MXPA00000271A - Nonaqueous sizing system for glass fibers and injection moldable polymers - Google Patents

Abstract

A nonaqueous sizing glass fibers useful for reinforcement of polymers. The sizing composition comprises one or more film formers miscible with the polymer to be reinforced and one or more coupling agents. The sizing composition of the invention provides a glass fiber (1A) which may be wirecoated with the polymer (2A) to be reinforced, eliminating the need for extrusion or pultrusion processing to make glass/polymer composite fibers, compounds or pellets.

Description

NON-AQUEOUS APPARATUS SYSTEM FOR GLASS FIBERS AND POLYMERS MOLDABLE BY INJECTION TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION The present invention provides a non-aqueous sizing composition for use in the manufacture of glass fibers, for the reinforcement of polymers such as nylon and polypropylene. The invention further relates to a non-aqueous sizing composition which can be hot applied directly to glass fibers in the forming process, to provide a wick with more sizing. In particular, the sizing composition allows a higher level of sizing in the glass fiber, such that it is now easier for the matrix resin to combine with the glass fibers. In addition, the invention is directed to the production of thermoplastic resin pellets containing glass fibers at a much higher speed and a greatly reduced cost. Specifically, the sizing improves the wetting efficiency, thus improving the wire coating process and making a preferable means for making nodules. Still further, the invention allows wire coating of the glass fiber prepared by the reinforced polymer, thereby eliminating the need for extrusion processing or extrusion by drawing to produce the glass / polymer composite nodules or fibers. The invention also it provides a high-sizing filler wick, which allows the glass and thermoplastic to combine more efficiently with uniform dispersion of the glass fibers within the polymer. BACKGROUND OF THE INVENTION Sizing compositions are well known and widely used in the manufacture of carbon or glass fibxes to improve their processing properties, such as: cohesion of fiber bundles, beam formation, dispersibility, resistance to lint formation , smoothness of fibers and softness, abrasion resistance and non-destructive development capacity of the bundled fiber bundles. The sizing compositions also affect the physical properties of the compound containing the treated fibers. The reinforced plastic industry has been using glass fibers in various ways to reinforce polymer matrices in producing a variety of products. Glass fibers have been used in the form of filaments, strands and continuous or chopped wicks as well as woven and nonwoven fabrics, meshes and thin canvases to reinforce polymers. Thermoplastic polymer matrices have been reinforced with a variety of different forms of glass fibers that result in the production of products such as: sheet, bulk molding compounds, stretch extrusion products, panel products, spray molding products, etc. The production of glass fibers for the polymer reinforcement market involves attenuating the glass fibers of the melt streams of fibrillable glass material, a bushing or similar devices connected to a furnace containing fibrillable glass material. The glass fibers are attenuated by conventional means such as reels or air jets with high pressure. In the process of producing glass fibers, a chemical composition is applied to them, shortly after they are attenuated like the melted glass streams. Prior to the present invention, the chemical composition has traditionally been a gel, foam or aqueous solution solution composition containing polymeric film-forming materials, coupling or handling agents, lubricants and sometimes processing aids. This sizing or chemical composition is necessary in order to retard abrasion between filaments of the glass fibers, when they are collected in a bundle of fibers or glass strands. It is also required in order to make the glass fibers compatible with the polymer matrices with which it is customary to reinforce. After application of the sizing, the fibers are then dried either in the form of package or in the form of strands, before they are used for reinforcement. Prior to the present invention, the next step for using glass fibers as reinforcement for molded polymers involves the production of either a long fiber composite or a short fiber composite. In general, the production of short fiber composites involved mixing pure polymer nodules with the chopped glass fibers such that the glass fibers would disperse through the polymer when they were extruded. Stretch extrusion is used to produce long fiber composites when they are hot, the thermoplastic polymer is forced through the glass wick in order to produce a compound. This manufacturing process of the glass polymer composite is expensive and very slow, primarily due to the high viscosity of the thermoplastic polymer. Cut glass fibers are commonly used as reinforcement materials in thermoplastic articles. Typically, these fibers are formed by extracting molten glass in filaments through a hole plate or bushing, applying a sizing composition containing lubricants, coupling agents and film-forming binder resins to the filaments, collecting the filaments into strands, cut the strands of fibers into segments of the desired length and drying the sizing composition. These segments of subsequently cut strands are mixed with a polymerizable resin, and the mixture is supplied to an injection or compression molding machine to form plastic articles reinforced with glass fibers. Typically the chopped strands are mixed with nodules of a polymerizable thermoplastic resin, and the mixture is supplied to an extruder, where the resin is melted and mixed with the strands cut in this way, the integrity of the strands of glass fibers is destroyed and the fibers are dispersed through the molten resin, the length of the fibers is decreased and the fiber / resin dispersion is formed into nodules. These nodules are then fed into the molding machine and formed into molded articles having a substantially homogeneous complete dispersion of the glass fibers. Unfortunately, however, the chopped glass fibers made by these processes are typically bulky and do not circulate well. Consequently, these fibers are sometimes difficult to handle and have sometimes been problematic in automated processing equipment. Most attempts to improve the process have been aimed at compacting the chopped strands. The work was aimed at improving the flowability of strands crushed, that supposedly would allow the use of an automated equipment to weigh and transport the glass fibers for mixing with thermoplastic resins. This process is described in the patent of the U.S.A. No. 4,840,755, wherein the wet chopped strands are rolled or laminated, preferably on a vibrating carrier, to encircle the strands and compact them into more dense cylindrical shaped nodules. However, while the described methods tend to provide more dense nodules of more cylindrical shape exhibiting better flowability, the described methods and apparatuses are undesirably limited in certain aspects. For example, nodule size and fiber content are generally limited by the size and number of fibers in the. drawn thread. Although separate strands or loose filaments allegedly adhere to other strands during the rolling process, the process is designed to avoid multiple segments of strand strands that adhere together to form nodes containing more fibers than those present in a strand cut. simple. Consequently, to obtain nodes having a convenient bulk density and a sufficient diameter to length ratio to exhibit good flowability, the strand from which the segments are cut, usually must be formed from a large number of filaments. Nevertheless, increasing the number of filaments requires forming and combining in a single strand, undesirably complicates the training operation. Although the disclosed nodes can be made by these various mixing processes, it has been found that many of these processes are too inefficient for commercial use or can not be adequately controlled to produce a uniform nodule product that provides the resulting composite article with strength characteristics comparable with those made from fibers of strands not pelleted. For example, the use of a modified disc pelletizer as described in U.S. Pat. No. 4,840,755, often results in excessive residence time of the nodes formed within the mixer, resulting in nodule degradation due to the abrasive nature of the glass fiber nodes rubbing together. This nodule degradation finally reduces the strength characteristics of the molded articles made with them. Accordingly, there is a need for a totally new approach that eliminates the need to handle the chopped glass fibers before mixing with the resin. This need is met by the process and composition of the invention described below.

