of 150 lbs. of polyvinyl alcohol, 100 lbs.

of starch, 12 lbs. of kettle wax, and 2 lbs. of 20 millimicron colloidal silica solids was cooked and applied to two warps of 65/35 polyester/cotton 351s cotton count yarn. These two warps were woven on projectile looms and compared with warps from the same yarn set sized without the addition of the colloidal silica.

Yarns collected from these warps exhibited lower tensile strength in laboratory testing and lower weaving performance than the warps sized with the composition which did not contain the colloidal silica. No polyester-colloidal silica complex of the i. invention was present. The effects of the abrasive, agglomerated 9 9 silica were apparent in lowered tensile strength and weaving efficiency.

EXAMPLE The compositions of Example 1 and Example 2 were 4*6 repeated on 1/2 set of yarn each of 50/50 polyester/cotton 06 cotton count yarn. The two 1/2 sets were woven on shuttle looms and compared directly by both total efficiency and industrial engineering studies. The 1/2 set sized with the composition of Example exhibited a weaving performance of 91.6% and a warp stop level of 0.804/hour. The 1/2 seb sized with the composition of Example 2 exhibited a weaving performance of 95.2% and a warp stop level of 0.497/hoUr.

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EXAMPLE 6 200 lbs. of carboxmethylated starch and 12 lbs. of kettle wax were cooked and applied to 100% cotton yarn, 14's cotton count. Industrial engineering studies of shuttle weaving indicated that a warp stop level of 0.83/hour was obtained with this composition, which did not include the silica/resin complex of the present invention.

EXAMPLE 7 The composJition of Example 6 was repeated with the addition of 80 lbs. of 25% polyester resin in water. Water was added to maintain the same solids and add-on as Example 6.

Industrial engineering studies of shuttle weaving indicatad a warp stop level of 0.69/hour with this composition, which did not 94 include silica and therefore did not include the silica/resin complex of the present invention.

44900 EXAMPLE 8 The composition of Example 7 was repeated with the addition of 2.5 Ibs. of 50 millimicron colloidal silica and applied to the same 14's 100% cotton count yarn utl.ised in Examples 6 and 7. Industrial engineering studies of sh weaving indicated that these warps performed at a warp stop ti *a of 0.42/hour, EXAMPLE 9 0o 00 A mixture of 100oo bs. of polyvinyl alcohol, 100 Ibs.

of ethoxylated corn starch and 1.2 ibs. of kettle was cooked and finished to 200 gallons and applied to 100% cotton 20' cotton count yarn and woven on a Jacquard loom. This size oposition 2.3 y f? t 1 performed at a warp stop level of 4.2/100,000 picks. This composition did not include the silica/resin complex of the present invention.

EXAMPLE A mixture of 100 lbs. of carboxymethyl cellulose, 100 lbs. of ethoxylated corn starch, and 12 Ibs. of kettle wax was finished to 200 gallons and applied to the yarn of Example 9 and woven on a Jacquard loom. This composition performed at a warp stop level of 4.4/100,000 picks. It did not include the silica/resin complex of the present invention.

EXAMPLE 11 A mixture of 180 ibs. of ethoxylated corn starch, 72 Ibs. of 25% polyester resin solids, 12 Ibs. of kettle waxi and 2.8 lbs. of 25 millimicron colloidal silica solids was finished to 200 gallons and applied to the yarn of Example 9, This sized cotton yarn was woven on a Jacquard loom and performed at a warp a ow w r stop level of 2.1/100,000 picks.

EXAMPLE 12 *400 grams of polyester resin at 25% solids in water was Z"o e mix-d with 10 grams of 25 millimicron colloidal silica solids and the mixture brought to a total of 500 grams with water. This mixture was brought to the boil to remove water from the polyester-colloidal silica complex. After approximately 90% of Sthe water had been removed, the mixture was transferred to a microwave oven and the remaining water removed from the product.

The resulting dried film contained no apparent agglomerated silica particles upon examination under a low power microscope.

Redispersion of the polymer film was accomplished at 200°F. in 14 if\ l 4 4ev "sia-* )p

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,'i i i i; i- i 1 water with the aid of small amounts of aqua ammonia. The redispersed polymer in water was cooled and filtered through paper. The procedure was utilized to establish the ra'uon of polyester resin solids to silica solids necessary to avoid the formation of agglomerated silica particles upon dry-down of the resin-silica complex.

