US3265516A - Glass fiber sizing composition - Google Patents

Glass fiber sizing composition Download PDF

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Publication number
US3265516A
US3265516A US188359A US18835962A US3265516A US 3265516 A US3265516 A US 3265516A US 188359 A US188359 A US 188359A US 18835962 A US18835962 A US 18835962A US 3265516 A US3265516 A US 3265516A
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Prior art keywords
starch
amylose
percent
strand
size
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Benny L Triplett
James J Fasnacht
Donald E Mcwilliams
George E Eilerman
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PPG Industries Inc
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Pittsburgh Plate Glass Co
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Priority to BE631196D priority Critical patent/BE631196A/xx
Priority to NL291319D priority patent/NL291319A/xx
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Priority to US188359A priority patent/US3265516A/en
Priority to GB14313/63A priority patent/GB997397A/en
Priority to FR931658A priority patent/FR1363976A/fr
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Definitions

  • This invention is directed to a process for preparing glass fibers, and it has particular relation to the application of a size to continuous filament glass fiber strand during the formation of the strand.
  • a number of individual glass filaments are drawn from an electrically heated, platinum alloy bushing containing a molten supply of the glass.
  • the glass passes through tips which define orifices in the bottom of the bushing and form inverted cones of glass at the ends of the tips.
  • Individual filaments are drawn from the cones of glass at a high rate of speed, i.e., 5,000 to 20,000 feet per minute, and are grouped into a strand as they pass over -a suitable guide.
  • the strand is thereafter wound on a rapidly rotating forming tube.
  • an aqueous size composed of an aqueous dispersion of a binder and a lubricant, such as dextrinized corn starch and a vegetable oil, is applied to the individual filaments prior to the time they are grouped into the strand and wound on the tube in order to bond them together and maintain the integrity of the strand.
  • the strand is wound on the tube with a slight traverse so that succeeding turns cr-oss each other at an angle rather than being parallel to each other so that the strand can be more easily removed from the tube.
  • Size migration is a phenomenon which occurs in the strand after it is wound on the forming tube.
  • the size is an aqueous dispersion of ,dextrinized corn starch and vegetable oil.
  • the solids content of the conventional dextrinized starch-oil size is about 12 percent by weight with the remainder being water. Some of this water must be removed from the strand before it is twisted to form yarn. This water is removed from the strand by drying the strand which is Wound upon the forming tube.
  • the strand forming package dries on the forming tube, the water moves from the inside of the forming package next to the tube to the outside of the forming package. This movement of the water carries with it some of the starch and oil of the size so that the strand in the outside layers of the package has a much higher size solids content than the strand in the layers beneath the surface.
  • Size migration creates a number of problems in subsequent fabrication of the strand. warping, quilling and weaving of glass fiber yarn there are a number of winding and unwinding operations where the tension exerted on the yarn is important. The tension exerted on the yarn during these operations must be relatively constant. If the tension on the yarn is uneven during these operations, the individual filaments making up the yarn are likely to be broken and produce fuzzy yarn. Fuzzy yarn clogs up the fabricating equipment and causes yarn breakout. Uneven tension on the yarn can be created by non-uniform size contents on the yarn throughout its length. Thus, it is desired that the size content on the yarn be uniform throughout its length.
  • Textured yarns are those continuous filament yarns which have been bulked by an air jet, such as de- In twisting, plying,
  • the size content of the yarn which is textured determines the resistance of the yarn to being textured or bulked by the air jet.
  • a variation in size content along the length of the yarn results in a variation in the degree of bulking. Any variation in the degree of bulking of the yarn shows up in the fabric and may be serious enough to result in rejection of the piece of goods.
  • the strand from the outside of the forming package which strand originally had the higher size-solids content shows up as a filling band in the fabric which reflects light to an extent dilferent from the rest of the fabric. Sometimes this band exhibits a moire effect. This results in an imperfection in the fabric which is of suflicient magnitude to cause rejection of the fabric.
  • Shedding is the removal of small pieces of binder size which is caused by a peeling of the size from the glass fibers as the sized glass fibers (e.g., sized glass fiber yarn) pass over some contact surface or point during a fabrication step, e.g., when sized strands are being warped. Shedding leaves an accumulation of powdery size on fabricating equipment, mostly on those parts of the equipment which contact the sized fibers.
  • the starch sizing composition of this invention has excellent shedding proporties in that very little shedding occurs during fabrication steps, such as twisting, plying, warping, weaving, etc.
  • starch sizing compositions of the instant invention demonstrate excellent runability and good wet out properties with almost complete freedom from binder throw-01f and strand break outs (breaking of filaments) during strand forming and sizing operations.
  • an object of this invention to provide an aqueous size which can be easily applied to glass fiber strand during its formation in uniform, controlled amounts and whose non-aqueous constituents will not migrate in the strand forming package upon drying of the package on the forming tube.
  • the objects of the invention are achieved by application to a strand during its formation of an aqueous size containing as the binder ingredient a high amylose containing starch of the formula X-OY wherein X is a starch having an amylose content of from about 50 percent to 100 percent by weight;
  • O is an oxygen atom from a hydroxyl group in the amylose portion of the starch molecule
  • Y is a substituent on the amylose portion of the said starch with I3.
