DE1469181A1 - Process for the production of glass fibers - Google Patents

Description

Pittsburgh Plate Glass Company, Pittsburgh, Pennsylvania,

V.St.A.

Process for the production of glass fibers

The invention relates to a method for producing glass fibers and, more particularly, to the application of a coating on fiberglass strand made of endless threads during the manufacture of the strand,

In the manufacture of glass fiber braid from endless threads, a number of individual glass threads become electrical from one Pulled a heated platinum alloy bowl containing a supply of molten glass. «The glass is running by points that delimit openings in the bottom of the bowl and form inverted glass cones at the end of the points · Individuals Threads are pulled from the glass cones at high speed, i.e. 1500 to 6000 m per minute, and passed over by guiding them a suitable guide combined into a strand. The strand is then wound onto a rapidly rotating shaped tube The strand is not twisted in this production,

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and an aqueous sizing composition comprising an aqueous dispersion of a binder and a lubricant, for example from dextrinierter corn starch and a vegetable oil is applied to the individual filaments before they comparable to the strand ^/ agree and wound onto the pipe, in order to each other connect and ensure the cohesion of the braid. The strand is wound onto the tube with a slight inclination so that successive layers cross each other at an angle and are not parallel, so that the strand can be more easily unwound from the tube.

One problem that arises in this manufacture of strand from endless threads is "sizing". Sizing is a phenomenon that occurs in the strand as it is wound onto the forming tube. As The size stated above is an aqueous dispersion of dextrinated corn starch and vegetable oil. Of the The solids content of the size is about 12% by weight, the re3t is water. Some of this water must come from the Strand can be removed before it is twisted into a yarn. This water is removed from the strand by this is dried while it is wound on the forming tube. When the strand roll dries on the forming tube, it migrates the water from the inside of the roll (forming package) near the pipe to the outer parts of the roll. at This movement of the water becomes part of the strength and of the

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oil taken with the sizing compound, so that the strand in the outer layers of the roll has a significantly higher sizing solids content than in the layers below the surface.

Through the Schlichtwanderung a number of Problems with the subsequent processing of the strand. When twisting, shearing, shearing, winding and weaving Fiberglass yarn undergoes a number of winding and unwinding operations that involve the tension applied to the yarn is essential. The tension exerted on the yarn during these operations must be relatively constant. if the tension on the yarn is uneven during these measures, the individual threads forming the yarn can easily break and form a fibrous yarn. Fibrous yarn clogs the processing equipment and leads to breakage. Uneven tension on the yarn can result from uneven sizing content of the yarn along its length. It it is therefore desirable that the sizing content of the yarn is uniform over its entire length.

Another processing operation in which an uneven sizing content of the yarn is harmful is the defibration or texturing. Frayed yarns are yarns made from endless threads that are loosened up by an air nozzle have been. The size content of the yarn that is defibrated determines the resistance of the yarn during defibration or

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Loosening up with the air jet. A change in the Sizing along the length of the yarn leads to a Fluctuation in the degree of loosening · Any fluctuation in the The degree of loosening of the yarn is evident in the fabric and can be so strong that the end product is flawed.

A further problem arises due to the sizing migration during the heat treatment of woven fabrics.Handle with a higher sizing solids content looks different than braid with a lower sizing solids content when the twisted braid is woven into a fabric and this is used to remove the sizing solids and to fix the fibers in the tissue is heated "the heat treatment 30 to 40 seconds is carried out at 650 - 76o ⁰ C and is sufficient to soften the solid substance to volatilize and from the tissue to be removed and the fibers in the fabric, to set it in its new position. After the heat treatment, the strand from the outer layers of the roll, which originally had the higher sizing solids content, can be seen as a band in the fabric, which reflects the light differently than the best of the fabric. Sometimes this tape has a water-luster effect · This leads to a defective fabric which can be so pronounced that the end product is unusable · It is not exactly known what causes the difference in the yarn in the fabric; but it is likely to be caused by incomplete removal of the

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temasse or by a different orientation of the Single threads in the yarn because of the increased heating activity arise in places where there is a bit of increased sizing if the fabric has been sufficiently heated is to remove the entire sole mass from the tissue Fabric production has been · The disadvantages mentioned occur This also applies to fabrics that have been woven from endless single threads with frayed glass yarns.