Ful. ,er laboratory tests were conducted to determine resin to silica ratios that would provide substantial silica encapsulation. The compositions were dried for observation of possible agglomeration rather than encapsulation and were also filtered to observe the presence of agglomerates. Results are set out in Table II below. The laboratory tests were performed 0 0 utilizing an intermediate molecular weight polyester resin o o 0. o S (approximately 5,000-7,000) and a colloidal silica which averages S 25 millimicrons. Film preparation of the higher resin/silica Scomplexes (4/1 and 5/1) was also accomplished by mild 0 o acidification of the aqueous mixture with dilute acetic acid followed by drying the precipitated complex. The resin/silica rations determined are based upon the specific particle size 0 colloidal silica utilized. Larger particle size sols will exhibit encapsulation at a lower resin/silica ratio due to the significant differences in surface area of the sols. In the same context, lower molecular weight polyester resins allow a lower 0 O resin-silica ratio due to the availability of a higher number of polymeric molecules per unit weight. In these tests the residue collected on the filter paper was washed with aqueous ammonia to remove any polyester resin. The agglomerated silica collected was not affected by the ammonia wash. The inorganic nature of f~4V~ u~ i ili-IIOI~ the residue collected on the filer paper was confirmed by ignition of the filter paper and granular residue.

TABLE II Effect of Polymer/Silica n Silica Encapsulation Parts Parts Dried Film Residue Collect Resin Silica Characteristics on Filter Paper 1.0 Grainy Yes inorganic 0.75 1.0 Grainy Yes inorganic 1.0 Grainy Yes inoriganic 3.0 1.0 Slightly Yes slight inorganic Grainy Residue on filter 1.0 Only a slight None haze in film a' 5.0 1.0 Clear None *EXAMPLE 13 A yar package conrtaining 600 grams of bleached 100% o cotton yarn, 8's cotton county, was placed in a Gaston County A e laboratory package dye machine and the pH of the aqueous phase adjusted to 6.5 with dilute acetic acid. The package was subjected to a 35 minute mock dye cycle, followed by a standard op, drying and conditioning cycle. This yarn exhibited a low end break factor of 450 grams on a Uster single-end test.

EXAMPLE 14 Water was added to a Gaston County laboratory package dye machine and the pH adjusted to 8.5 by the addition of dilute aqueous ammonia. 7.3 grams of pulverized dry silica/resin complex containing 6.25 grams of polyester resin solids and 1.05 grams of 25 millimicron colloidal silica solids were added and the mixture circulated for a total of 20 minutes at ambient -i II i: i; -n 1 1 temperature. At the and of the 20 minute circulation cycle, the pH of the aqueous solution was adjusted to 6.5 with dilute acetic acid. A yarn package containing 600 grams of bleached 100% cotton yarn from the same lot cited in Example 13 was placed in the Gaston County package dye machine and a 35 minute mock dye cycle performed under the same conditions cited in Example 13.

After a standard drying and conditioning cycle, the yarn exhibited a low end break factor of 525 grams on a Usher singleend test. These results were consistent throughout the yarn package, indicated that the complex was exhausted uniformly in the mock dye procedure. A comparison of these results with those of Example 13 clearly indicates the advantage of the present invention, and that silica/resin complex of the present invention will perform in the same efficient manner as the complex formed in situ with the two components.

The present invention may be practiced by forming the composition before application, by preparing the silica/resin complex as a dry powder for in situ application, or by forming '0:o the composition in situ during an operation such as dyeing.

It is contemplated that the resin used in the present invention may be of molecular weight range other than S intermediate and may be neutralized with basic nitrogen o o containing materials other than amines.

It is expected that colloidal silica particles of sizes different than in the foregoing examples may be used, such as in the range of 3 to 150 millimicrons, but only if the silica is in the form of a sol. Further, it is contemplated that additives,

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_-_IIICIR CII- i ~U~U1PI~IU^- )I I~jju~ja~i~)~ S I such as alumina may be usable with silica in the colloidal silica sol.

It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of a broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications, and equivalent arrangements will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made 0 o merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended to be contrued to limit the present invention or otherwise to 0 0 exclude any such other embodiment, adaptations, variations, modifications, and equivalent arrangements, the present invention being limited only by the claims appended hereto and the t equivalents thereof.

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Claims

1. A sizing composition for treating fibrous materials comprising a complex of colloidal silica particles and polymeric resin in an aqueous medium, with said silica particles being substantially encapsulated in said resin.

2. A sizing composition according to claim 1 and characterized further in that said polymeric resin is a polyester resin.

3. A sizing composition according to claim 2 and characterized further in that said polyester resin is of an intermediate molecular weight in the range of 5,000 to 7,000.

4. A sizing composition according to claim 1 and characterized further in that said colloidal silica particles are of a size in the range of 20-50 millimicrons.

5. A sizing composition according to claim 2 and Scharacterized further in that said polyester resin is a resin prepared from isophthalic acid, diethylene glycol and tri.ellitic anhydride neutralized with amine containing materials to render it reducible in water.

6. A sizing composition according to claim 1 and characterized further in that said colloidal silica particles are of a size of approximately 20 millimicrons, said polymeric resin S is an aqueous based polyester resin, and said composition includes modified starch, polyvinyl alcohol and libricant which S'*o act as sizing components.