  • weight average frequency of occurrence of from about 0.1 to about 30 Y substituents, and preferably about to 20 Y substituents, per 100 d-glucopyranose units of the amylose portion of the starch.
  • the above formula includes not only high amylose content starches having homogeneous (regular) hydroxyalkylsubstitution, viz., where each group of 100 d-glucopyranose units has from 1 to 30 Y substituents, but also 4 is 1 Y substituent per 100 d-gluoopyranose units. If the entire amylose polymer has an equivalent pattern of substitution, then the weight average frequency of occurrence of Y substituents per 100 d-glucopyranose units of the amylose polymer would be 1.0.
  • the size also contains other ingredients, such as a vegetable oil as a lubricant, a bactericide such as formaldehyde, a softening agent and a wetting agent.
  • additional film forming agents other than the previously mentioned amylose containing starch of the above-said formula, can also be included, such as for example: other starches; modified starches or starch derivatives; aqueous emulsions of readily emulsifiable low molecular weight linear polyolefins, e.g., polyethylene and polypropylene having a low molecular weight of about 1400 to 2500; etc.
  • These 'adjuvant film forming materials are sold by Eastman Chemicals under the trade name Epilene, and can be employed to make a more durable strand.
  • the basic amylose containing starch from which the derivatives of the above formula are secured, can be derived from any sources including high amylose containing starch hybrids of corn, wheat, potato, tapioca, sago, or rice.
  • thehigh amylose containing starch can also be derived through fractionation of the starch content of ordinary corn, Wheat, potato, tapioca, sago, or rice to obtain a high amylose content fraction.
  • the expression high amylose containing starch means a hybrid starch or fraction of a naturally occurring or synthesized starch containing from about 50 to 100 percent by weight of amylose (with the remaining 0 to 50 percent being amylopectin or a derivative thereof).
  • hydroxyalkyl derivatives of the aforesaid high amylose containing starches can readily be prepared by reacting a lower alkylene oxide, e.g., ethylene oxide or propylene oxide, with any of the aforesaid high amylose containing hybrids or high a r n ylose containing fractions of naturally occurring or synthesized starches.
  • hydroxyalkyl derivatives can be prepared by reacting a high amylose containing potato starch with ethylene oxide to prepare a high amylose containing starch having hydroxy lower alkyl, in this case hydroxyethyl, substituents on the reoccurring d-glucopyranose units of the amylose polymer.
  • amylose starch While in the above formula, XO-Y, the high amylose starch has been shown as X, it will be realized that this has been done for purposes of simplifying the discussion in conjunction therewith.
  • amylose such as obtained from potato starch, is conventionally thought to be a linear polymer containing successively linked C H O (d-glucopyranose) units according to the formula:
  • heterogeneous (irregular) hydroxyalkyl substitution viz., where any given group of 100 d-glucopyranose units can have zero (no) Y substituents but other groups of 100 d-glucopyranose units have sufficient Y substituents to satisfy the limitation of from 0.1 to 30 Y substituents per 100 d-glucopyranose units based on the total amylose polymer. For example, if one group of 100 d-glucopyranose units has no Y substituents and an adjacent group of 100 d-glucopyranose units has 2 Y substituents, then the weight average frequency of occurrence of Y where N is the number of reoccurring C H O units in the polymer.
  • the C H O (d-glucopyranose) units are joined by 1,4 alpha linkages.
  • the molecular weight of amylose varies from about 100,000 to about 200,000 as calculated from intrinsic viscosity measurementsin l N potassium hydroxide according to the method outlined by Potter and Hassid in 70 J.A.C.S. 3774-77.
  • X in the formula, X-OY designates the amylose polymer of the high amylose conunits for those two groups of 100 d-glucopyranose units taining starch.
  • Y can be present many times on the amylose polymer backbone.
  • Each monomeric C H O (dglucopyranose) unit has three hydroxyl groups available for reaction with the lower alkylene oxide, and the lower alkylene oxide can react with any one(s) or all of them.
  • the lower alkylene oxide can be reacted with substantially pure amylose, such as an amylose starch having an amylose content of about 80 to 100 percent by weight.
  • substantially pure amylose starch wherein the Y substituents are hydroxyethyl is most preferred according to this invention.
  • Hydroxyethy-l lamylose starches having an amylose content of from about 50 to 100 percent by weight, and more preferably from 80 to 100 percent by weight, are the preferred high amylose containing starch derivatives employed in accordance with this invention.
  • hydroxyalkyl amylose starches coming within the formula, X-O-Y, as defined hereinabove, are water soluble, or water dispersible depending upon the degree of hydroxyalkyl substitution, with the higher substituted amylose products giving the greater water solubility.
  • Hydroxyethyl Superlose is essentially hydroxyethyl amylose formed by reacting essentially pure amylose (derived by fractionation of potato starch) with ethylene oxide. The fractionation procedure can be conducted conveniently according to US. Patent Nos. 2,829,- 987; 2,829,988; 2,829,989; and 2,829,990.