As can be seen from the description of the defects that occur in fabrics due to size changes these lead to considerable difficulties and require energetic measures to eliminate them Roll to remove the part of the roll, the strand with a higher sizing content than the rest of the roll contains · This means a substantial loss in the manufacture of braid and also requires an expensive one and undesirable interference between manufacture and twisting the strand *

Besides the difficulties caused by the Schlioht - If there are wanderings, the usual starch-oil-soling agents are difficult to experience using the above-mentioned air jet fiberize · Bas starch binder is atomized and removed from the

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treated yarn blown away · This pollutes the air and annoys workers. Furthermore, di Air nozzle clogged and the yarn frayed unevenly Starch deposits collect in the nozzle and decrease Ib over time the shredding effect · The pressure in the Nozzle rises until finally it is enough to expel all the accumulated starch with a shark and it starts again the complete fiberization effect This leads to xu a scattering effect in the nozzle and an uneven defibration of the yarn that passes through the nozzle

The subject of the invention is an aqueous sizing mass which can easily be applied to glass fiber strand during its manufacture in uniform, controllable amounts and their non-aqueous constituents do not migrate in the pile when the pile dries on the molding tube · Another The object is a sizing compound which allows the strand to be twisted, if necessary evenly frayed, spooled or topped, and to form a fabric with a more uniform texture Chip mang to interweave, whereby the number of broken threads in these different processing measures is limited to a minimum. Another item is one aqueous sizing mass, the solid constituents of which are light and Can be completely removed from a fabric by the usual heat treatment that is applied to the sizing to remove constituents and to increase the fibers in the fabric

fix·

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U69181

According to the invention a process for the production of clay glass fibers is provided, which consists in pulling glass threads from a supply of molten glass at high speed, taking up the threads and combining them into a strand _t applying an aqueous sizing mass to the threads at elevated temperature during the drawing , winds the sized strand onto a fast-running molded tube and conditions the strand wound onto the molded tube in order to reduce its moisture content to such an extent that it can be twisted into a yarn on a conventional textile twisting device, the sole mass being essentially composed of an aqueous dispersion of about 4 to 7% by weight of a starch-amine reaction product described below, about 25 to 70% by weight of a lubricant, based on the weight of the starch-amine reaction product, and a fungicide, and a viscosity has from about 1 to 20 centipoise at 20 ⁰ C.

The sizing compound can also contain other ingredients, e.g. an enhancer and a wetting agent. Small amounts of additional non-starch film-forming ingredients can be added, e.g. Gelatin or polyvinyl alcohol to make a more durable strand. With "starch" here is any starch-like substance meant as untreated starch, as well as starch derivatives, e.g. dextrinated, hydrolyzed, oxidized, esterified and esterified

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ethereal starches that still have starch-like substance. the Starch can be of any origin, e.g. corn, wheat, potato, tapioca, Turkish wheat, sago or Be rice starch.

The starch-amine reaction products used according to the invention are made by reacting starch with an esterification or etherifying agent prepared which serves to introduce an amino group into the starch. The middle can be a nitrogen containing compound, e.g. an aminoalkyl anhydride, alkylimine, alkyl epoxide and alkylamino halide, as well as a corresponding compound which, in addition to the alkyl groups, contains aryl groups. All these substances have the property of reacting with hydroxyl groups of the starch to form an ester or ether bond and thereby a To introduce amino group into the starch.

