BRPI0620728A2 - two-part ironing composition for reinforcing fibers - Google Patents

Abstract

TWO-PART IRONING COMPOSITION FOR REINFORCEMENT FIBERS A two-part ironing formulation that provides improved strength for reinforced compounds including an ironing composition and a binder composition is provided. The ironing composition can include one or more coupling agents and one or more film forming agents. The binder composition includes a high acid number copolymer formed from the polymerization of maleic anhydride or maleic acid and at least one other desired monomer and / or a high acid number polycarboxylic acid. In a preferred embodiment, the binder composition includes an ethylene-maleic acid polymer formed by the hydrolysis of a maleic anhydride and ethylene copolymer. The ironing composition can be applied to a reinforcing fiber material before the ironing binder material is applied. Two-part ironing arrangement can be applied to a reinforcement fiber material to form a reinforcement fiber product which can then be densified or compacted to form a densified reinforcement fiber product, such as a pellet.

Description

"TWO-PART IRONING COMPOSITION FOR STRENGTH FIBERS"

TECHNICAL AREA AND INDUSTRIAL APPLICABILITY OF THE INVENTION

The present invention generally relates to a sizing composition for a fiber reinforcing material and more particularly to a two-part sizing formulation which provides improved resistance to reinforced compounds including a gum composition and a composition. ligand. A composite article formed from a starch reinforcing fiber material with a two-part ironing formulation is also provided.

BACKGROUND OF THE INVENTION

Glass fibers are useful in a variety of technologies. For example, glass fibers are commonly used as reinforcements in polymeric matrices to form glass fiber reinforced composites or plastics. Glass fibers were used in the form of filaments, continuous or cut yarns, preliminary spinning, fabrics, nonwoven fabrics, weft and strong fabrics to reinforce polymers. It is known in the art that glass fiber reinforced polymeric compounds have higher mechanical properties compared to unreinforced polymeric compounds as long as the surface of the reinforcing fiber is suitably modified by a sizing composition. Thus, dimensional stability, modulus and tensile strength, modulus and flexural strength, impact strength and drag resistance can be obtained with fiberglass reinforced compounds.

Cut glass fibers are commonly used as materials in reinforced composites. Conventionally, glass fibers are formed by attenuating jets of a molten glass material from a bushing or hole. Glass fibers can be attenuated by a winder that collects filaments joined by a package or by rollers that pull the fibers before they are collected and cut. An aqueous sizing composition or chemical treatment is typically applied to the fibers after they are removed from the plug. After the fibers are treated with the aqueous ironing composition, they can be dried into a bundled or cut yarn form.

Cut wire segments may be mixed with a polymeric resin and supplied to a compression or injection molding machine to be formed into fiberglass reinforced composites. Typically, the cut wire segments are mixed with pellets of a thermoplastic polymer resin in an expeller. In a conventional method, polymeric pellets are fed into a first aperture of a twin screw expeller and the cut glass fibers are fed into a second expeller port with the melt polymer to form a fiber / fiber mixture. resin. Otherwise, the polymerized pellets and cut yarn segments are dry blended and fed together into a single screw expeller where the resin is fused, the integrity of the fiberglass yarns is destroyed and the fiber yarns are dispersed throughout. the resin is fused to form a fiber / resin mixture. Then the fiber / resin mixture is

degassed and formed in sedimented. These dry fiber resin / yarn dispersion pellets are then fed into a modeling machine and made up of molded composite articles that have a homogeneous dispersion of fiberglass yarns throughout the composite article.

Unfortunately, broken glass fibers are often bulky and do not flow well on automated equipment. As a result, chopped fiber yarns can be compacted into sediment or rod-shaped bundles to improve their flowability and to allow the use of automated equipment, such as for transporting the sedimented and mixing the sedimented with the fibers. polymeric resins. US Patent No. 5,578,535 to Hill et al. It discloses fiberglass pellets that are about 20% to 30% denser than individual glass threads from which they are made and about 5 to 15 times larger in diameter. These pellets are prepared by hydrating the fiber yarn segments to a level of hydration sufficient to prevent the separation of the fiber yarn segments into individual filaments, but insufficient to cause the fiber yarn segments to agglomerate into one. lump.

The hydrated yarn segments are then mixed for a sufficient period of time for the yarn segments to settle. Suitable mixing methods include processes that keep the fibers moving over and around each other, such as rolling, shaking, mixing, blending, shaking and / or intermingling the fibers.