  • Amylomaize is a hybrid corn starch having approximately 55 percent by Weight amylose.
  • Hydroxyethyl Superlose and Amylomaize are both products of Stein Hall and Company, Inc., New York, New York. These starches, when formulated into aqueous systems with the addition of other adjuvants, such as lubricants, bactericides, and various softening and conditioning agents, are eminently suitable as aqueous sizing compositions for application to glass fiber strands during their formation to impart non-migratory characteristics and superior abrasion resistance thereto. It is also observed that by the application of aqueous sizing compositions containing amylose starch derivatives of the aforesaid formula, the problems of shedding, break out and binder throw off are substantially eliminated. Moreover, the instant invention allows the uniform application of the aqueous sizing composition with good runability throughout the sizing process, viz., the sizing composition can be applied to the glass fibers easily without clogging the apparatus.
  • the said sizing composition can be easily and uniformly removed from the glass fibers (after the fabrication has been completed, e.g., after the strands have been woven into fabric) during the burn-off procedure without leaving unsightly grey bands which cause variance in the light reflecting properties of woven glass fabric.
  • rejects can be substantially reduced by avoiding the aforementioned defects of nonuniform size application, size migration, variance in light reflectance, etc.
  • the average frequency of occurrence of the Y substituents per 100 d-glucopyranose units of the high amylose containing starch is from about 0.1 to about 30.0 Y substituents per 100 d-glucopyranose units.
  • the frequency of the Y substit-uents is from about to about 20 Y substituents per 100 d-glucopyranose units.
  • Any amylose fraction of a starch can be employed in accordance with this invention as long as the said fraction contains from about 50 to about 100 percent by weight of amylose.
  • aqueous size compositions suitable for use as non migratory, abrasion resistant starch sizes for glass fiber strands in accordance with this invention are conveniently prepared in the following manner:
  • the amylose containing starch of the formula, XO-Y is mixed with a lubricant, such as a water-soluble mixture of'ethylene oxide and propylene oxide, 21 surface active wetting agent, such as an ethylene oxide derivative of a sorbitol ester, and a textile softener, such as 'an alkyl 'imidazoline reaction product of tetraethylene pentamine and stearic acid.
  • a bactericide such as formaldehyde, is usually added in sufficient amounts to prevent mold attack on the said high amylose containing starch derivative.
  • a sizing composition is conveniently prepared by first adding about half the total amount of water to a mixing kettle. Suitable amounts of high amylose containing starch derivative of the formula, XOY, as defined above, are then added to the water to form a slurry. The pH of the slurry is about 4.5. This slurry is heated (cooked) at a sufficient temperature and for a sufficient length of time to allow the said high amylose containing starch derivative to go into aqueous solution. A processing oil, such as a hydrogenated vegetable oil, is then added to the batch.
  • the said oil is generally a solid material having the consistency of lard, and it is first melted and then emulsified with water, the wetting agent, and a small amount of the aqueous high amylose containing starch derivative solution before it is added to the main portion of the aqueous size.
  • the textile softener, dispersed in water, is next added to the sizing batch, and the bactericide is thereafter added.
  • the aqueous sizing composition as thus prepared has a pH of about 5.0 to 5.4.
  • the sizing solution is adjusted to or maintained on the acid side to facilitate better solubility of the soluble constituents of the size.
  • the aqueous sizing composition has a viscosity of about 1 to 100, and preferably about 1 to 20 centipoises at 20 C. using a Brookfield viscometer (Model No. LVP with spindle size No. 1 rotating at 30 revolutions per minute), and a high amylose containing starch derivative content of about 2 to 4 weight percent. If the aqueous sizing composition contains the high amylose containing starch derivative in a weight percent substantially in excess of 4, then the outer layers of the sized strands on the forming package are bonded too tightly to permit removal thereof without filament breakage.
  • aqueous sizing composition of this invention to be picked up by the glass strands is enhanced by including in the aqueous sizing composition other starch materials, such as unmodified corn starch, as adjuvant film forming materials.
  • starch materials such as unmodified corn starch
  • a lesser or greater proportion of the unmodified adjuvant starch material can be employed as compared to the amount of high amylose containing starch derivative.
  • other adjuvant starch materials can be employed in conjunction with the high amylose containing starch derivative in accordance with the present invention.
  • Such starch materials as cross-linked starches, e.g., starches cross-linked with phosphorus oxychloride as described in US. Patent No.
  • Acid treated corn starches e.g., corn starches prepared by hydrolyzing corn starch with sulfuric acid to correspond to a fluidity of about 30 to 50 and preferably a fluidity of about 40.
  • the term fluidity as used herein is indicative of the number of cubic centimeters of an aqueous alkaline starch solution which runs from a funnel in seconds at 25 C.
  • the term fluidity is defined more fully in Chemistry and Industry of Starch, second edition (1950) by Ralph W. Kerr, at pages 133-134, Academic Press, Inc.
  • Emulsions of low molecular weight polyolefins e.g., polyethylene and polypropylene, can also be used as adjuvant film forming materials to make a more durable strand.
  • the aqueous sizing composition is applied to the glass fiber strand during forming.