Examples of substances suitable for producing such starch derivatives are ethyleneimine; Propylenimine isatoic anhydride j Quinolinic anhydride j ß-Diethylaminoäthylehloridf ß-methylaminoisopropyl chloride} ß-dimethylaminoethyl chloride j 3-diethylamino-1,2-epoxypropane. 3-dibutylamino-1,2-epoxypropane j 2-bromo-5-diethylaminopentane hydrobromide; N- (2,3-Epoxypropyl) -piperidinj N- (2,3-Epoxypropyl) -methylaniline and N, N- (2,3-epoxypropyl) methylaniline. The different halides (e.g. chlorides, bromides, etc.) can be found in be used in each case. Instead of the given free amines (e.g. ß-diethylaminoethyl chloride) you can also use the

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Use hydrochloride or other salts (e.g. ß-diethylaminoethyl chloride hydrochloride). Usually the salts are preferred because they are often less toxic lind eich more convenient to use · The hydrochloride content does not participate in the reaction. In addition to the alkyl, aryl and aralkyl compounds, substances with cyclic Substituents can be used. So if alkyl, aryl and Aralkyl groups are mentioned, the compounds with cyclic substituents are of course equivalent to these The starch-amine reaction product can also be treated to form the quaternary ammonium salt.

The starch-amine reaction products can be prepared by known methods such as those disclosed in U.S. Patents 2,813 and 2,946,705. In the manufacture of the starch-amine reaction products, the starch preferably treated with one of the substances described above in the presence of an alkaline medium. this happens by suspending the starch in water to which (either before or after the addition of the starch) a sufficient amount of base, e.g. alkali hydroxide, alkaline hydroxide, quaternary ammonium hydroxide, or the like, has been added to the mixture during to keep the reaction alkaline · Then the required amount of amine compound is added and stirring is continued until the desired implementation is complete. If necessary, it can be heated in order to accelerate the implementation, since the usual Relationship between time and temperature applies. The amount of

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etherifying or esterifying agent varies with the selected substance (because these have different reactivity and reaction efficiency) and the desired degree of substitution. The amine-starch reaction product can 0.5 to 30 wt. # Based on the weight of the starch Containing amino groups

The starch-amine reaction product can either be in gelatinized or in ungelatinized form · To prevent the gelatinization of the starch during the implementation with the amine in cases where the degree of alkalinity or heat is so high that gelatinization would take place, a gelatinization-inhibiting substance, e.g. sodium sulfate, the mixture of starch, Alkali, water and reactants added.

The starch-amine reaction product prepared in this way and used in the present invention has the following general structural formula:

XORNR ₂

wherein X is a starch, R is a divalent alkyl, hydroxyalkyl, acyl or aroyl radical and R ₁ and R _{2 are} hydrogen, alkyl, aryl or aralkyl radicals. Menu the derivative is in the salt form or in the form of the quaternary saix, it has the following formula:

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XOHNR ₀ II

R ₃ Y

in which X, R- and R _{2 have} the meaning given above and R, hydrogen or an alkyl radical and Y is a chlorine, bromine or iodine atom, examples of the above groups are taken from the corresponding products used for the preparation of the starch-amine reaction products substances specified above

The following are examples of the size for fiberglass strand

Example I.

The following table shows various sizes that can be used according to the invention, wherein the starch-amine reaction product is an alkylamino halide salt obtained by reacting corn starch with ß-Diethylaminoethyl chloride hydrochloride is obtained.

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Parts by weight (g)

uuouuu / υ υ «3 H
component 1 2 3 4th 5 5 6th 7th 8th 5 -12 Starch-amine reaction product 1000 1000 800 600 780 7th 600 600 910 11 I. Pureco oil 308 308 410.5 410.5 322 17ccm 410 308 210 - Tween 81 40.9 40.9 40.9 40.9 32 4.5 40.9 40.9 21 5.0 Cation Σ 44.3 44.3 44.3 44.3 68 6.0 88.6 44.3 44 6.07 Glycerin - 200 80 60 - 1.0 100 60 - 1.04 gelatin - - - - '- - Elvanol MM - - - - - formaldehyde 17ccm 17ccm 17ccm 17ccb 17 cents 17ccm pH 4.0 4.0 4.0 3.9 3.5 3.3 io solids 6.41 7.17 6.27 5.47 5.15 4.59 $> Zueatz 0.97 1.02 1.16 1.03 0.84 0.82

