US3167468A - Method of applying an aqueous size to strands formed of glass filaments and product produced thereby - Google Patents

Method of applying an aqueous size to strands formed of glass filaments and product produced thereby Download PDF

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US3167468A
US3167468A US112631A US11263161A US3167468A US 3167468 A US3167468 A US 3167468A US 112631 A US112631 A US 112631A US 11263161 A US11263161 A US 11263161A US 3167468 A US3167468 A US 3167468A
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Prior art keywords
size
starch
strand
weight
alkyl
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US112631A
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Joe B Lovelace
William E Patterson
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PPG Industries Inc
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Pittsburgh Plate Glass Co
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Priority to NL278607D priority Critical patent/NL278607A/xx
Application filed by Pittsburgh Plate Glass Co filed Critical Pittsburgh Plate Glass Co
Priority to US112631A priority patent/US3167468A/en
Priority to GB19981/62A priority patent/GB997051A/en
Priority to DE19621469181 priority patent/DE1469181A1/de
Priority to BE618146A priority patent/BE618146A/fr
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/321—Starch; Starch derivatives
    • 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
    • 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
    • Y10T428/2964—Artificial fiber or filament
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate

Definitions

  • This invention relates 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 forms 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 tie 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 cross each other at an angle rather than being parallel to each other so the strand can be more easily removed from the tube.
  • Size migration creates a number of problems in subsequent fabrication of the strand.
  • twisting, plying, warpingyquilling 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 content on the yarn through out its length. Thus, it is desired that the size content on the yarn be uniform throughout its length.
  • Textured yarns are those continuous fila- Edfilidd ice ment yarns which have been bulked by an air jet such as described in US. Patent No. 2,783,699.
  • 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 originally had the higher size solids contents shows up as a band in the fabric which reflects light to a different extent than the rest of the fabric. Sometimes this band exhibits a moire efiect. This results in an imperfection in the fabric which is of sufiicient magnitude to cause rejection of the piece of goods. It is not known exactly what causes the difference in the yarn in the fabric; however, it is believed that it may be due to incomplete re moval of the size or it may be due to a difference in the orientation of the individual filaments in the yarn due to the increased heating activity which occurs in the areas of increased size solids content when the fabric has been sufiiciently heated to remove all of the size throughout the fabric. In any event, this difference has definitely been noted and has been a cause for serious concern with the yarn manufactue-rs and weavers. The above defects have also occurred in fabrics woven with textured, continuous filament glass yarns.
  • 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. It is a further object of the invention to provide such a size which will permit the strand to be twisted, uniformly textured if desired, quilled or warped, and woven into cloth with uniform tension and with a minimum of broken filaments in these various fabricating operations. It is also an object of the invention to provide an aqueous size whose solids constituents can be readily and completely removed from a woven fabric by the conventional heat treatments which are applied to fabrics to remove the size ingredients and set the fibers in the fabric.
  • the objects of the invention are achieved by the application to a strand during its formation of an aqueous size containing as the binder ingredient a starch-amine reaction product.
  • the size also contains other ingredients such as a vegetable oil as a lubricant, a fungicide such as formaldehyde, a softening agent and a wetting agent.
  • Small amounts of additional film forming ingredients other than starch may be included, such as for example, gelatin or polyvinyl alcohol to make a more durable strand.
  • starch includes any amylaceous substance such as untreated starch, as Well as starch derivatives including dextrinized, hydrolyzed, oxidized, esterified and etherified starches still retaining amylaceous material.
  • the starches may be derived from any sources including corn, wheat, potato, tapioca, waxy maize, sago or rice.