Sizing compositions as used in reinforced compounds are well known in the art and conventionally include a polyacid polymeric component, a film-forming polymeric component, a coupling agent and a lubricant. A polyacid sizing composition is typically added to glass fibers to reduce interfiling abrasion and to make the glass fibers compatible with the polymeric matrices they are intended to reinforce. The sizing composition also ensures the integrity of the glass fiber strands, for example, the interconnection of the glass strands forming the strand.

A fundamental problem associated with conventional polyacid ironing compositions used in reinforced compounds is the presence of a dicathonic species, such as a metal salt of a long chain carboxylic acid, in the polymer used to form a reinforced composite article. The interaction of dicathonic lubricant with conventional polyacid sizing compositions causes a decrease in mechanical strength. For example, polyamide compounds reinforced with conventional sizing compositions often demonstrate a reduction in impact forces (eg, Charpy or Izod, fixed or not fixed) as well as a reduction in tensile strength and elongation at pauses when such tests are performed. made of hydro-aged composite pieces. Thus, there is a need in the art for a sizing composition that provides improved mechanical strength for reinforced compounds containing a dicathonic lubricant.

Summary of the Invention

It is an object of the present invention to provide a two-part sizing formulation that provides hydrolysis resistance and improved dry-patterned mechanical properties (DaM) to reinforced polymeric compounds (e.g. reinforced polyamide compounds), even when such compounds contain higher valence dicathionic additives or cation such as a calcium stearate lubricant. The two-part ironing formulation includes a gum composition and a binder composition. The gum composition may be applied to a reinforced fiber material before the binder composition is applied. The reinforcing fiber material may be one or more strands of glass (e.g. Advantex® glass), natural fibers, carbon fibers, or one or more synthetic polymers. According to at least one exemplary embodiment of the present invention, the gum composition includes one or more coupling agents and one or more resinous film forming agents. Preferably, the coupling agent is an aminosilane or a diaminosilane. In addition, the gum composition may optionally include conventional additives such as lubricants, wetting agents, pH adjusters, antioxidants, antifoam agents, processing aids, antistatic agents and / or nonionic surfactants.

The gum composition includes a high acid number copolymer formed from the polymerization of maleic anhydride or maleic acid and at least one other desired monomer and / or a high acid number polycarboxylic acid. The maleic anhydride or acid copolymer may be a pure copolymer or a derivative in the form of anhydride, acid, salt or imide, amide or partial ester. Suitable copolymers include C 2 -C 5 α-olefins, such as butadiene-, ethylene-, propylene- or (iso) butylene- and copolymers of methyl vinyl ether-maleic acid. In a preferred embodiment, the binder composition includes an ethylene-maleic acid copolymer formed by hydrolysis of an ethylene-maleic anhydride copolymer. The binder composition may also include a film-forming agent which may be the same as or different from the film-forming agent in the gum composition. Conventional additives such as lubricants, surfactants and antistatic agents may also be included in the binder composition.

It is yet another object of the present invention to provide a process for making a densified reinforcing fiber product. The process for making a densified reinforcement fiber product may be an in-line process that includes applying a two-part sizing formulation as described above to a yarn of a stiffening fiber material, cutting the yarn of stiffened stiffening fiber into segments, apply a binder composition as described above to the segments and sediment and / or densify the segments to form the densified reinforcing fiber product. Sediment formation and densification may occur in separate rolling apparatus such as a rotating drum (eg sedimenter) and zigzag rotary tube (eg densifier). Otherwise, sediment formation and densification may occur in separate regions in a single apparatus, such as in a zigzag blender commercially available from Patterson Kelly. The gum composition may be applied to the fibers as they are being formed and the binder composition may be applied to the starched fibers in a settler. By applying the binder composition to the sedimenter, an application efficiency of approximately 95% to 100% for the binder composition can be obtained. In addition, applying the binder composition separately allows for the inclusion of materials that are not desirably applied during the fiber forming process due to safety, flammability, irritation, stability, low aminosilane compatibility, viscosity, toxicity, cleanliness, odor. , cost and / or sensitivity to shearing.

It is an advantage of the present invention that a high ignition weight loss (LOI) of the high acidic maleic anhydride copolymer, ethylene maleic acid copolymer, or polycarboxylic acid in the sizing composition provides dry mechanical properties as improved molding and improved hydrolysis resistance.