  • the sized strands are conditioned (dried at a temperature of 70 F. and 70 percent relative humidity) to reduce their moisture content prior to twisting.
  • the amount of conditioning will depend upon the diameter and number of filaments in the strand and upon the amount of twist (turns per inch) that is to be put in the strand.
  • a 204 filament strand package is conditioned for 24 to 72 hours and a 400 filament strand package is conditioned for 8 to 20 hours.
  • the moisture content of the strand is reduced to about 4 to 6 percent by weight preparatory to twisting.
  • the amount of size solids on the strand can vary from about 0.7 to about 2.0 percent and preferably from 1.0 to 1.5 percent.
  • One of the distinct advantages attendant to this invention resides in the fact that lesser amounts of size solids can be deposited on the glass fibers to accompilish the function of a starch size binder, viz., hold the glass fibers together in strand form until the fabrication of the strands has been completed.
  • solid contents of from 1.7 to 2.0 percent were customarily required to insure adequate film strength and binding.
  • the same objectives can be secured with the use of solids contents of from 1.0 to 1.5 percent, thus facilitating the removal of the size solids by volatilization during the subsequent heat treatment, viz., coronization or burnolf. While solids content in excess of 1.5 percent can be used, no beneficial results are secured thereby, and this merely creates more of a problem in volatilization.
  • the ability of applicants invention to impart the desired binding power and fabrication properties to glass fibers while depositing fewer solids on a percentage basis is significant. This facilitates size removal because there is less size to burn off the fibers. Moreover, the coronizing equipment can handle more fabric in a given length of time, therelby permitting an increased productivity of the coronizing equipment.
  • the aqueous glass fiber sizing compositions of the present invention are applied to the glass fibers during their forming While the size is at an elevated temperature, i.e., 125 to 135 F., and more preferably at a temperature of about 130 F. This is necessary in order to keep all of the ingredients of the size, especially the hydrogenated vegetable oil and the amylose containing starch derivative of the aforementioned formula, uniformly dispersed in the size. If the size is allowed to cool to, say for example, room temperature, these ingredients tend to sepa rate from the size.
  • FIGURE 1 is a diagrammatic elevation of a continuous filament, glass fiber strand operation
  • FIGURE 2 is a graph illustrating the improvement '8 of the present invention over the prior art with respect to size migration in the forming package.
  • FIGURE 1 of the drawing there is shown an electrically heated, platinum alloy bushing 6 containing a supply of molten glass 7.
  • the bushing is provided with a series of orifices in the form of tips 8 through which the glass flows and forms in small inverted cones 9 suspended from the bottoms of the tips 8.
  • the tips are usually formed in a number of rows, for-example, 4 to 20 or more rows, having a great many tips in each row so that the total number of tips is about 200 to 400 or even more in number.
  • Glass filaments 10 are pulled from the cones of glass 9 at a very high rate of speed, i.e., 5,000 to 20,000 feet per minute and wound up on a rapidly rota-ting forming tube 12.
  • the glass filaments are grouped into a strand 13 as they pass over the guide 14 prior to their being wound on the tube 12.
  • the size is applied by means of applicator 18 to the individual filaments in the strand prior to the time they pass over the guide.
  • the size 20 is supplied to a reservoir 22 of applicator 18 which has a rotating roller or belt 19 mounted so as to dip into the size in the reservoir.
  • the size is transferred from the rotating roller or belt to the filaments as the filaments pass over the surface of the wetted roller or belt.
  • a suitable size applicator is shown in U.S. Patent No. 2,873,718.
  • the sizes of the present invention are easily applied to the strand during its formation, and the strand forming proceeds smoothly.
  • each forming package containing, for example, about 3.5 pounds of strand, is formed (204 filaments having a diameter such that there are 15,000 yards to the pound of strand)
  • the forming tube and package are removed from the winder and the end of strand is found on the forming package.
  • the forming package containing about 9.5 to 10 percent by weight moisture, is then allowed to sit in an atmosphere of about 70 F. and 70 percent relative humidity for about 24 hours in order to reduce the moisture content on the strand to a range of about 4 to 6 percent by Weight.
  • the strand is removed from the forming package and twisted into yarn.
  • the twisting is accomplished on conventional textile apparatus with very few broken filaments.
  • the twisted yarn is warped or transferred onto quills for weaving, and the yarn weaves very well with very few broken filaments.
  • the woven material can be heat treated satisfactorily.
  • FIGURE 2 the graph shows a size solids content of the strand in the forming packages produced according to the present invention as compared with the prior art.
  • the ordinate shows the percent of size solids on the strand after 21 hours conditioning at 70 percent relative humidity and 70 F.
  • the abscissa shows the number of yards of strand as it is removed from the outside to the inside of the forming package.
  • the dotted line represents the amount of solids of a conventional dextrinized corn starch-vegetable oil size and the solid line represents the amounts of solids of the high amylose containing starch derivative of the formula, XOY, as defined above, exhibited by the size set forth below in Example V at various points along the strand in the forming package after conditioning as described above.
  • the strand (or yarn) handles well, and there are very few filaments broken during these fabricating steps.