  • the starch-amine reaction products which are useful in the invention are made by reacting starch with an esterification or etherification reagent which will serve to introduce an amine group to the starch.
  • Said reagent may be selected from the group of nitrogen containing compounds consisting of amino alkyl anhydrides, alkyl imines, alkyl epoxides and alkyl amino halides, as Well as the corresponding compounds containing aryl groups in addition to the alkyl groups. All of the various types of reagents listed herein have the common characteristic of reacting with hydroxyl groups in the starch to introduce an ester or ether linkage and thereby introduce an amine radical into the starch.
  • Representative examples of specific reagents for the purpose of making such starch derivatives include ethylene imine; propylene imine; isatoic anhydride; quinolinic anhydride; b-diethyl amino ethyl chloride; bmethyl amino isopropyl chloride; b-dimethyl amino ethyl chloride; 3-diethyl amino 1,2-epoxypropane; 3-dibutyl amino 1,2-epoxypropane; Z-bromo-S-diethyl amino pentane hydrobromide; N-(2,3-epoxypropyl)-piperidine; and N,N-(2,3-epoxypropyl) methyl aniline.
  • the various halides eg.
  • chloro-, bromo-, etc. can be used interchangeably.
  • the free amines e.g. b-diethyl amino ethyl chloride
  • the hydrochloride or other salts of these reagents e.g. b-diethyl amino ethyl chloride hydrochloride.
  • the salts since these are often less toxic and more convenient to handle.
  • the hydrochloride moiety takes no part in the reaction. It Will be seen that besides the alkyl, aryl and aralkyl types, the reagents may also include those containing cyclic groups.
  • the starch-amine reaction product may also be treated so as to result in the quaternary ammonium salt.
  • the starch-amine reaction products can be produced by known methods such as those set forth in US. Patents Nos. 2,813,093 and2,946,70 5.
  • the starch is preferably treated with any of the previously described reagents in the presence of an alkaline medium. This is accomplished by suspending the starch in water, to Which has been added (either before or after the addition of the starch) suflicient base, such as alkali metal hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide, or the like,
  • the amine-starch reaction product may contain 0.5 to 30 percent by weight of an amine introducing reagent based on the weight of the starch.
  • the starch-amine reaction product can be prepared in either gelatinized or ungelatinized form.
  • a gelatinization retarding chemical such as sodium sulfate, is added to the starch-alkali-water-reagent mixture.
  • each of R and R is a radical selected from the group consisting ofhydro'gen, alkyl or aralkyl radicals. If the derivative is in the form of the salt, or if it is in the form of the quaternary salt, the formula is then represented as follows:
  • R is again a radical selected from the group consisting of substituted alkyl, hydroxyl alkyl, acyl or aroyl radicals, and each of R and R is 'a radical selected from the group consisting of hydrogen, alkyl or aralkyl radicals, and where R, is hydrogen or an alkyl group and Y is a chloride, bromide or an' iodide radical.
  • Example I The following table lists various sizing formulations which are useful forthe practice of the invention wherein the starch-amine reaction product is an alkyl amino halide salt resulting from the reaction of corn starch with b-diethyl amino ethyl chloride hydrochloride.
  • the above formulations are given in the amounts required for making five gallon mixtures of the size. All of the amounts are in grams as indicated in the heading for the table with the exception of the formaldehyde which is set forth in cubic centimeters.
  • the starch-amine reaction product is prepared by reacting corn starch with b-diethyl amino ethyl chloride hydrochloride in the following manner. Four pounds of sodium hydroxide are dissolved in 150 pounds of water and 50 pounds of sodium sulfate are added. Agitation is continued until the reagents have wherein X is a starch, R is a radical selected from the dissolved and 100 pounds of corn starch are then added with continued agitation.
  • a textile softener is an alkyl imidazoline reaction product of tetraethylene pcntamine and stearic acid as made by the Onyx Oil and Chemical Company.
  • the size is prepared by first adding 2 /2 gallons of water to a mixing kettle.
  • the starch-amine reaction product is then added to the water to form a slurry and the pH of the slurry is adjusted to 3.5 plus or minus 0.2 with acetic acid.
  • the slurry is heated to 200 F. and held at this temperature for about 15 minutes in order to gelatinize the starch-amine reaction product.
  • the gelatinized starcharnine reaction product in the aqueous diluent is then cooled to 160 F.