In addition, the previous methods of processing sizing fibers have required the use of ovens in the process in order to dry the drawn fibers. The aqueous sizing also contains a significant amount of volatile organic compounds (VOCs = Volatile Organic Components). "Industry, in an effort to avoid environmental problems, has tried to find ways of minimizing VOC levels while maintaining the physical properties of the fibers The present invention of a nonaqueous sizing composition used to produce continuous wick packages with square edges, surprisingly not only meets and exceeds the environmental concerns for VOCs, but also significantly reduces the amount of time required as well as the total cost of producing the treated fibers by eliminating the need for drying ovens and detachment of the package (usually due to In addition, the present invention provides a sizing composition which, once applied to glass fibers, allows the glass fiber to be directly coated with the reinforced polymer material, overcoming the previous disadvantages of fibers. long ones that have a cost glass impregnation process bear and slow- Specifically, the high sizing load allows that the glass strand is uniformly dispersed within the polymer during the molding process. SUMMARY OF THE INVENTION _ The present invention surprisingly provides a non-aqueous sizing composition having an ignition loss (LOI = Loss on Ignition) in the range of 2 to 10%. Prior to the discovery of the present invention, the application of a sizing level in this range was unattainable due to splattering of sizing, migration, hanging of the package and drying problems. However, this invention provides a sizing that is applied at high temperatures directly to the glass fibers in the fiber-forming environment resulting in a wick package that can be shipped in a stage without drying in the furnace without migration and without stripping. The composition of the sizing allows the production of a composite material of long fibers. Specifically, the sizing composition of the invention results in a glass wick with high sizing load which subsequently can be wire coated at high speeds, possibly as high as 304.8 meters / minute (1,000 feet / minute), with the thermoplastic polymer and cut into nodules. One embodiment of a non-aqueous sizing of the present invention contains one or more film that are miscible with the polymer to be reinforced and one or more coupling agents. The sizing does not contain water and is applied at high temperatures. Since the present invention is a non-aqueous sizing, the resins are not emulsified or mixed with solvents, therefore the VOCs are significantly reduced. Furthermore, in the present invention, the coupling agents or more particularly the silanes do not mix in water, this in some cases reduces the hydrolyzation and can decrease the release of VOCs in the production environment. Another embodiment of the present invention provides a method for the online manufacture of composite materials. The process involves application of the non-aqueous sizing with the wire coating by subsequent wire of the glass fibers in line and then cooled, cut and shipped. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 and 2 illustrate a cross-sectional comparison of the long-fiber composite wire-coated composite of the present invention (Fig. 1), against the glass fiber composite completely impregnated with the prior art, known as Celstran ™ N66G50 ( Fig. 2). Figure 1 shows a wick of the present invention with 4% by weight sizing, to glass, and 2% sizing with respect to the total long fiber composite coated with NYLOBT wire, a polyamide. Item IA represents a beam of 4,000 filaments that has a 4% sizing on the glass. Item 2A is shown on NYLON wire cladding which is 48% of total fibers by weight. Figure 2 shows a cross section of a CeIstran ™ N66, G50 nodule composed of homogeneous long fibers. Item IB is a beam of 4000 filaments that has a size of 0.6% in the glass and 0.25% in size in relation to the total fibers. DETAILED DESCRIPTION AND MODALITIES PREFERRED OF THE INVENTION The non-aqueous sizing composition in the present invention is constituted by one or more film formers and one or more coupling agents.