  • the yarn as sized according to the method as described above is exceptionally useful for bulking by means of the texturing air jet described in the above-mentioned patent.
  • the uniformity of size content on the yarn permits uniform conditions in the texturing operation and the production of acceptable textured yarn.
  • EXAMPLE II Ingredient: P Amount Hydroxyethyl amylose grams 600.0 Pureco Oil (hydrogenated cotton-seed oil) grams 410.5 Tween '81 (ethylene oxide derivative of a :sorbitol ester-wetting agent) grams 40.9 Cation X do 88.7 Formaldehyde cc 17.0 Water (suflicient to bring to a volume of 5 gallons).
  • hydroxyethyl amylose 600 grams to 2 /2 gallons of water in a mixing kettle to form a slurry, and adjust the pH of the slurry to about 4 to 5 with acetic acid. Heat the slurry at 180 F. for 30 minutes to allow the hydroxyethyl amylose to go into aqueous solution.
  • Add fPureco Oil 410.5 grams, by first melting the Pureco Oil and then emulsifying it with water, Tween 81 (40.9 grams) and a small amount(200 to 400 cubic centimeters) of the aqueous hydroxyethyl amylose solution before adding to the main portion of the aqueous size.
  • EXAMPLE III Ingredient: Amount Hydroxyethyl amylose grams 300.0 Unmodified corn starch do 700.0 Pureco Oil do 410.0 Tween 81 do 41.0 Cation X do 88.0 Formaldehyde cc.. 17.0 Water (sufiicient to bring to a volume of 5 gallons).
  • Example II The procedure of Example II was repeated with the exception that unmodified corn starch, 700 grams, was included in the sizing batch by cooking 700 grams of unmodified corn starch in about -2 gallons of water for 15 minutes at F. This was then added to the previously cooked hydroxyethyl amylose solution, which had been cooked'at -190 F. for 20 minutes and then cooled to 140 F. prior to the addition of the unmodified corn starch.
  • the glass fiber yarn sized with this formulation had adequate binder pick-up (averaging 1.7 percent, dry basis), essentially no migration of binder, and in general good fabrication properties including excellent quilling properties.
  • Example III The procedure of Example III was repeated with the exception that the Tween 81 of Example III was replaced with Ethomid HT/ 15 and the unmodified corn starch was cooked in water at 1'60-170 F. for 2 to 5 minutes to partially hydrate the unmodified corn starch prior to adding it to the previously cooked hydroxyethyl amylose solution. With this formulation properties equal to those secured in Example III were obtained, and in ad-.
  • the abrasion resistance values were obtained from a simple testing apparatus and indicate the number of oscillating movement cycles (number of abrading rubs) given to the tensioned yarn prior to breakage.
  • the apparatus involved essentially four winding posts arranged in rectangular fashion with the two upper posts being generally parellel to the bottom posts.
  • a smooth sur faced round post is provided to allow the yarns to be crossed by one another in abrading contact in the same manner as links in a chain.
  • the four outside posts were spaced apart fboth vertically and horizontally.
  • the center smooth surfaced round post is spaced slightly to the left of the vertical center of the rectangle refined by the four outer posts.
  • a first yarn specimen is clamped to the upper lefthand post, guided around the central round post under slight tension and clamped at the lower lefthand post.
  • the said first specimen is cut to allow about /2 inch yarn to protrude from the said posts.
  • a second yarn specimen is pulled through the loop formed by the first specimen from front to back.
  • One free end of the second yarn specimen is then threaded around the upper righthand post up to and around another post located outside of the said rectangle (above and slightly to the right of the upper righthand post located in the rectangle) and down to the tensioning post (located below the lower righthand post in the said rectangle.)
  • the other (lower) free end of the said second yarn specimen is passed around the lower righthand post in the said rectangle and then passed downwardly and clamped to the said tensioning post.
  • a weighted tension of 80 grams is then applied to the tensioning post.
  • a horizontally disposed bar is eccentrically secured to the tensioning post on one end and to an oscillating device on the other. The bar is then oscillated causing the second yarn specimen to rub against and therefore abrade the first yarn specimen. The number of oscillations (rubs) were counted. The abrasion resistance of the sized strands is reflected by the number of rubs prior to breakage.
  • EXAMPLE V Ingredient: Amount Hydroxyethyl amylose grams 1000.0 Corn Products 5341 (40 fluidity sulfuric acid treated corn starch) grams 300.0 Stein Hall ARD-1370 (partially cross- ⁇ bonded corn starch wherein the crossbonding agent is phosphorous oxychloride) grams 300.0 Pureco Oil do. 600.0 Tween 81 do 80.0 Carbowax 300 (polyethylene glycol with an approximate molecular weight of 300) grams 3 00.0 Cation X do 176.0 Diglycol stearate do 30.0 Water (Sufiieient to bring to a volume of 10 gallons).
  • Example III The procedure of Example III was followed with the exceptions that (a) Stein Hall ARD-1370 and Corn Products 5341 were cooked in water (approximately 5 gallons at 212 F. for 30 minutes before adding to the hydroxyethyl amylose solution, which had been cooked previously at a temperature of 180 F. for 15 minutes; and (b) the Pureco Oil was emulsified with diglycol stearate and Tween 81 prior to adding it to the size.