  • the Pureco oil is added next.
  • the Pureco oil is a solid material having the consistency of lard and it is first melted and then emulsified with water, Tween 81 and a small amount (200 to 400 cubic centimeters) of the gelatinized starch-amine reaction product before it is added to the main portion of the gelatinized starch-amine reaction product.
  • Cation X dispersed in about gallon of water, is next added to the size and formaldehyde is thereafter added.
  • the size as thus prepared is adjusted to a pH of about 3.3 to 5 by the addition of acetic or hydrochloric acid.
  • the size has a viscosity of about 1 to 20 centipoises at 20 C. and a solids content of about 4 to 7.5 percent by weight of the size as shown in the examples.
  • glycerine When glycerine is employed in the size, it is added prior to the addition of the Pureco oil. This is accomplished by just pouring it into the cooked starch-amine reaction product and mixing it therewith. The gelatin is dispersed in water at 140 F. with vigorous agitation and it also is added to the gelatinized starch-amine reaction product prior to the addition of the Pureco oil. Elvanol (polyvinyl alcohol sold by du Pont) is dissolved inwater at 140 F. and is added in the size preparation right after the Pureco oil.
  • Example 11 The following is an example of a size formulation utilizin a reaction product of starch and an alkylene imine.
  • the hydroxyethyl ether of corn starch is reacted in the manner described in Example I with 30 percent by weight-of ethylene imine based upon the weight of, the hydroxyethyl ether of corn starch.
  • a size is prepared in the same manner as in Example I utilizing the following ingredients:
  • Example III A size utilizing the reaction product of corn starch and 5 percent by weight of propylene imine based upon the weight of the corn starch is prepared in the same manner as set forth in Example ll.
  • Example IV The following is an example of a size formulation utilizing a reaction product of starch and an alkyl amino epoxide.
  • Sago starch is reacted in the same manner as set forth in Example I with 10 percent by weight of 3- dibutyl amino 1,2-epoxy propane based upon the weight of the sago starch.
  • the size is prepared in the same manner as described in Example I utilizing the following ingredien-ts:
  • Gelatin 5 Polyvinyl alcohol 7. Formaldehyde 17 cubic centimeters per 5 gallon size mix.
  • Example V The following is an example of a size formulation utilizing a reaction product of starch and an amino alkyl anhydride.
  • Potatostarch is reacted in'the same manner as set forth in Example I with 20 percent by weight of isatoic anhydride based'upo-n the weight of the potato starch.
  • the size is prepared in the same manner as described in Example I utilizing the following ingredients:
  • Example VI A size utilizing the reaction product of corn starch and 10 percent by weight of quinoline anhydr-ide based upon the weight of the corn starch is prepared in the same mannor as set forth in Example V.
  • Example VII The following is an example of a size formulation utilizing a reaction product of starch and an alkyl amino anhydride. Tapioca starch is reacted in the same manner as set forth in Example. I with 3 percent by weight of b-dimethyl amino isoprcpyl chloride based upon the weight of the tapioca starch. The size is prepared inthe same manner as described in Example I utilizing the following ingredients:
  • Example VIII Formaldehyde 17 cubic. centimeters per 5 gallon size
  • Example VIII The following is an example of a size formulation utilizing a reaction product of starch and an alkyl amino halide which is difierent from that set forth in Example V.
  • Corn starch which is acid-converted to a degree known in the trade as 60 fluidity, is reacted in the same manner as set forth in Example I with 0.5 percent by weight of b-dimethyl amino ethyl chloride based upon the weight of corn starch.
  • the size is prepared in the same manner as described in Example I utilizing the following ingredients:
  • Example IX Potato starch is reacted with 1 percent by weight of 2- bromo-S-diethyl amino pentane hydrobromide based upon the weight of the potato starch. The size is prepared in the same manner as described in Example I utilizing the following ingredients:
  • Example X A starch-amine reaction product suitable for use in the invention is prepared in the manner set forth in Example I by reacting waxy maize starch with 25 percent by weight of N-(2,3 epoxypropyl) piperidine based upon the weight of the waxy maize. The size is prepared in the same manner as described in Example I utilizing the following ingredients:
  • Example XI A size utilizing the reaction product of rice starch and 30 percent by weight of N,N-(2,3 epoxypropyl methyl aniline) based upon the weight of the rice starch is prepared in the same manner as set forth in Example X.