CD CO -a,

The above mixtures are given in the amounts required for Production of 18.75 1 sore mass is required. All quantities are - as can be seen from the head of the table in g specified, only formaldehyde in ecm. The starch-amine reaction product is made by reacting corn starch with ß-diethylaminoethyl chloride hydrochloride in the following Way made. 1.81 kg of sodium hydroxide are used in 68 kg Dissolve water and add 22.7 kg of sodium sulfate · Stir until the substances have dissolved and then 45.3 kg of corn starch are added with constant stirring. When the suspension is uniform, a solution will be found of 1.81 kg of ß-diethylaminoethyl chloride hydrochloride in 11.3 kg Water added. The mixture is stirred for 24 hours, after which sufficient dilute hydrochloric acid is added to bring the pH up to Bring about 3 »The starch product is then filtered, washed thoroughly with water and dried to a powder. The Pureco oil in the blends is a partially hydrogenated one vegetable oil from ier Capital City Products Company. Tween 81 is a wetting agent, namely an ethylene oxide derivative of a sorbital ester from the Atlas Powder Company. Cation X is a fabric softener and is an alkyl imidazoline reaction product of tetraethylene pentamine and stearic acid manufactured by Onyx Oil and Chemical Company.

The size is prepared by first adding 9.37 liters of water to a mixing vessel. That

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-H-

Starch-amine reaction product is then added to the water, forming a slurry, and the pH of the slurry is adjusted to 3.5 + 0.2 with acetic acid. The slurry is ^{heated to 93 °} C. and about 15 minutes held at this temperature to gelatinize the starch-amine reaction product. The gelatinized starch-amine reaction product in the aqueous diluent is then cooled to 71 ⁰ C · Then, the Pureco oil is added. The Purecoöl is a solid substance with the consistency of lard and is first melted and then emulsified with water, Tween 81 and a small amount (200 to 400 ecm) of the gelatinized starch-amine reaction product, before the main amount of the gelatinized starch-amine Reaction product is added. Then Cation X is dispersed in about 950 ecm of water, and finally the formaldehyde is added to the size. The sizing composition has a viscosity of about 1 to 20 centipoise at 20 ⁰ C and a Peststoffgehalt of about 4 to 7.5 wt, - # show, as the examples.

If glycerin is added to the size, this is done before the Pureco- pulse is added; it is simply poured into the cooked starch-amine reaction product and mixed with it. The gelatin is diepergiert in water at 60 ⁰ C under vigorous stirring and also prior to the addition of the oil with the Pureoo-gelatinized starch-amine reaction product

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mixed. Elvanol (polyvinyl alcohol from DuPont) is dissolved in water at 6O ⁰ C and the Schlichteinasse after Pureco oil added ·

Example II

The following is an example of a size comprising a reaction product of starch and an alkylene imine
The hydroxyethyl ether of corn starch is reacted in the manner indicated in Example I with 30% by weight of ethylene imine, "based on the weight of the hydroxyethyl ether of corn starch. A size is prepared in the same way as in Example I from the following ingredients:

Component parts by weight

Starch-ethyleneimine reaction product 800 Hydrogenated vegetable oil 410.5

Wetting agent (Tween 81) 40.9

Plasticizer (Cation X) 44.3

Glycerin 80.0

Formaldehyde 17 ecm 18.75 each

Sizing compound

Example III

A size made from the reaction product of
Corn starch with 5 wt _# - # propylenimine, based on the weight of the corn starch, is prepared in the same way as in Example II.

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Example IY

Eb follows an example of a sizing compound with a reaction product of starch and an alkylamino epoxide. Sago starch is used in the same way as in example I with 10 wt .- ^ 3-dibutylamino-1,2-epoxypropane on based on the weight of the sago starch, "You size is implemented in the same way as in Example I from the the following components:

Component parts by weight

Saga starch epoxy reaction product Example V 780 Pureco oil 322 Twee «81 32 Cation X 68 gelatin VJl Polyvinyl alcohol 7th formaldehyde 17 ecm each 18.75:
Sizing compound

An example of a sizing compound follows a reaction product of starch and an aminoalkyl anhydride · potato starch is prepared in the same manner as in Example I given, with 20 wt., - # Isatoic anhydride based on the weight of the potato starch, implemented. The size is prepared in the same way as in Example I. made from the following components:

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600 9 410 6th 40, 88

-17-

Beat ^ ndteil Sewiohtsteile

Potato starch-isatic anhydride reaction product Schalermittel (Pureco oil) Wetting agent (Tween 81)
Plasticizer (cation X)

Fungicide (formaldehyde) 17 ecm 18.75 each 1

Sizing compound

Example YI

A size of the reaction product of corn starch and 10 wt .- # quinolinic anhydride, on the Weight of corn starch based, is prepared in the same way as in Example V.