It is another advantage of the present invention that polyurethane film formers present in the ironing composition demonstrate good compatibility with polyamide matrices which help to improve the dispersion of reinforcing fiber bundles in the melt (e.g. extrusion process or injection molding process) when a composite article is formed. This increased fiber dispersion may cause a reduction in defects such as visual defects in the finished product, a reduction in processing interruptions and / or low mechanical properties in the final article.

It is an additional advantage of the present invention that the polyurethane dispersion present in the ironing composition improves the compatibility of the ironing composition with the dicathonic species containing polymer to improve fiber dispersion during further processing to form a composite article. .

It is yet another advantage of the present invention to provide improved physical properties such as improved dry molding (DaM) mechanical properties of the composite part or after aging of the composite part under severe hydrolysis conditions for compounds formed from industrially processable sediments and easily expendable.

It is also an advantage of the present invention that the two-part sizing formulation has improved stability over conventional sizing formulations containing an aminosilane and a polyacid in the same mixture.

The foregoing and other objects, features and advantages of the invention will appear more fully hereinafter from a consideration of the following detailed description.

BRIEF DESCRIPTION OF ILLUSTRATIONS

The advantages of this invention will be apparent from consideration of the following detailed disclosure of the invention, especially when taken in conjunction with the accompanying illustrations where:

FIG. 1 is a graphical illustration of Izod's unfixed dry molding impact (DaM) testing

FIG. 2 is a graphical illustration of Charpy's non-fixed molded dry impact (DaM) testing on pieces composed of calcium stearate / polyamide 6 and polyamide 6;

FIG. 3 is a graphical illustration of Charpy's non-fixed Impact tests after hydro aging of pieces composed of calcium stearate / polyamide 6 and polyamide 6;

FIG. 4 is a graphical illustration of Charpy's non-fixed molded dry impact (DaM) tests on pieces composed of calcium stearate / polyamide 6 and polyamide 6; and

FIG. 5 is a graphical illustration of Charpy's non-fixed molded dry impact (DaM) tests on pieces composed of calcium stearate / polyamide 6 and polyamide 6;

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. While any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, preferred methods and materials are described herein. All references cited herein, including foreign or corresponding US or published patent applications, US filed or foreign patents and any other references, are each incorporated by reference in their entirety, including all data, tables, figures and text presented in the mentioned references. The terms "film forming agent" and "film forming agent" may be used interchangeably here. Further, the terms "reinforcing fiber material" and "reinforcing fiber" may be used interchangeably herein.

The present invention relates to a two-part sizing formulation that improves the mechanical performance of reinforced compounds. In particular, the two-part sizing formulation of the invention confers hydrolysis resistance and improved molding dry mechanical properties for polymer reinforcing compounds, such as a polyamide reinforcing compound, even when compounds contain dicathonic or higher valence additives such as as a calcium stearate lubricant. It is to be appreciated that while any higher valence dication or cation may be applicable to the present invention, dications are discussed in detail herein for ease of discussion. The two-part ironing formulation includes a gum composition and a binder composition. The two-part sizing formulation may be applied to a stiffening fiber material to form a stiffening fiber product, which may then be densified or compacted to form a densified stiffening fiber product, as sedimented. Densified pellets provide a convenient way to store and handle cut fibers used as reinforcement materials in composite structures.

The gum composition may be applied to a reinforcing fiber material before the binder composition is applied. The reinforcing fiber material may be one or more glass strands formed by conventional techniques such as by extracting molten glass through a heated bushing to form considerably continuous glass fibers. These fibers can subsequently be collected on a glass wire. Any type of glass, such as type A glass, type C glass, type E glass, type S glass, or type ECR glass such as Owen Corning Advantex® glass fibers. Preferably, the reinforcing fiber material is E-glass or Advantex® glass.

Otherwise, the reinforcing fiber material may be made of one or more synthetic polymers such as polyester, polyamide, aramid and mixtures thereof. Polymer yarns may be used alone as the reinforcing fiber material, or they may be used in combination with glass yarns such as those described above. As an additional alternative, natural fibers may be used as the reinforcing fiber material. The term "natural fiber" as used in conjunction with the present invention refers to plant fibers extracted from any part of a plant, including but not limited to stem, seeds, leaves, roots or phloem. Examples of natural fibers suitable for use as reinforcing fiber material include cotton, jute, bamboo, ramie, sugarcane bagasse, hemp, coconut fiber, flax, hibiscus, sisal, flax fiber, henna - who and combinations of these. Carbon or polyamide fibers may also be used as the reinforcing fiber material.