  • the size is added to the fibers during their forming while it is at an elevated temperature, i.e. 125 to 135 F for example about 130 F. This is necessary in order to keep all of the ingredients of the size, especially the hydrogenated vegetable oil and the starch-amine reaction product, uniformly dispersed in the size. If the size is allowed to cool to, say for example room temperature, these ingredients tends to separate from the size.
  • FIG. 1 is a diagrammatic elevation of a continuous filament, glass fiber strand operation
  • FIG. 2 is a graph illustrating the improvement of the present invention over-the prior art with respect to size migration in the forming package.
  • FIG. 1 of the drawing there is shown a glass melting furnace or forehearth thereof containing a supply of molten glass 11 and having an electrically heated, platinum alloy bushing 13 attached to the bottom of the furnace.
  • the bushing is provided with a series of orifices in the form of tips 14 through which the glass flows and forms in small inverted cones 15 suspended from the bottoms of the tips 14.
  • 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 more in number.
  • Glass filaments 16 are pulled from the cones of glass 15 at a very high rate of speed, i.e., 5,000 to 20,000 feet per minute, and wound on the rapidly rotating forming tube 18.
  • the glass filaments are grouped into a strand 22 as they pass over the guide 24 prior to their being wound on the tube 18.
  • the size is applied to the individual filaments in the strand prior to the time they pass over the guide.
  • a size applicator is supplied to a reservoir 28 which has a rotating roller or belt 30 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 US. 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 about 3.5 pounds of 150 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 the strand is found onthe forming package.
  • the forming package containing about 9 percent by weight moisture, is then allowed to sit in an atmosphere of about 75 to 85 F. and to percent relative humidity for about 21 hours in order to reduce the moisture content on the strand to a range of about 5 to 7 percent by weight.
  • the strand is removed from the. forming package and twisted into yarn. Glass fiber strand having glycerine in its size is easier to end-find than strand without the glycerine in its size.
  • the twisting is accomplished on conventional textile apparatus with very few broken filaments. The twisted yarn is.
  • the woven material can be heat treated satisfactorily.
  • the heat treated fabrics woven from yarn having glycerine in its size are'slightly less brittle and more crease resistant than heat treated fabrics woven with yarn coated with a size not having the glycerine.
  • the graph shows the size solids content of the strand in the forming package 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 45 to 55 percent relative humidity and to degrees 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 representsthe amounts of solids of the starch-amine reaction product size described in this invention "as illustrated by sizeNo. 5 of the table in Example I 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 de scribed above is exceptionally useful for bulking by means of the texturing air jet described in the abovementioned patent.
  • the uniformity of size content on the yarn permits uniform conditions in the texturing operation and the production of acceptable textured yarn.
  • the size does not blow off of the yarn during the texturing as does the conventional dextrinized corn starch-oil size.
  • Heat treated fabrics Woven from twisted strand formed in accordance with the present invention are free from the appearance defects discussed above which are due to size migration in the strand forming package.
  • Water makes up about 91 to 96 percent by weight of the size.
  • the starch-amine reaction product makes up about 4 to 7 percent by weight of the size, preferably about percent by Weight of the size.
  • the lubricant is present in the size in amounts of 25 to 70 percent by weight of the starch-amine reaction product, preferably about 45 percent by weight of the starch-amine reaction product.
  • 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.
  • the Cation X is an example of such a material wherein the alkyd imidazoline derivative is the reaction product of stearic acid, tetraethylene pentamine and acetic acid.
  • a stearic acid-chromic chloride complex sold by du Pont under the tradename Quilon may serve as a softener.
  • An acid solubilized water dispersible stearic amide, an anhydrous acid solubilized, water dispersible lower molecular weight fatty acid amide or an anhydrous acid solubilized polyunsaturated, lower molecular Weight fatty acid amide may be used as :a softener.