  • This aqueous size composition had a solids content of about 7.3 weight percent. With this formulation the size content of 54,000 yards of glass fiber yarn varied from 1.69 percent on the outside 300 yards of the forming package to 1.40 percent on the inside 300 yards.
  • the average size content was 1.4 percent (ignition loss) after drying and conditioning the sized strands as in Example I.
  • the abrasion resistance of the glass fiber yarn sized with this sizing composition was 43 cycles.
  • This size formulation showed excellent results in Warping trials, viz., 0.13 break/million end yards, and also possessed excellent quilting, weaving, and general forming propersizing materials (for example, warp sizes).
  • Example V The procedure of Example V was followed and the sized yarn possessed essentially the same abrasion resistance (42 cycles) and general forming properties as in Example V.
  • the average size content was 1.4 percent (ignition loss). Practically no migration occurred.
  • EXAMPLE VII Ingredient: Amount Hydroxyethyl Amylomaize (hydroxyethyl derivative of hybrid corn starch having an amylose content of approximately 55 percent by weight prepared by reacting ethylene oxide, 10 to 20 weight percent, with Amylomaize) grams 1000.0 Corn Products 5341 do 300.0 Stein Hall ARD-1370 do 300.0 Pureco Oil do 600.0 Tween 81 do 80.0 Carbowax 300 do 300.0 Cation X do 176.0 Diglycol sterate do 30.0 Water (Sufficient to bring to a volume of 10 gallons).
  • Example V The procedure of Example V was repeated with the exception that hydroxyethyl Amylomaize was employed in place of hydroxyethyl amylose, and the sized glass fiber yarn possessed essentially the same abrasion resistance (44 cycles) and general forming properties as in Example V.
  • the average size content was 1.4 percent (ignition loss). Substantially no migration occurred.
  • EXAMPLE VIII Ingredient: Amount Hydroxyethyl Superlose grams 1000.0 Corn Products 5341 do 300.0 Stein Hall ARD1370 do 300.0
  • Polyethylene glycol stearate Water dispersible sterate of polyethylene glycol having a molecular weight of approximately 400
  • grams 680.0 Cation X do 176.0 Water (Sufiicient to bring to a volume of 10 gallons).
  • Example V The procedure of Example V was followed with the exception that polyoxyethylene glycol sterate was substituted for Pureco Oil and Tween 81.
  • the abrasion resistance and general forming properties of the sized yarn were the same as those attained in Example V. Essentially no migration occurred.
  • EXAMPLE IX Ingredient: Amount Hydroxyethyl Superlose grams 1000.0 Epolene (readily emulsifiable low molecular weight linear polyethylene having a molecular weight of 1400 to 2500) grams 600.0 Pureco Oil do 600.0 Tween 81 do 80.0 Carbowax 3-00 do 300.0 Cation X do 176.0 Diglycol stearate do 30.0 vWater (Sufiicientto bring to a volume of gallons).
  • Example V The procedure of Example V was followed with the exception that the Epolene was substituted for both the Corn Products 5341 and Stein Hall ARD-1370 of Example V. Essentially no migration occurred, and the sized yarn had an abrasion resistance of 42. The general forming characteristics were excellent.
  • Suitable textile softeners are alkyl imidazoline derivatives such as described in US. Patents Nos. 2,200,815; 2,267,965; 2,- 268,273 and 2,355,837.
  • Cation X is an example of such a material wherein the alkyl imidazoline derivative is the reaction product of stearic acid, tetraethylene pentamine and acetic acid.
  • Acid solubilized, water-dispersible stearic amides and auhydrous, acid solubilized, water dispersible lower molecular weight fatty acid amides, as well as anhydrous, acidsolubilized, polyunsaturated, lower molecular weight fatty acid amides can also be used as a softener. Some of these softeners also serve .as wetting agents, for example, the alkyl imidazoline derivatives.
  • wetting agents similar to Tween 81 can be employed in the size in sufficient amounts to permit adequate wetting of the sizing ingredients to the glass surface with suitable amounts of Wetting agent ranging from 8 to 13 weight percent of wetting agent based on the weight of lubricant, and preferably about 10 percent by weight of the lubricant.
  • Suitable wetting agents include cetyl or stearyl monoarnine hydrochloride or acetate, dodecyl amine, hexadecylamine and secondary and tertiary derivatives of the same, for example, dodecylmethylamine and salts thereof.
  • Quaternary ammonium compounds such as trimethyl stearyl or cetyl ammonium bromides and chlorides, and generally any of the amine compounds which dissociate in aqueous systems to provide a positive radical containing a group of more than 10, preferably 12 or more carbon atoms can be employed. These materials are cationic active substances.
  • Non-ionic wetting agents can also be used. They are not as surface active as cationic wetting agents, and therefore are generally used in greater amounts to provide the same degree of wetting.
  • suitable non-ionic wetting agents include polyalkylene derivatives of esters,
  • fatty acids fatty alcohols, fatty amides, alkyl phenyl ethers and other derivatives.