The reinforcing fiber material may include fibers having a diameter of about 6 microns to about 24 microns and may be cut into segments of approximately 1 mm to about 50 mm in length. Preferably, the fibers have a diameter of about 7 microns to about 14 microns and a length of about 3 mm to about 6 mm. Most preferably, the fibers have a diameter of approximately 10 microns. Prior to the densification of the reinforcing fiber material as described below, each yarn may contain from approximately 500 fibers to approximately 8,000 fibers.

After the reinforcement fibers are formed and before they are collected on a wire, they may be coated with a gum composition. A suitable gum composition according to at least one exemplary embodiment of the present invention includes one or more coupling agents and one or more film forming agents. Optionally, conventional additives such as, but not limited to, lubricants, wetting agents, pH adjusters, antioxidants, defoaming agents, processing aids, antistatic agents and nonionic surfactants may be present in the gum composition. The gum composition may be applied to the reinforcing fibers in an amount sufficient to achieve an ignition weight loss (LOI) of from about 0.05% to about 1.0% on the dry fiber and preferably on a dry fiber. from about 0.15% to about 0.40%. LOI can be defined as the percentage of organic solid matter deposited on fiberglass surfaces as measured by the weight reduction experienced by the fibers after heating them to a temperature sufficient to burn or pyrolyze the organic gum of the fibers.

The gum composition includes one or more coupling agents. Preferably, the coupling agent is a silane coupling agent. In addition to their function of copying the surface of the reinforcement fibers and the plastic matrix, silanes also function to increase the adhesion of the carboxylic acid component to the reinforcement fibers and to reduce the flake level, or broken fiber filaments during subsequent processing. Examples of silane coupling agents that may be used in the present gum composition may be χ by the amino, epoxy, vinyl, methacryloxy, ureido, isocyanate and azamido functional groups. In preferred embodiments, silane coupling agents include silanes containing one or more nitrogen atoms that have one or more functional groups such as amino (primary, secondary, tertiary and quaternary), amino, imino, ureido, isocyanate or azamido.

Suitable silane coupling agents include, but are not limited to, aminosilanes, silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, and ureido silanes and isocyanate silanes. Specific non-limiting examples of silane coupling agents for use in the present invention include γ-aminopropylthiethoxysilane (A-1100), n-phenyl-γ-aminopropyltrimethoxysilane (Y-9669), n-trimeoxy-silyl-propyl-ethylene- diamino (A-1120), methyltrichlorosilane (A-154), γ-chloropropyl trimethoxy silane (A-143), vinyl triacethoxy silane (A-188), methyltrimethoxysilane (A-1630), γ-ureidopropyltrimethoxysilane ( A-1524). Other examples of suitable silane coupling agents are set forth in Table 1. All silane coupling agents identified above and Table 1 are commercially available from GE Silicones.

TABLE 1

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Additional examples of suitable silane coupling agents include Chisso products having the trade names set forth in Table 1A.

<table> table see original document page 18 </column> </row> <table>

The silane coupling agents used in the present invention may be substituted by alternative coupling agents or mixtures. For example, A-1387 may be replaced by a version wherein the methanol solvent is replaced by ethanol. A-1126, an aminosilane coupling agent including a mixture of approximately 24% by weight of a surfactant-modified diaminosilane in a methanol solution (GE Silicones), may be substituted by trimethoxy-silyl-propyl-ethylene-diamino (Z-6020 by Dow Corning). A-1120 or Z-6020 may be replaced by a prehydrolyzed version Z-6020 may be replaced by Z-6137, a prehydrolyzed version which lacks an alcohol solvent and including 33% diaminosilane in water in a 24% solids concentration (commercially available from Dow Corning). In addition, A-1100 may be substituted for its hydrolyzed form Y-9244, which will reduce or eliminate ethanol emission.

Preferably the silane coupling agent is an aminosilane or a diaminosilane. The gum composition may include one or more of the above coupled agents. The coupling agent may be applied to the fibers in an amount sufficient to obtain an ignition weight loss (LOI) of from about 0.02% to about 0.30% in the dry fiber and preferably in an amount of about 0.04% to about 0.08%.