The preferred film former should be a solid at room temperature and melt in the range of 30 to 60 ° C and is a liquid at 100 ° C with a viscosity of 75 to 400 cPs. The preferred coupling agent should be a liquid at room temperature and have a boiling point greater than 100 ° C. Suitable coupling agents include organofunctional silanes, 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane. The preferred coupling agent for used in the invention is 3-aminopropyltriethoxysilane commercially available from ITC's OSI Specialties under the trade designation A-1100. Preferably, the organofunctional silanes are employed in an amount from about 0.1 to 5% of the sizing composition. Film formers useful in the invention include the film formers missable with the polymer to be reinforced. For example, with nylon, suitable film formers include polycaprolactones such as Tone 031O and 0260 which is obtained from Union Carbide. For reinforcing polypropylenes, suitable film formers include amorphous waxes such as Vybar 260 and 825 which is obtained from Petrolite. In addition to the required components necessary to prepare the invention, other components usually added to sizing compositions in glass carbon fibers may also be present. For example, the sizing composition in the invention may contain antistatic agents, entangling agents or hardeners, antioxidants, cationic lubricants to reduce lint or broken filaments, nonionic lubricants, nucleating agents or small amounts of pigment, etc. An example of an entanglement agent would be bis-silane.

In the process of the invention, a strand of substantially continuous glass fibers is formed by conventional techniques such as extracting molten glass through a heated bushing to form a multitude of substantially continuous glass fibers and collecting the fibers in a strand. Any apparatus known in the art for producing these fibers and collecting them in a strand can conveniently be used in the present invention. Convenient fibers are fibers having a diameter from about 10 to 30 microns, and convenient strands containing from about 50 to 4,500 fibers. Preferably, the strands formed in the process of the invention contain from about 4000 to 5000 fibers having a diameter from about 17 to 25 microns. The non-aqueous sizing composition can be applied to the glass or carbon fibers by any method known to those skilled in the art such as during the formation of glass fibers or after the glass fibers have been cooled to a temperature sufficient to allow the application of the non-aqueous sizing composition. The non-aqueous sizing application can be applied to glass fibers by applicators having hot melt strips, rolls, sprinklers and applicators.

Preferably, the sizing composition is dosed by a heated applicator that is capable of applying or dosing small amounts of sizing uniformly to a continuous glass strand. Stationary and dual roller applicators can be used, however, the preferred applicators are 1.9050 cm (3/4") roll-sizing applicators, 3/8" slot-roller sizing applicators, Dual roller applicators and split multi-slot applicators. Most preferred is a 1.9050 cm (3/4") slot-sizer applicator.The 3/4" (1.9050 cm) (3/4") slot-roller applicator typically has a diameter of 1.9050 cm (3/4"). With a graphite or steel roller, the bottom block is heated.This applicator provides a one-step sizing flow with reduced entrainment compared to a standard applicator such as those typically employed in the specialty.With this applicator, there is also the In addition, it is well suited for viscosities in the range of 50 to 400 cPs and handles addition rates in the range of 0.5 to 8% or more. A .9525 cm (3/8") slot-roller applicator differs in that the diameter of the roller is .9525 cm (3/8") and bottom block heats up This applicator also provides a one-step sizing flow with slightly lower drag compared to a 1.9050 cm (3/4") groove. Like the 1.9050 cm (3/4") applicator, the roller speed is adjusted by the inverter drive gear train, and this applicator has shown that it is useful for viscosities in the range of 50 to 400 cPs while driving speeds of addition from about .3 to 3% by weight or more An apparatus for producing sizing glass fibers is provided The apparatus comprises: a heated bushing for supplying streams of molten glass to be drawn into continuous fibers; to extract the streams into fibers, and a sizing applicator The sizing applicator includes a housing and a roller applicator that rotatably engages the housing The housing has a supply gate adapted to receive the sizing composition under pressure from a source of sizing supply, an outlet slot and a passageway extending from the supply gate to the exit slot. "sizing composition from the supply gate and provides the sizing composition to the outlet slot, such that the sizing composition leaves the housing and is received at an outer surface of the roller applicator. The roller applicator is separated from the housing such that the housing does not substantially contact and alter the thickness of the de-sizing composition of the sizing composition received in the roller applicator. The roller applicator preferably rotates about a central axis that is in a generally horizontal plane. The outlet groove can be placed on the horizontal plane such that the sizing composition leaves the housing and is received on the outer surface of the roller applicator on the horizontal plane. The roller applicator further includes first and second end portions. In one embodiment, the first end portion has first coils or threads and the second end portion has second coils or threads. The first and second spirals are of opposite directions, so as to deflect the weight composition contacting the first and second end portions inward as the rhodium tooth applicator rotates. Preferably, the passage has a cross-sectional area that is generally constant from the supply gate to the exit slot.