  • a bactericide such as formaldehyde, is usually employed in suflicient amount to prevent mold attack on the amylose containing starch derivative.
  • Suitable effective amounts of the bactericide are about 3 milliliters to 1 gallon of the sizing composition.
  • the overall solids content of the size can vary from about 2.0 to 8.0 percent by weight. Generally the solids content will range from 6.0 to 7.5 percent by weight and preferably from 7.1 to 7.3 percent by weight. By solids content is meant the residual solids remaining after drying the sizing composition at 105 C. to constant weight.
  • An aqueous glass fiber sizing composition consisting essentially of in percent by weight, 91 to 96 percent water, 1.5 to 4 percent of an amylose containing starch derivative of the formula, XOY,
  • X is a high amylose containing starch having an amylose content of from about 50 percent to 100 percent by weight
  • 0 is an oxygen atom from a hydroxyl group in the amylose portion of the starch molecule
  • Y represents hydroxy lower alkyl radicals, and wherein Y is a substituent on the said amylose with a weight average frequency of occurrence of from about 0.1 to 30.0 Y substituents per 100 d-glucopyranose units of the amylose portion of the said starch,
  • said aqueous sizing composition having a viscosity of about 1 to 100 centipoises at 20 C.
  • composition of claim 1 where the film forming agent is unmodified corn starch.
  • composition of claim 1 Where the film forming agents are a partially cross-bonded starch and an acidtreated corn starch having a fluidity of approximately 30 to 50.
  • composition of claim 1 wherein the film forming agent is a readily emulsifiable low molecular weight polyolefin selected from the group consisting of:
  • a dried forming package of non-migratory sized glass fiber strand comprising a support for the strand and a dried, sized continuous glass fiber strand wrapped therearound, the filaments of said strand being coated with the dried residue of the sizing composition set forth in claim 1, and said strand being characterized by having a substantially uniform size solid content throughout the extent of the strand on the forming package.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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GB14313/63A GB997397A (en) 1962-04-18 1963-04-10 Glass fiber sizing composition
FR931658A FR1363976A (fr) 1962-04-18 1963-04-16 Composition d'encollage pour fibres de verre

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887389A (en) * 1973-01-26 1975-06-03 Ppg Industries Inc Fiber glass sizing for use in tire cord manufacturing
US3946132A (en) * 1973-01-26 1976-03-23 Ppg Industries, Inc. Tire cord containing glass fibers sized with a starch based size
US4066106A (en) * 1975-09-02 1978-01-03 Ppg Industries, Inc. Sized woven glass fabric
US4166872A (en) * 1972-08-31 1979-09-04 Owens-Corning Fiberglas Corporation Migration-resistant forming size compositions for fibrous glass
US4244844A (en) * 1977-01-19 1981-01-13 Saint-Gobain Industries Aqueous size for glass fibers
US4681805A (en) * 1985-12-23 1987-07-21 Ppg Industries, Inc. Strands of chemically treated glass fibers having a reduced tendency to give gumming deposits
US5038555A (en) * 1989-02-28 1991-08-13 Ppg Industries, Inc. Twistable chemically treated glass fibers, fabrics and coated articles
US5286562A (en) * 1988-07-01 1994-02-15 Ppg Industries, Inc. Weavable textile glass strand
US5354829A (en) * 1992-06-30 1994-10-11 Ppg Industries, Inc. Silylated polyamine polymers and a method of treating fibers
US5466528A (en) * 1992-08-21 1995-11-14 Ppg Industries, Inc. Chemically treated glass type substrates with vinyl polymer compatibility
US5524841A (en) * 1994-05-26 1996-06-11 Ppg Industries, Inc. Apparatus and methods for winding a plurality of strands
US5773146A (en) * 1995-06-05 1998-06-30 Ppg Industries, Inc. Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers
US20050084675A1 (en) * 2003-10-17 2005-04-21 Boy-Chy Wang Sizing composition for glass fibers
US20050255316A1 (en) * 2004-05-17 2005-11-17 Puckett Garry D Sizing compositions for glass fibers and sized fiber glass products
WO2014150732A1 (en) 2013-03-14 2014-09-25 Ppg Industries Ohio, Inc. Sizing compositions for glass fibers and sized fiber glass products
US20150246463A1 (en) * 2012-10-04 2015-09-03 Saudi Basic Industries Corporation Method and device for manufacturing of a fibre-reinforced polymer composition
CN105481989A (zh) * 2015-07-15 2016-04-13 河南恒瑞淀粉科技股份有限公司 一种添加改性淀粉的玻璃纤维浸润剂

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US2710275A (en) * 1951-05-01 1955-06-07 Owens Corning Fiberglass Corp Method of bulking glass fiber strands
US2771659A (en) * 1953-07-02 1956-11-27 Bay State Abrasive Products Co Process of forming a durable open mesh fabric