  • Some of these softeners also serve as wetting agents, for example the alkyl imidazoline derivatives.
  • various wetting agents similar to Tween 81 may be employed in the size in sufficient amount to permit adequate wetting of the sizing ingredients to the glass surface; suitable amounts ranging from 8 to 13 percent by weight of the lubricant, preferably about 10 percent by weight of the lubricant.
  • Quaternary ammonium compounds such as trimethyl stearyl or cetyl amonium bromides and chlorides and generally any of the amine compounds that dissociate in water systems to provide a positive radical containing a group of more than 8 and preferably 12 or more carbon atoms may be used. These materials are cationic active substances. Non-ionic wetting agents may also be used. They are not as active as cationic wetting agents and therefore must be used in greater amounts to provide the same degree of wetting. Examples of suitable non-ionic wetting agents include polyalkylene oxide derivatives of esters, fatty acids, fatty alcohols, fatty amides, alkyl phenyl ethers and other derivatives.
  • a fungicide such as formaldehyde, is usually used in sufficient amount to prevent mold attack on the starchamine reaction product. Suitable effective amounts of the fungicide are about 3 milliliters to one gallon of the size.
  • Glycerine is believed to serve as a plasticizer for the starch-amine reaction roduct.
  • the glycerine is preferably present in amounts of about 5 to 20 percent by weight of the starch-amine reaction product, preferably about 10 Suitable wetting agents include i percent by weight of the starch-amine reaction product. Glycerine has been found to be useful in the size in order to make end-finding of the strand easier and to lessen the brittleness of the strand.
  • the combination of gelatin and polyvinyl alcohol in the size is desirable because of the added film strength properties which these materials impart.
  • the ratio of polyvinyl alcohol to gelatin when used in combination ranges from about 1:1 to 2:1.
  • the combined amount of gelatin and polyvinyl alcohol in the size is about 0.1 to 0.2 percent by weight of the starch-amine reaction product.
  • a method of forming glass fibers which comprises drawing glass filaments from a molten supply of glass at a high rate of speed, gathering the filaments and combining them into a strand, applying an aqueous size to the filaments as they are being drawn, said size being at an elevated temperature at the time of application and consisting essentially of an aqueous dispersion containing about 4 to 7 percent by weight of a starch-amine reaction product selected from the class consisting of starchamine reaction products having the following structural formulae:
  • R is a radical selected from the group consisting of substituted alkyl, hydroxyalkyl, acyl, and aroyl radicals
  • each of R and R is a radical selected from the group consisting of hydrogen, alkyl, and aralkyl radicals
  • X is starch
  • R is a radical selected from the group consisting of substituted alkyl, hydroxyl alkyl, acyl and aroyl radicals
  • each of R and R is a radical selected from the group consisting of hydrogen, alkyl and aralkyl radicals and where R, is a radical selected from the group consisting of hydrogen and alkyl radicals
  • Y is a radical selected from the group consisting of chloride, bromide and iodide radicals, about 25 to 70 percent by weight of a lubricant based upon the weight of the starchamine reaction product and an efifective amount of a fungicide, said size having a viscosity of about 1 to 20 centipoises at 20 C., winding the sized strand on a rapidly rotating forming tube and conditioning the strand wound on the forming tube to reduce the moisture content of the strand to that amount which is acceptable for twisting the strand into yarn on conventional textile twisting apparatus.
  • the size contains 8 to 13 percent by weight of a Wetting agent based upon the weight of the lubricant and 4 to 15 percent by weight of a textile softener based upon the weight of the starch-amine reaction product.
  • the size contains about 0.1 to 0.2 percent by weight of gelatin and polyvinyl alcohol, based upon the weight of the starchamine'reaction product, with the Weight ratio of polyvinyl alcohol to gelatin ranging from about 1:1 to 2:1.
  • the size contains 8 to 13 percent by weight of a wetting agent based upon the Weight of the lubricant, 4 to 15 percent by weight of a textile softener based upon the Weight of the l 1 starch-amine reaction product, 5 to 20 percent by Weight of a plasticizer for the starch-amine reaction product based upon the weight of the starch-amine reaction product and 0.1 to 0.2 percent by Weight of gelatin and polyvinyl alco hol based upon the weight of the starch-amine reaction product, with the Weight ratio of polyvinyl alcohol to gelatin ranging from about 1:1 to 2:1.