The apparatus further includes an impeller for rotating the roller applicator. The driving apparatus comprises a drive structure and a clutch structure. The drive structure includes a motor having an output shaft and a pulse pulley coupled to the output shaft to rotate with the output shaft. The clutch structure includes: a clutch housing; a first arrow mounted rotatably in the housing including an inner bore; a second arrow positioned in the bore and "including an annular shoulder and a distal end portion adapted to engage the roller applicator such that the rotation of the second arrow effects rotation of the roller applicator; a spring placed in the bore and engaging the annular shoulder of the second arrow, a spring retainer attached to the first arrow to rotate with the first arrow and engaging and retaining the spring in the bore, and a band positioned relative to the impulse pulley and portion of the first arrow in such a way that the rotation of the impulse pulley effects rotation of the first arrow The spring effects rotation of the second arrow before rotation of the first arrow The portion of the first arrow may comprise a mounted impulse pulley on the first arrow.

The distal end portion of the second arrow preferably includes a pin extending generally transverse to a central axis of the second arrow. The pin is adapted to engage a pin receiving groove that is provided in the roller applicator. According to a second aspect of the preferred apparatus, a sizing applicator for a coating of sizing composition is provided to the glass fibers. The applicator comprises a housing and a roller applicator that rotatably engages with the housing. The housing has a supply gate adapted to receive the sizing composition from a sizing supply source, an outlet slot and a passage extending from the supply gate to the exit slot. The passage receives the sizing composition from the supply gate and provides the sizing composition to the exit slot such that the sizing composition leaves the housing and is received on an exterior surface of the roller applicator. The roller applicator is separated from the housing such that the housing does not substantially alter the thickness of the sizing composition received in the roller applicator.