In addition, the gum composition may include at least one resinous film forming agent. Any conventional film-forming agent known to those skilled in the art may be used in the gum composition. Further, the film former may be the same as or different from the film former present in the binder composition described in detail below. In the gum composition, the film former acts as a polymeric binder to provide additional protection to the reinforcing fibers and improve processability, such as a flake reduction generated by high speed cutting. The film-forming agent may be present in the reinforcing fibers in an amount sufficient to provide an LOI of from about 0% to about 1.0%. Preferably, the film-forming agent is present in the fibers in an amount sufficient to provide an LOI of from about 0.15% to about 0.60%.

In an alternative embodiment of the present invention, the gum composition contains a lubricant to facilitate manufacture instead of or in addition to a film-forming agent. Examples of suitable lubricants include, but are not limited to, lubricants such as water soluble ethylene glycol stearates (e.g., polyethylene glycol monostearate, butoxyethyl stearate, polyethylene glycol and butoxyethyl stearate monooleate), ethylene glycol fatty acid amines ethoxylates, glycerin, emulsified mineral oils and organopolysiloxane emulsions. Other examples of lubricants include alkyl imidazoline derivatives (e.g., a cationic attenuator that has a solid content of approximately 90% and is commercially available from Th. Goldschmidt AG), stearic ethanolamide (e.g. Lubesize K12 (AOC )) and a commercially available 50% polyethyleneimine polyamide salt of Cognis active solid under the tradename Emery 67 60. The lubricant may be present in the fibers in an amount sufficient to provide an LOI of up to about 0.10%.

Although the gum composition is effective at any pH level, the pH preferably falls in the range of about 7 to 11. The pH may be adjusted depending on the desired application, or to facilitate compatibility of the composition ingredients. Gum Any suitable pH adjuster (for example, a weak organic acid such as acetic acid or a base such as ammonia) may be added to the gum composition in an amount sufficient to adjust the pH to a desired level.

The gum composition can be made by dissolving each ingredient in a premix with stirring. Separate premixes may then be combined with deionized water to form a master mixture and to achieve the appropriate concentration and control of the solids mixture. Premixes can be added in any order. If necessary, the pH of the main mixture may be adjusted to a desired level. The premixes may be added separately, or they may be added at the same time to form the master mix.

As described above, the two-part ironing formulation also includes a binder composition. The binder composition includes a high acid number copolymer formed from the polymerization of maleic anhydride or maleic acid and at least one other desired monomer and / or a high acid number polyacid. As used herein, the term "high acid number" is intended to mean a polyacid having an acid number or acid value greater than about 300. In addition, the binder composition may include any suitable additive identified by one of ordinary skill in the art. such as, for example, adhesive film forming polymers, lubricants, a surfactant or a mixture of surfactants, antistatic agents and cross-linking agents. The binder composition may be applied to the fiber with an LOI of from about 0.20% to about 2.0%, depending on the desired application.

The maleic acid or maleic anhydride copolymer may be a pure copolymer or a derivative in an acid anhydride, partial salt, partial ester, partial amide or partial imide form. Suitable copolymers include C2 -C5 α-olefins, such as ethylene-, propylene-, (ies) butylene-, or butadiene-maleic acid copolymers and methyl vinyl-maleic acid ether copolymers. The copolymer is poorly soluble when dispersed in water at room temperature, but when it is heated to temperatures above about 90 ° C, it dissolves due to hydrolysis of the polymer anhydride groups to form the corresponding polyacids. In such a reaction, one mole of anhydride is hydrolyzed to two moles of diacid in an exothermic reaction. The aqueous solution formed by hydrolysis can then be used to formulate the binder composition. Similar reactions may be employed using ammonia or an amine in water, or an alcohol or amine in a nonreactive solvent, to form solutions of the partial imide, partial amide, partial ester, or salt of derivatives respectively. partial ammonium.

In a preferred embodiment, the binder composition includes an ethylene-maleic acid (EMA) copolymer formed by hydrolysis of an ethylene-maleic anhydride copolymer.

The ethylene maleic anhydride copolymer may be formed by radical copolymerization between ethylene and maleic anhydride in the presence of a peroxide catalyst. This copolymerization leads to an alternating copolymer that includes a high level of maleic fractions that give the ethylene maleic acid copolymer a high polyacid functionality.