Example YII

The following is an example of a size containing the reaction product of starch and an alkylamino anhydride. Tapioca starch is reacted in the same way as in Example I with 3 wt. _# - # ß-dimethylaminoisopropyl chloride, based on the weight of the tapioca starch.

Component parts by weight

Starch-alkyl amino halide reaction product 1000

Pureco Oil 308

Tween 81 40.9

Cation X 44.3

Formaldehyde 17 ecm 18.75 each 3

Sizing compound

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Example VIII

The following is an example of a size with a reaction product of starch and an alkylamino halide different from that given in Example V. is. Corn starch, which in one as flowability 60 (English: 60 fluidity) known has been converted by acid, is in the same way as in Example I with 0.5 wt .- ^ ß-dimethylaminoethyl chloride, based on the weight of the corn starch related, implemented. The size is prepared in the same way as in Example I from the following ingredients.

Part by weight

Cornstarch puree oil Tween 81 Cation X gelatin polyvinyl alcohol formaldehyde

780

322

17 ecm 18.75 each 1 slide dimensions

Example IX

Potato starch with 1 wt .- # 2-bromo-5-diethylaminopentane hydrobromide, based on the weight of the potato starch, implemented. The sizing mass is in the same Made as in Example I from the following ingredients:

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Ingredient parts by weight

Potato starch amine

Reaction product 600

Pureco oil 410

Tween 81 40.9

Cation X 88.6

Glycerin 100

Example X

A starch-amine reaction product used in the present invention Suitable use is made in the manner indicated in Example I by reacting starch Turkish wheat with 25 wt .- # N- (2,3-epoxypropyl) -piperidine, based on the weight of the starch. The size is prepared in the same way as in Example I from the the following components:

Part of the weight point

Strength 910

Pureco oil 210

Tween 81 21

Cation X 44

Gelatin 5

Polyvinyl alcohol _ 11

Formaldehyde 17 ecm 18.75 each 1

Sizing compound

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Example XI

A size made from the reaction product of rice starch and 30% by weight of N, N- (2,3-epoxypropylmethylaniline), based on the weight of the rice starch, is prepared in the same manner as in Example X.

The sizing composition is the fibers during their production at an elevated temperature, ie, 52-57 ⁰ C, for example, is added at about 54 ⁰ G. This is necessary to keep all the constituents of the size, especially the hydrogenated vegetable oil and the starch-amine reaction product, uniformly dispersed. If the sizing is allowed to cool, for example to room temperature, these ingredients can separate out. The procedure for adding the size to the strands and examining the amount of size on the strand after manufacture and conditioning is described below in conjunction with the accompanying drawings:

Fig. 1 is a schematic view of the manufacture of glass fiber strand with endless threads}

Figure 2 is a graph showing the progress of the method of the present invention over the prior art the technique demonstrated in terms of sizing in the role.

In Figure 1, a glass melting furnace or a forehearth of the same 10 is shown, which has a supply of molten glass

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contains and an electrically heated shell 13 made of platinum alloy at the bottom of the stove. The shell is provided with a series of openings in the form of tips 14 through which the glass flows and forms into small inverted cones 15 hanging from the lower end of the tips 14. The tips are usually arranged in a number of rows, e.g. 4 to 20 rows or more with a large number of tips in each row, so that their total number is about 200 to 400 or more.