According to a third aspect of the preferred apparatus, a sizing applicator is provided for applying a coating of sizing composition to the glass fibers. The sizing applicator includes a housing and a roller applicator that rotatably engages with the housing. The housing has a supply gate adapted to receive the sizing composition from a sizing supply source, an outlet slot and a passage extending from the supply gate to the exit slot. The passage receives the sizing composition from the supply gate and provides the sizing composition to the exit slot, such that the sizing composition leaves the housing and is received on an exterior surface of the roller applicator. The roller applicator is separated from the housing such that the housing does not substantially contact the sizing composition once it is received in the roller applicator. A dual roller applicator is useful when handling sizes that have viscosities in the range of 1 to 200 cPs while requiring addition rates in the range of 1 to 15%. This type of applicator allows precise control of film thickness. The sizing is applied using a heated applicator capable of applying or dosing small quantities 3-225 gm / minute of sizing evenly distributed to a glass strand. Preferably, the applicator system has a diameter from .6350 cm (1/4") to 2.54 cm (1") and is fed by a Zenith Series H pump. The non-aqueous sizing of the present invention can be applied at temperatures in the range from 30 to 150 ° C. Preferably, the apparatus is applied in the range of 80 to 110 ° C. In a particularly preferred embodiment, the sizing is applied at 100 ° C. Sizing can be applied at viscosities in the range of 75 to 400 cPs. Preferably, the sizing in the range of 100 to 250. In a particularly preferred embodiment, the non-aqueous sizing is applied at a viscosity of about 200 cPs. Another important variable is the amount of sizing applied to glass. In traditional chopped strands, the weight percent of LOI sizing in the glass or carbon fibers is 1% or less, with short fiber composites that are normally approximately .5 to 1% sizing. In this way, the influence of sizing on the matrix is relatively small. In contrast, the size of the present invention has an amount of sizing that is in the range of 2 to 10%. As a result, the sizing function is expanded in a way that not only provides good adhesion while offering protection and good processing characteristics, but it also becomes a significant component of the matrix. In particular, for the present invention the large amount of sizing in the glass allows the wire-coated glass fibers to be uniformly dispersed throughout the thermoplastic polymer during the molding process. One method for determining the LOI to be used is to apply sizing in an amount sufficient to essentially fill the interstices of the glass strand. This requires a determination and measurement of the interstices. The calculation uses the density of the glass filament and the density of the sizing. The formula is as follows: Area of a hexagon circumscribing a circle of radius r = n * r * r * tan (p / 6). - - "Considering r = 1 cm Hexagon area (glass + sizing) = 3.4641 cm2 Circle area (glass) = p cm2) Sizing area = 3.4641 = p = .225 cm2 Volume of each one (considering height = 1 cm) Sizing = .3225 cm3 Glass = p cm3 Sizing weight = 1 gm / cm3 (.3225 cm3) = .3225 gm Glass weight = (2.53 gm / cm3) (p cm3) = 7.948 gm Total sizing weight and glass = 8.2707 gm% by weight of sizing = 33.9% Sizing can be applied in quantities_ in the range of 2 to 10%. Preferably, the sizing is applied in the range of 2 to 5%. In a particularly preferred embodiment, the sizing is applied to a glass fiber for nylon reinforcement at a LOI from 3.0 to 4.0 with more preferred LOI which is 3.5%. In a particularly preferred embodiment, the sizing is applied to a glass fiber for polypropylene reinforcement coupled to an LOI from two to 5% with the most preferred LOI of 3.5%. However, as can be recognized from the above discussion and formula, the preferred LOI will vary with the glass filament density and the sizing density. For example, a filament of 23 micras has a preferred LOI of about 3.5%; while a filament of 20 microns has a preferred LOI of approximately 4.1%; a filament of 16 micras has a preferred LOI of about 5.0; and a filament of 13 micras has a preferred LOI of approximately 6.2%. In this way, with more surface area per gram of glass, more sizing is required. Another aspect of sizing chemistry is the requirement that some materials be able to withstand the wire coating process without undergoing degradation. There is the potential for starting sizing by losing mass when exposed to temperatures used in injection molding and wire coating processes. This Thus, the sizing chemistry must be able to withstand the temperatures encountered in operations up to 120-315 ° C and 250 to 600 ° F, the process temperatures for injection molding and wire coating. Thus, in one embodiment, a sizing composition for treating glass fibers is provided comprising: one or more film formers miscible with the polymer to be reinforced or used for wire coating and one or more coupling agents. The film former can be any film former which is of sufficient molecular weight to be essentially non-volatile, has a viscosity range of 500 to 400 cPs at 100 ° C and is compatible with the thermoplastic matrix. For example, a film former such as polycaprolactone should be used to be miscible with a molding compound such as NYLON 66, a polyamide having a repeating unit comprising two carbon chains, each chain containing 6 carbon atoms. The coupling agents may be any that are compatible with the selected film formers. For example, coupling agents compatible with polycaprolactone film formers would be various amine functional silanes. Suitable coupling agents for the non-aqueous sizing composition will generally have Ethoxy or silicon hydrolyzable groups, since they have a methoxy group generally yield a more dangerous material when hydrolyzed. In addition, the coupling agents are chosen to avoid any significant chemical side reactions. After application of the sizing, the glass fiber is then constituted in the composite by continuous wiring of the wick in line or out of line with the polymer. The resulting glass fiber composite is then cut into nodules and shipped to the moulder. The wire coating is carried out by passing continuous wick through a wire coating matrix. The die is connected to an extruder that supplies molten thermoplastic polymer through an opening perpendicular to the direction of the wick through the die. The action of the thermoplastic is basically to encapsulate the wick which is the "wire" to be coated. The speed at which the wick is pulled and the feed cost of the extruder determines the amount of thermoplastic that surrounds the wick. The size of the die exit hole also determines the amount of thermoplastic that surrounds the wick. Another important variable is the viscosity of the thermoplastic that is controlled by the temperature.

Prior to the actual fiberglass cladding, in a system where the glass is coated with polypropylene, the polypropylene nodules are mixed by hand with a polypropylene additive having suitable maleate reactive groups to aid in polypropylene bonding to the glass. A preferred additive is Polybond (PB-3001) obtained from UniRoyal Chemical. The additive is mixed with the polypropylene, by hand in the amount of about 2 to 15% and preferably 10%. Once formed, the strand is cut into sections of approximately .03175 cm (1/8") to 3.1750 cm (1 1/4"). Any convenient means known in the art of shredding polymer strands of glass fibers in those sections can be employed in the process. Suitable fiber cutting devices include the apparatus of Conair-Jethro Model # 204T 90O60, Bay City, Michigan. EXAMPLE 1 Nonaqueous sizing agent for nylon glass fiber composites. The sizing formula is as shown below (designated NI): Actual amount used R-5662 (alkyd polyester) 49.5% TONE 0260 (polycaprolactone) 49.5% A-1100 (amine-based silane) 1.0 100% Alkyd polyester R-5762, is prepared as follows: Table 1 R-5662 - Alkyd polyester characterization Starting materials 1.- Propoxylated bisphenol A 2. - Maleic anhydride polyester R-5762 Monomers in polystyrene, _ _ 1.- Maleic acid .04% by weight 2.- Fumaric acid .04% by weight 3.- Propoxylated bisphenol A 34.3% by weight Detector Rl UV detector Numerical average molecular weight, Mn 550 510 Weight average molecular weight, Mw 620 600 Average molecular weight Z, Mz, 750 710 Polydispersity, d 1. 13 1. 17 VOC,% .74 Acid number 60.3 Vise- ICI, cp 140 The water content, weight percent is: .01 to .06%. The point of instantaneous evaporation is: greater than 204.44 ° C (400 ° F). The viscosity at 25 ° C is 3,200,000. The Sizing formulation is a solid at 25 ° C and has the following viscosity to temperature ratio. Temperature in ° C Viscosity, cPs 75 620 100 260 125 120 150 60 TONE 0260 (polycaprolactone) is obtained from Union Carbide and has the following formula: H { 0 (CH2) 5C (= 0)} m-0-R_0_ { C (= 0) (CH2) 5 ?} mH TONE 0260, chemical formula Table 2 gives its characteristics. - Table 2 TONE 0260 Molecular weight 3,000 Acid number mg KOH / g 0.09 Melting point C 50-60 Viscosity, 55C, cPs 1500 Hydroxyl number VOC% 0.29 mg KOH / g 37 Silane A-1100 is obtained from Osi Specialties and has the following formula and characteristics:? -aminopropyltriethoxysilane Molecular weight - _ 22-1.4 Specific gravity .946 Clear liquid The sizing is heated in a bucket and pumped to a convenient, double-roller type applicator. The glass fibers are attenuated and allowed to contact the applicator; the sizing, at approximately 115 ° C, then transferred to the glass. The fibers were collected in the primary shoe and wound in a sleeve making a packet of square edges. The package was then left to cool. Then it was coated with wire and cut into nodules for eventual use in injection molding applications. Table 3 APPLY OF NYLON LONG FIBER NI SECTION 1 - PURCHASE SPECIFICATION AND SECURITY VALUES NFPA.