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US112631A 1961-05-25 1961-05-25 Method of applying an aqueous size to strands formed of glass filaments and product produced thereby Expired - Lifetime US3167468A (en)

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Application Number Priority Date Filing Date Title
NL278607D NL278607A (enrdf_load_stackoverflow) 1961-05-25
US112631A US3167468A (en) 1961-05-25 1961-05-25 Method of applying an aqueous size to strands formed of glass filaments and product produced thereby
GB19981/62A GB997051A (en) 1961-05-25 1962-05-24 Method of forming glass fibres
DE19621469181 DE1469181A1 (de) 1961-05-25 1962-05-24 Verfahren zur Herstellung von Glasfasern
BE618146A BE618146A (fr) 1961-05-25 1962-05-25 Procédé de formation de fibres de verre

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US112631A US3167468A (en) 1961-05-25 1961-05-25 Method of applying an aqueous size to strands formed of glass filaments and product produced thereby

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BE (1) BE618146A (enrdf_load_stackoverflow)
DE (1) DE1469181A1 (enrdf_load_stackoverflow)
GB (1) GB997051A (enrdf_load_stackoverflow)
NL (1) NL278607A (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459585A (en) * 1966-12-05 1969-08-05 Ppg Industries Inc Novel reaction product and use thereof as a glass fiber size
US3512232A (en) * 1966-11-23 1970-05-19 Deering Milliken Res Corp Process for preparing twistless yarns
US3615311A (en) * 1969-11-12 1971-10-26 Owens Corning Fiberglass Corp Starch coated fibers having improved drying characteristics
US3887752A (en) * 1972-11-24 1975-06-03 Hubinger Co Textile treatment with amphoteric starch esters
USB452293I5 (enrdf_load_stackoverflow) * 1974-03-18 1976-03-30
US3971871A (en) * 1973-10-19 1976-07-27 Owens-Corning Fiberglas Corporation Texturizing size and glass fibers coated with same
US3993805A (en) * 1972-07-31 1976-11-23 Concorde Fibers Inc. Method of applying liquid finish composition to filaments
US4066106A (en) * 1975-09-02 1978-01-03 Ppg Industries, Inc. Sized woven glass fabric
US4517916A (en) * 1982-09-30 1985-05-21 Ppg Industries, Inc. Applicator for treating textile filaments with chemical treatments
US4839449A (en) * 1987-10-26 1989-06-13 National Starch And Chemical Corporation Polysaccharides containing aromatic aldehydes and their derivatization via amine-aldehyde interactions
US4973680A (en) * 1989-03-03 1990-11-27 National Starch And Chemical Investment Holding Corporation Organosiloxane-containing polysaccharides
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
US20080241533A1 (en) * 2006-12-15 2008-10-02 Jacob Cornelis Dijt Sizing compositions and glass fiber reinforced thermoplastic composites

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4224439A (en) 1977-02-08 1980-09-23 Development Finance Corporation Of New Zealand Activated matrix and method of activation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2446119A (en) * 1944-07-27 1948-07-27 Owens Corning Fiberglass Corp Glass fiber reinforced plastics
US2511887A (en) * 1950-06-20 Battery separator
US2946705A (en) * 1958-08-26 1960-07-26 Nat Starch Chem Corp Warp sizing process
US2970140A (en) * 1957-08-09 1961-01-31 American Maize Prod Co Process for preparing amino ethers of starch

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511887A (en) * 1950-06-20 Battery separator
US2446119A (en) * 1944-07-27 1948-07-27 Owens Corning Fiberglass Corp Glass fiber reinforced plastics
US2970140A (en) * 1957-08-09 1961-01-31 American Maize Prod Co Process for preparing amino ethers of starch
US2946705A (en) * 1958-08-26 1960-07-26 Nat Starch Chem Corp Warp sizing process

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3512232A (en) * 1966-11-23 1970-05-19 Deering Milliken Res Corp Process for preparing twistless yarns
US3459585A (en) * 1966-12-05 1969-08-05 Ppg Industries Inc Novel reaction product and use thereof as a glass fiber size
US3615311A (en) * 1969-11-12 1971-10-26 Owens Corning Fiberglass Corp Starch coated fibers having improved drying characteristics
US3993805A (en) * 1972-07-31 1976-11-23 Concorde Fibers Inc. Method of applying liquid finish composition to filaments
US3887752A (en) * 1972-11-24 1975-06-03 Hubinger Co Textile treatment with amphoteric starch esters
US3971871A (en) * 1973-10-19 1976-07-27 Owens-Corning Fiberglas Corporation Texturizing size and glass fibers coated with same
USB452293I5 (enrdf_load_stackoverflow) * 1974-03-18 1976-03-30
US4014726A (en) * 1974-03-18 1977-03-29 Owens-Corning Fiberglas Corporation Production of glass fiber products
US4066106A (en) * 1975-09-02 1978-01-03 Ppg Industries, Inc. Sized woven glass fabric
US4517916A (en) * 1982-09-30 1985-05-21 Ppg Industries, Inc. Applicator for treating textile filaments with chemical treatments
US4839449A (en) * 1987-10-26 1989-06-13 National Starch And Chemical Corporation Polysaccharides containing aromatic aldehydes and their derivatization via amine-aldehyde interactions
US4973680A (en) * 1989-03-03 1990-11-27 National Starch And Chemical Investment Holding Corporation Organosiloxane-containing polysaccharides
US5004791A (en) * 1989-03-03 1991-04-02 National Starch And Chemical Investment Holding Corporation Organosiloxane-containing polysaccharides
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
US20080241533A1 (en) * 2006-12-15 2008-10-02 Jacob Cornelis Dijt Sizing compositions and glass fiber reinforced thermoplastic composites
US9758429B2 (en) 2006-12-15 2017-09-12 Ppg Industries Ohio, Inc. Sizing compositions and glass fiber reinforced thermoplastic composites

Also Published As

Publication number Publication date
GB997051A (en) 1965-06-30
DE1469181A1 (de) 1968-11-14
NL278607A (enrdf_load_stackoverflow) 1900-01-01
BE618146A (fr) 1962-11-26

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