Glass threads 16 are made from the glass cones 15 at a very high speed. ie _o 1,500 to 6,000 meters per minute and pulled "wound on the rapidly rotating forming tube 18. Glass filaments are combined into a strand 22 as they pass the guide 24 before being wound onto the tube 18. When the strand 22 is wound onto the tube 18 it is swiftly reciprocated by the transverse guide 26. The sizing mass becomes applied to the individual threads of the braid before they run over the guide. The size is taken from a reservoir 28 which contains a rotating roller or belt 30 mounted so that it is immersed in the size in the reservoir A suitable device for applying sizing compounds is shown in US Pat. No. 2,873,718.

The sizing compositions according to the invention can easily be applied to the strand during its manufacture, and

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the formation of the strand runs smoothly after a roll with about 1.59 kg of 150 strand has been wound (204 strands with such a diameter that 13,700 m per 453 g strand), the forming tube and the roll are removed from the axis of rotation, and looked for the end of the strand on the reel. The roll, which contains about 9% by weight of moisture, is then left in an atmosphere of about 24 to 29 ^° C. and 45 to 55% relative humidity for about 21 hours to bring the moisture content of the strand to about 5 to 7% by weight. ^ lower. The strand is then removed from the roll and twisted into yarn _β glass fiber strand with glycerine in the sizing compound reveals its end more easily than those without glycerine in the compound. Twisting takes place on a conventional textile machine, with very few threads breaking. The twisted yarn is sheared or transferred to bobbins for weaving, and the yarn is very easy to interweave, with very few threads breaking. The woven product can be treated satisfactorily in the heat. The heat treated fabrics woven from yarn with glycerin in the size are slightly less brittle and slightly more crease resistant than the heat treated fabrics woven with yarn coated with a non-glycerin size is.

The graph in Figure 2 shows the sizing solids content of the strand in the roll, which after the method according to the invention has been produced, in the

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Equal to that produced in a known manner · The ordinate gives the sizing solids content of the strand in percent after conditioning for 21 hours at 45 to 55 # relative humidity and 24 to 29 ° C. The abscissa indicates the length of the strand in m when the roll is unwound from the outside to the inside The dashed line indicates the level of pesticides in one the usual sizing mass of dextrinated corn starch and vegetable oil, and the solid line means that Content of pesticides in a size according to the invention composed of a starch-amine reaction product, e.g. size Νγ · 5 of the table of Example I along the strand in the roll after the specified conditioning.

It can be seen that the starch-amine finishing composition apparently no sizing migration occurred while significant migration of the usual dextrinated Corn starch sizing mass is made in the outer 3600 m strand · An equivalent sizing and binding can be done with smaller amounts of starch-amine size compared to the normal starch sling mass can be achieved · By the even amount of sizing solids on the strand Applying the starch-amine sizing compound will ensure a uniform low tension of the strand during winding and unwinding until it is converted into a yarn and a woven product. During these various processing operations the strand or yarn can be handled easily, with very few threads breaking. That after the one described above

Π R / 0 5 9 U

The process of sized yarn can be done extremely well Use to loosen up using the disintegration air nozzle described in the above-mentioned patent specification. the Uniformity of the size content on the yarn enables uniform conditions to be maintained during the defibration and the production of useful fiberized yarn. The size does not become detached from the yarn during fiberization blown away like the usual dextrinated size Corn starch and oil. Heat treated fabrics woven from twisted strand made in accordance with the present invention has been made have no flawed appearance, such as it occurs in the manner described above through the sizing migration in the strand roll.

In various experiments according to the invention were different amounts of the different ingredients are used in the size. The amount of water is about 91-96 Weight # of the size. The starch-amine reaction product makes up about 4-7% by weight of the mass, preferably about 5% by weight. The lubricant is used in an amount of 25-70 wt. #, Preferably about 45 wt. #, Based on the starch-amine reaction product applied.