7. A sizing composition according to claim 1 and characterized further in that said colloidal silica particles are 19 -I I of a size of approximately 50 millimicrons, said polymeric resin is an aqueous based polyester resin, and said composition includes modified starch and lubricant.

8. A sizing composition according to claim 1 and characterized further in that said colloidal silica particles are of a size of approximately 25 millimicrons, said polymeric resin is an aqueous based polyester resin, and said composition includes modified corn starch.

9. A composition soluble in water to form a size for fibrous materials comprising a pulverized dry complex of polyester resin and colloidal silica particles. A composition according to claim 9 and characterized further in that the ratio of resin to silica in the o complex is sufficiently high to result in substantial encapsulation of silica particles in resin.

11. A composition according to claim 10 and characterized further in that said silica particles are of a size of approximately 25 millimicrons and said ratio of resin to silica is at least 3 to 1.

12. A method of preparing a composition for sizing 0 6. textile material comprising mixing colloidal silica particles with polymeric resin in an aqueous medium to substantially encapsulate said silica particles in said resin.

13. A method according to claim 12 and characterized further in that said polymeric resin is a polyester resin.

14. A method according to clai 13 and characterized further in that said polyester resin is of an intermediate molecular weight in the range of 5,000 to 7,000. 8ia I~riS j firllQ~ZUC -0 1 1"NOW__ _W_ A method according to claim 12 and characterized further in that said colloidal silica particles are of a size in the range of 20-50 millimicrons.

16. A method according to claim 13 and characterized further in that said polyester resin is a resin prepared from isophthalic acid, kiethylene glycol and trimellitic anhydride, neutralized with amine containing materials to render it reducible in water.

17. A method according to claim 16 and characterized further in that said colloidal silica particles are of a size of approximately 20 millimicrons, said polymeric resin is an aqueous based polyester resin, and said composition includes modified 5*o starch, polyvinyl alcohol and lubricant. o 18. A method according to claim 12 and characterized further in that said colloidal silica particles are of a size of a o 0: approximately 20 millimicrons, said polymeric resin is an aqueous based polyester resin, and said silica constitutes approximately 5 part by weight of solids and said resin is approximately 0: solids and'constitutes approximately 200 parts by weight. o" 19. A method according to claim 16 and characterized further in that included in th mixing are approximately 300 0 0 parts by weight ethoxylated corn starch, approximately 100 parts 1by weight polyvinyl alcohol, approximately 50 parts by weight potato starch ard approximately 30 parts by weight lubricant. A method according to claim 12 and characterized further in that said colloidal silica particles are of a size of approximately 50 millimicrons, said polymeric resin is an aqueous 21 r 0 "4 4 i i based polyester resin, and said composition includes modified starch and lubricant.

21. A method according to claim 12 and characterized further in that said colloidal silica particles are of a size of approximately 50 millimicrons, said polymeric resin is an aqueous based polyester resin, and said silica constitutes approximately 2.5 parts by weight of solids and said resin is approximately solids and constitutes approximately 30 parts by nt.

22. A method according to claim 21 .laracterized further in that included in the mixing are approximately 200 parts by weight modified cornstarch and approximately 12 parts by weight lubricant. 0 00 co o 23. A method according to claim 12 and characterized 00 So:, further in that said colloidal silica particles are of a size of t 6 approximately 25 millimicrons, said polymeric resin is an aqueous6 based polyester resin, and said silica constitutes approximately 2.8 parts by weight of solids and said resin is approximately solids and constitutes approximately 72 parts by weight. 0

24. A method according to claim 23 and characterized 0 0 o* o further in that included in the mixing are approximately 180 i'o°o parts by weight ethoxylated corn starch and approximately 12 parts by weight kettle wax. 0 25. A fibrous product sized with a sizing composition comprising a complex of colloidal silica particles and water soluble polymeric resin with said silica particles substantially encapsulated in said resin. rv'v j 26. A fibrous product according to claim 25 and Scharacterized further in that said polymeric resin is a polyester resin.

27. A fibrous product according to claim 26 and characterized further in that said polyester resin is of an intermediate molecular weight in the range of 5,000 to 7,000.

28. A fibrous product according to claim 25 and characterized further in that said colloidal silica particles are of a size in the range of 20-50 millimicrons.

29. A fibrous product according to claim 25 and characterized further in that said composition includes modified corn starch, polyvinyl alcohol and lubricant. 00 0 0,4 30. A fibrous product according to claim 25 and S characterized further in that said composition includes modified corn starch and lubricant. 6

31. A sizing composition for treating fibrous materials substantially as described herein in conjunction with any one of the Examples, not being control Examples.

32. A method of preparing a composition for sizing n4 textile material substantially as disclosed herein in conjunction with any one of the Examples, not being control Examples. *o I!

33. A fibrous product sized with a sizing composition substantially as disclosed herein in conjunction with any one of the Examples, not being control Examples. Dated this 4th day of March 1991. JOHN C. LARK By his Patent Attorneys GIRFFITH HACK CO. 23 A4