MATERIAL HEALTH NFPA FLAMAB1LITY REACTIVITY NFPA NFPA- - R-5762 2 1 0 TONE 0260 1 1 0 - A-1100 3 1 2 SECTION 2 - FORMULATION MATERIAL% SOLIDS% IN WEIGHT KG X 100 KG ASSETS LIKE (LBS / 100 LB ) IS RECEIVED AS RECEIVED R-5762 100 49.5 49.5 TONE 0260 100 49.5 49-5 A-1100 61 1 1 Tolerances The weights listed above are target weights. +/- 2% variation in a target weight is acceptable for this formulation. Sizing should be maintained at room temperature during storage. When the sizing is used, the equipment to handle it should be constituted from FRP (plastic reinforced with glass fibers) PVC, stainless steel or glass. Black or galvanized iron and most non-ferrous metals are prohibited when the sizing is mixed, the preparation should be carried out as follows. In a main mixing tank, the drum or tank of R-5762 should be heated to 100 ° C. Then it should be weighed and added directly into the main mix tank; then the agitation should begin. Subsequently, TONE 0260 should be added directly to the main mixing tank as a solid with a temperature of 70 ° C maintained. An alternate method is that the TONE 0260 is heated to 80 ° C and emptied directly into the main mix. At a temperature of 70 ° C +/- 5 ° C, the A1100 silane should be added slowly with constant stirring. Agitation should be maintained until the dispersion is complete. Once "this is finished, the mixing is complete." For final mixing, stirring should be for 5 to 10 minutes to achieve dispersion and then the viscosity should be measured by a Brookfield or cone and plate measurement at 100 ° C. Table 4 Sizing for nylon Condition: Designation: NI NI NORMA LOI 5.0 5.0% Packing density, g / cm3 (lb / in3) 1.80 1.85 (.065X (.067) Strand tension, ksi 327 (25) 341 (19) Fluff, mg 10-15 < 15 Excellent good packaging stability Good good packing density Table 5 Type Impact Modulus Fiber content the glass notched tensile traction kg * 106 (ksi) (psi * 106) (ft-lb / in) (%) Short fiber 198 492A * 26.9 (2.82] 2.8 29.3 10 microns CelstrnMR .195 16 microns 23.6 (2.78) 4.2 27.7 Table 5 (Cont.) Type Resistance to Impact Module fiber content the traction traction notched glass kg * 106 kg-m / cm2 (ksi) (psi * 106) (ft-lb / in) (%) NI 19 micras 23.7 (2.78: 4. 1 2: 9.5 NI 23 micras 22.6 (2.78) 4 .2 3 0 .5 * obtained from Owens Corning Resist.Resistance Impact Impact Impact on the at notched notched tensile Wet flexion kg-m / cm2 m / kg (ksi) (ksi) (ksi) (ft-lb / in) (ft / lb) CelstranM 34.2 20.4 55.6.111 4.45 (16 micras) (5.2: (24.9) NI 29.4 16.1 47.9 .062 2.63 (19 micras) (4.3) (14.7) Example II _ Another sizing was prepared for aluminum nylon defibers compounds having the formula shown below (designated N2): Current quantity used TONE 0310 (polycaprolactone) 99% by weight AllOuO (amine silane) 1% TONE 0130 was obtained from Union Carbide and had the following formula: TONE 0130 (polycaprolactone) HO ((CH2) 5C = 0)) 3- GOLD- (C = 0 (CH2) 5) 3OH 0 (C = 0 (CH2) 5) 30H PM = 900 P.F. = 27-32 ° C Hydroxyl number = 187 The size is prepared as in Example I and samples were prepared. A 23-micron fiber was made and tested against Celstran N66 G 50 (16-micron fiber used as control). The mechanical properties were as follows below. Mechanical Properties _ Celstran N66G50 (control) N2 fiber M (16 microns) Fiber T (23 microns) Traction ksi 35.3 30.4 Traction 24H boiling, ksi 22.5 18.4 Flexural, ksi 55.6 49.6 Izod notched, m-kg / cm .13 .137 (ft-lbs / in) (6.04) (6.41) Mechanical Properties Celstran N66G50 (control) __ JKT2 fiber M (16 micras) Fiber T (23 micras) Without notching m-kg / cm .521 .467 (FT / LBS / IN) (24.3) (21.8)% glass 49.6 51.5 Example III Another sizing is prepared for nylon glass fiber composites. The formula was designated N3 and is illustrated below as: N3_ Current Quantity-employed TONE 0367 38.5% TONE 0260 60.0% A1100 1.5% The sizing is prepared as in Example 1 and a sample is prepared. Micro fibers A-23 are prepared and tested against Celtran N66 G50 (15 microns). The mechanical properties were as illustrated in Table 6 below.