Various textile softeners, the Cation X equivalent can be added in sufficient quantity to soften the sized strand, e.g. 4 to 15 Weight # of the starch-amine reaction product, preferably about 10 wt .- ^. Suitable fabric softeners are alkylimidazoline

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derivatives · Cation X is an example of such a substance, wherein the alkylimidazoline derivative is the reaction product of Stearic acid, tetraethylene pentamine and acetic acid. A stearic acid-chromium chloride complex, of which du Pont under the Trade name "Quillon" offered can act as a plasticizer serve an acid-solubilized, water-dispersible stearic acid amide, an anhydrous acid-solubilized, low molecular weight fatty acid amide dispersible in water or an anhydrous, acid-solubilized, polyunsaturated, low molecular weight fatty acid amide used as plasticizers «Some of these plasticizers also act as wetting agents, e.g. the alkylimidazoline derivatives. Various wetting agents similar to Tween 81 can also be added to the size in sufficient quantities to allow sufficient wetting of the glass surface by the size constituents; suitable Kengen are between 8 and 13 wt * - # of the lubricant, preferably at about 10 wt. or stearyl monoamine hydrochloride or acetate, dodecylamine, Hexadecylamine and secondary and tertiary derivatives thereof, ζ »Β« dodecylmethylamine and its salts, quaternary ammonium compounds, such as trimethylstearyl or cetylammonium bromide and chloride and, in general, all amine compounds described in dissociate in aqueous solution to a positive radical which is a group of more than 8 and preferably 12 or more carbon atoms Contains can be used · These substances are

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cation-active substances, non-ionic wetting agents can also be used. They are not as active as cationic wetting agents and must therefore be used in larger quantities to achieve the same effect. Examples of suitable nonionic wetting agents are polyalkylene oxide derivatives of esters, fatty acids, fatty alcohols, fatty amides, alkylphenyl ethers and other derivatives,

A fungicide, such as formaldehyde, is usually added in sufficient amount to mold the starch-amine reaction product to prevent. Suitable effective amounts of the fungicide are about 3 ecm per 3.75 liters of size.

Glycerin likely acts as a plasticizer for the starch-amine reaction products. Glycerin is preferred in an amount of about 5 to 20% by weight, based on the Starch-amine reaction product, preferably from about 10 wt .- ^, added A glycerine addition has proven to be useful to make it easier to find the end of the strand and to reduce the brittleness of the strand.

The combination of gelatin and polyvinyl alcohol in the size is useful because these substances give extra strength to the film · When both are used in combination, the ratio of polyvinyl alcohol will be to gelatin between about 1: 1 and 2: 1. The total amount of gelatin and polyvinyl alcohol in the sizing is about 0.1 to 0.2 weight percent of the starch-amine reaction product.

- Claims 809808/0594

Claims (1)

Patent claims: 1, Process for the production of glass fibers, in which one draws glass threads from a supply of molten glass at high speed, takes up the threads and combines them into a strand, an aqueous sizing compound is applied to the threads during the drawing, the sized strand on a rapidly twisted one The forming tube is wound and the wound strand is conditioned in order to reduce its moisture content to such an extent that it can be twisted into yarn on a conventional textile twisting device, characterized in that the size consists essentially of an aqueous dispersion of about 4 to 7 wt .- ^ a starch-amine reaction product of the structural formula I or II, wherein X is starch, R is a divalent alkyl, hydroxyalkyl, acyl or aroyl radical, R ₁ and R «are hydrogen, alkyl, aryl or aralkyl radicals, R is hydrogen or alkyl and Y is chlorine, bromine, or iodine, from about 25 to 70 weight percent of a lubricant based on the weight of the starch-amine -Reaction product, and contains a fungicide, the size having a viscosity of about 1 to 20 centipoise at 20 ⁰ C. 2. The method according to claim 1, characterized in that that the size 8 to 13 wt, - # of a wetting agent on based on the weight of the lubricant, and 4 to 15 wt .- ^ of a fabric softener, based on the weight of the starch-amine reaction product based. 809808/0594 3, method Mach claim 1 or 2, characterized in that the Schliohtemasse 5 to 20 wt, - # of a softener for the starch-amine reaction product, on its Weight related, contains 4. The method according to one of the claims that go through the goal, characterized in that the size is about 0.1 to 0.2 wt .- # gelatin and polyvinyl alcohol, based on the weight of the starch-amine reaction product contains, which Weight ratio τοη polyvinyl alcohol to gelatin between is approximately 1: 1 and 2: 1 809808/0594