US2798020A (en) * 1953-06-23 1957-07-02 Lof Glass Fibers Co Method of making a glass fiber reinforced resinous product
US2799598A (en) * 1951-08-17 1957-07-16 Owens Corning Fiberglass Corp Process of forming coated twisted yarns and woven fabrics and resultant article
US2993872A (en) * 1957-12-23 1961-07-25 Owens Corning Fiberglass Corp Aqueous composition comprising werner complex, a starch, hydrogenated vegetable oil and emulsifying agent and method of preparing same
US3036935A (en) * 1958-03-24 1962-05-29 Scholten Chemische Fab Method of sizing textile yarns
US3051700A (en) * 1959-07-17 1962-08-28 Hubinger Co Cationic, nitrogenated, starch products containing at least fifty percent amylose
US3108891A (en) * 1961-04-24 1963-10-29 Owens Corning Fiberglass Corp Amylaceous forming size compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2710275A (en) * 1951-05-01 1955-06-07 Owens Corning Fiberglass Corp Method of bulking glass fiber strands
US2799598A (en) * 1951-08-17 1957-07-16 Owens Corning Fiberglass Corp Process of forming coated twisted yarns and woven fabrics and resultant article
US2798020A (en) * 1953-06-23 1957-07-02 Lof Glass Fibers Co Method of making a glass fiber reinforced resinous product
US2771659A (en) * 1953-07-02 1956-11-27 Bay State Abrasive Products Co Process of forming a durable open mesh fabric
US2993872A (en) * 1957-12-23 1961-07-25 Owens Corning Fiberglass Corp Aqueous composition comprising werner complex, a starch, hydrogenated vegetable oil and emulsifying agent and method of preparing same
US3036935A (en) * 1958-03-24 1962-05-29 Scholten Chemische Fab Method of sizing textile yarns
US3051700A (en) * 1959-07-17 1962-08-28 Hubinger Co Cationic, nitrogenated, starch products containing at least fifty percent amylose
US3108891A (en) * 1961-04-24 1963-10-29 Owens Corning Fiberglass Corp Amylaceous forming size compositions

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4166872A (en) * 1972-08-31 1979-09-04 Owens-Corning Fiberglas Corporation Migration-resistant forming size compositions for fibrous glass
US3887389A (en) * 1973-01-26 1975-06-03 Ppg Industries Inc Fiber glass sizing for use in tire cord manufacturing
US3946132A (en) * 1973-01-26 1976-03-23 Ppg Industries, Inc. Tire cord containing glass fibers sized with a starch based size
US4066106A (en) * 1975-09-02 1978-01-03 Ppg Industries, Inc. Sized woven glass fabric
US4244844A (en) * 1977-01-19 1981-01-13 Saint-Gobain Industries Aqueous size for glass fibers
US4246145A (en) * 1977-01-19 1981-01-20 Saint-Gobain Industries Aqueous size for glass fibers
US4681805A (en) * 1985-12-23 1987-07-21 Ppg Industries, Inc. Strands of chemically treated glass fibers having a reduced tendency to give gumming deposits
US5286562A (en) * 1988-07-01 1994-02-15 Ppg Industries, Inc. Weavable textile glass strand
US5038555A (en) * 1989-02-28 1991-08-13 Ppg Industries, Inc. Twistable chemically treated glass fibers, fabrics and coated articles
US5354829A (en) * 1992-06-30 1994-10-11 Ppg Industries, Inc. Silylated polyamine polymers and a method of treating fibers
US5466528A (en) * 1992-08-21 1995-11-14 Ppg Industries, Inc. Chemically treated glass type substrates with vinyl polymer compatibility
US5524841A (en) * 1994-05-26 1996-06-11 Ppg Industries, Inc. Apparatus and methods for winding a plurality of strands
US5773146A (en) * 1995-06-05 1998-06-30 Ppg Industries, Inc. Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers
US20050084675A1 (en) * 2003-10-17 2005-04-21 Boy-Chy Wang Sizing composition for glass fibers
US20050255316A1 (en) * 2004-05-17 2005-11-17 Puckett Garry D Sizing compositions for glass fibers and sized fiber glass products
US7892641B2 (en) 2004-05-17 2011-02-22 Ppg Industries Ohio, Inc. Sizing compositions for glass fibers and sized fiber glass products
US20150246463A1 (en) * 2012-10-04 2015-09-03 Saudi Basic Industries Corporation Method and device for manufacturing of a fibre-reinforced polymer composition
US20170361498A1 (en) * 2012-10-04 2017-12-21 Saudi Basic Industries Corporation Device for manufacturing of a fibre-reinforced polymer composition
US10493658B2 (en) * 2012-10-04 2019-12-03 Saudi Basic Industries Corporation Method and device for manufacturing of a fibre-reinforced polymer composition
US10611058B2 (en) 2012-10-04 2020-04-07 Saudi Basic Industries Corporation Device for manufacturing of a fibre-reinforced polymer composition
WO2014150732A1 (en) 2013-03-14 2014-09-25 Ppg Industries Ohio, Inc. Sizing compositions for glass fibers and sized fiber glass products
CN105481989A (zh) * 2015-07-15 2016-04-13 河南恒瑞淀粉科技股份有限公司 一种添加改性淀粉的玻璃纤维浸润剂

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BE631196A (xx)
NL291319A (xx)

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