Table 6 Mechanical properties data FD Microns FD Microns 16 23 _ Description Celstran N3 T225 N66G50 - Dry traction (ksi) 36.7 32.3 Modular drive kg / cm •, 22 .184 .177 (psi x 106) (2.62) (2.52) Traction 24 hr boiling (ksi.)) 2211..55 - 18.7% Ret 59 58 Flexural resistance (KSI) 57.0 51.2 Flexural module (PSI x 106) 2.24 2.17 Izod notched kg-m / cm .31 28 (ft-lb / in) (5.7) (5.2) Izod not notched kg-m 4.02 4.36 (ft-lb) (29.1) (31.5) Glass content (%) 49.4 49.1 DTIL ° C 260"260" (° F) (500) (500) Example IV Non-aqueous primer for coupled polypropylene The formulation for this example is (designated "Pl"): VYBAR 260 - 80% ~ VYBAR 825 - 18% Silane A-1100 - 2% _ The sizing formulation is prepared by heating VYBAR waxes to approximately 71.1111 ° C (160 ° F) while mixing together. The silane is then added slowly and mixed thoroughly through the wax. The sizing is hot applied at 180 ° F (82.2222 ° C) to the glass fibers to form a strip of 453.17 m / kg (225 yd / lb) of 23 microns (The strand is pulled from a bushing that has 2,000 strands ) using a pump and a roller application system of 1.9050 cm (3/4"). The sizing is applied in order to achieve a sizing load of approximately 3.5%. _ Table 7 TYPICAL PROPERTIES Poly-Density- Visco-Point Penetra- Penetra- mole ispity to the ation of the body 25 ° C 99 ° C soft- 25 ° C 44 ° C (77 ° F) ( 210 ° F) damiento (77 ° F) (110 ° F) Methods ASTM ASTM ASTM ASTM ASTM ASTM test pressure test -? Rj- D792 D3236 D36 D1321 D1321 Mw / Mn steam Units Mw grams / cc cP ° C ' F 0.1 mm 0.1 mm Polymer VYBARc2ec 2600 11.5 0.90 358 54 130 12 110 Polymer VYBARc825 1500 3 0_se 795"* -30 -34 <; * Point of runoff **, Gel Permeation Chromatography *** @ 32 ° C (90 ° F) Table 8 * Note Celstran is a commercial product used as a control.

** The non-aqueous sizing formulation Pl is a filament with a diameter of 23 microns and Celstran * is 16 micras. Example V Another size is prepared for polypropylene glass fiber composites. The formula is designated P2 and is illustrated below as: P2 Actual amount employed VYBAR 260 80% VYBAR 825 19% A-1100 1% The sizing is prepared as in Example IV and a sample is prepared. Figures have been prepared at 16j 20 and 23 micras and tested against Celtran (16 micras). The mechanical properties were as illustrated in table 9 below. - Table 9 Data of Mechanical Properties FD Microns FD Microns FD Misrons FD Microns 16 23 20 16 Description Celstran, P2, mold P2, mold P2, mold Mold aa 237.78 ° C at 237.78 ° C at 237.78ßC 215.56 ° C (420 ° F) ) (460 ° F) (460 ° F) (460 ° F) Dry traction (ksi) 16.4 14.5 14.9 14.9 Table 9 Mechanical Properties Data (Cont.) FD Microns FD Microns FD Microns FD Microns 16 23 20 16 Modular drive kg / cm2 xlO6 .08 .072 .074 .071 (psi x 10s) (1.14) (1.03) (1.05) (1.01) Traction 24 hr boiling (ksi) 13.8 10.6 10.3 10.2 % Ret 84 73 69 68 Flexural resistance (KSI) 23.4 20.5 21.8 22.5 Flexural module .057 .055 .055 .054 (PSI x 10s) (.81) (.78) (.78) (, 77) Izod notched kg-m / cm .23 .28 .27 .267 (ft-lb / in) (4.2) (5.2) (5.0) (4.9) Izod not notched kg-m 2 2..1122 1.94 2.09 2.02 (ft-lb) (15.3) (14.0) (15.1) (14.6) Glass content (%) 3 300..55 29.4 28.7 29.9

Claims (18)

1. CLAIMS 1.- A nonaqueous sizing for application of glass reinforcement, characterized in that it comprises: a) one or more film formers that are miscible with the polymer to be reinforced, the film former has a melting point in the range from 30 at 60 ° C and a viscosity of 75 to 400 cPs; and b) from about 0.1 to 5% by weight of one or more coupling agents, selected from the group consisting of silanes; wherein the sizing has a loss in ignition speed from 2 to 10%, when applied to glass reinforcing fibers.
2. 2. - The nonaqueous sizing composition of claim 1, characterized in that the coupling agent is selected from the group consisting of 3-g1-i1-ox-ipr-op1-tri-toxy-silane and 3-methacryloxypropyltrimethoxy-silane and 3-aminopropyltriethoxy ? silane.
3. 3. The non-aqueous sizing composition of claim 1, characterized in that the film formers are selected from the group consisting of polyamide, polypropylene, polybutylterephthalate, polyamide having a carbon chain containing 6 carbon atoms, polyamide having a repeating unit comprising two carbon chains, each chain contains 6 carbon atoms, chemically coupled polypropylene, polycarbonate, polyphenylene sulfide, thermoplastic polyurethane, acetal and HDPE.
4. 4. - The nonaqueous sizing composition of claim 1, characterized in that the film formers are selected from the group consisting of high molecular weight waxes, low molecular weight waxes, lower molecular weight alkyd polyester, polycaprolactones, male polypropylenes of low molecular weight.
5. 5. A nonaqueous sizing for application of glass fibers to reinforce polyamide, characterized in that it comprises: a) one or more film formers that are miscible with the polymer to be reinforced, the film former has a melting point in the range from 30 to 60 ° C and a viscosity of 75 to 400 cPs; and b) one or more coupling agents, selected from the group consisting of silanes; where the sizing has a loss in ignition speed from 2 to 10% when applied to glass fibers to reinforce polyamide.
6. 6. The non-aqueous sizing according to claim 5, characterized in that the film former is selected from the group consisting of low molecular weight polyurethanes, polycaprolactones, polyesters, unsaturated polyesters.
7. 7. The non-aqueous sizing according to claim 5, characterized in that the formers of The films are polycaprolactones, and the coupling agent is amino silane.
8. 8. - A nonaqueous sizing composition for application to glass fibers to reinforce polypropylene, characterized in that it comprises: a) one or more film formers that are miscible with the polymer to be reinforced, the film former has a melting point in the range from 30 to 60 ° C and a viscosity of 75 to 400 cPs; and b) one or more coupling agents, selected from the group consisting of silanes; where the sizing has a loss in ignition speed from 2 to 10%, when applied to glass fibers to reinforce polypropylene.
9. 9. The non-aqueous sizing according to claim 8, characterized in that the film former is selected from the group consisting of amorphous waxes, microcrystalline waxes, mallowed low molecular weight polypropylenes, hydrocarbon resins.
10. 10. The non-aqueous sizing according to claim 8, characterized in that the film foxers are amorphous waxes, and the coupling agent is an amine silane.
11. 11. Fibers of glass having at least a portion of its surface covered with the dry residue of a non-aqueous sizing composition according to claim 1.
12. 12. - Glass fibers according to claim 11, characterized in that the sizing composition is the composition according to claim 7.
13. 13. - Glass fibers according to claim 11, characterized in that the sizing composition is the composition according to claim 10.
14. 14. - Glass fibers according to claim 11, coated with polymer selected from the group consisting of polyamide, polypropylene, polycarbonate, polybutylterephthalate.
15. 15. Process for producing glass fibers containing a molding compound, comprising the steps of: a) forming a strand of glass fibers; b) coating the strand of glass fibers with the non-aqueous sizing composition of claim 1; and e) applying a wire coating of polymer resins to the glass fiber, which has at least a portion of its surface covered with the dry residue of the non-aqueous sizing composition of claim 1.
16. 16. - The compliance procedure with claim 15, characterized by the step of coating the strand of glass fibers with the aqueous sizing composition, it is carried out at high temperatures.
17. 17. - A non-aqueous sizing composition for application to glass reinforcing fibers comprising: one or more polycaprolactone as film formers; and b) an amine silane coupling agent.
18. 18.- Glass fibers having at least a portion of their surfaces covered with the dry residue of a non-aqueous sizing composition, characterized in that they comprise: a) one or more polycaprolactones as film formers; and b) an amine silane coupling agent.