In at least one exemplary embodiment, the copolymer is an aqueous solution of the partial imide derivative, partial amide, partial ester, ammonium salt (partial), or polyacid of an alternate blocking blocker of sodium anhydride, or mixtures of these. Mixtures of different ethylene and maleic acid copolymers or maleic anhydride copolymers with other high acid number polycarboxylic acids such as maleic or acrylic acid homo- or copolymers or derivatives thereof as described above may be used in the composition binder to obtain desired properties, such as improved strength in the fiber reinforcement product or improved fiber processability and also to reduce the total binder cost.

As discussed above, the binder composition may include a high acid number polyacid (e.g., high acid value) if not, or in addition to the maleic acid or maleic anhydride copolymer. Desirably, the polyacid is a carboxylic acid. A suitable polycarboxylic acid polymer for use in the binder composition is an organic polymer that contains numerous pendant carboxylic acid groups and is characterized by a high acid number. The acid number or acid value of a substance may be described as a measure of the free acid content and may be expressed as the number of milligrams of potassium hydroxide neutralized by the free acid present in one gram of the substance. In the binder composition, the high acid number polyacid may have an acid number of at least about 300. In at least one exemplary embodiment, the binder composition has an acid number of about 300 to about 950 carboxylic acid polymer may be a homopolymer or copolymer prepared from unsaturated carboxylic acids including, but not limited to, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2-methylmalic acid, itaconic acid, 2-methylitaconic acid and α, β-methylenoglutaric acid. Otherwise, the carboxylic acid polymer may be prepared from unsaturated anhydrides such as maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride and mixtures thereof. Methods for polymerizing these acids and anhydrides are known to those of ordinary skill in the art and will not be discussed in detail here. In addition, the carboxylic acid polymer may include a copolymer of one or more of the unsaturated carboxylic acid anhydrides described above and one or more vinyl compounds including, but not limited to, styrene, α-ethylstyrene, acrylonitrile, methacrylonitrile, acrylate. methyl, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, methyl vinyl ether, vinyl acetate, 1-oleyl ethers (eg ethylene, isobutene) vinyl and allyl alkyl ethers (eg methyl vinyl ether, ethyl vinyl ether), substituted acrylamides and sulfonic and sulphonate monomers (eg allylsulfonic acid, vinyl sulfonic acid). Such polyacids are described in detail in US Patent No. 5,236,982 to Cossement et al., Which is hereby incorporated by reference in its entirety.

The high acid maleic anhydride copolymer, high acid maleic ethylene copolymer, or high acid polycarboxylic acid in the binder composition may be present in the fibers in an amount sufficient to provide an LOI of up to about 2 0.0%, preferably from about 0.10% to about 2.0% and most preferably from about 0.40% to about 1.0%. It is to be appreciated that when the high acidic mamalic anhydride copolymer, high acidic ethylene and maleic acid copolymer, or high acidic polycarboxylic acid contacts a polymer containing a dication, there is a interaction between the carboxylic acid fractions and the dications in which the carboxylic acid fractions are consumed or otherwise unskillful to interact favorably with the polymer matrix. While not wishing to be bound by theory, it is believed that a ratio greater than 2: 1 (polyacid equivalent carboxylic acid: equivalent dication, respectively) retains the presence of carboxylic acid fractions after the polyacid fractions interact. with dication. Therefore, it is desirable that an excess of carboxylic acid moieties be present in the gum / binder composition to compensate for the polyacid that is consumed by dications such that improved mechanical properties as improved molding and resistance to improved hydrolysis. can be obtained. However, the specific amount of carboxylic acid fractions present in the binder composition required to achieve an excess (and improved physical properties) is dependent on the amount of dications present in the polymer. It is believed that it is the difference between the number of equivalents of carboxylic acid fractions present in the reinforcing fiber and the number of equivalents of dicathonic additives present in the polymer that directs the% LOI of the maleic anhydride copolymer, ethylene copolymer. and maleic acid, or high acid polycarboxylic acid. It is to be noted that the use of a high LOI polyacid does not alter the efficiency of calcium stearate in its primary function as a lubricant / demodelant. In addition to a maleic anhydride copolymer, an ethylene maleic acid copolymer, or a high acid polycarboxylic acid, the binder composition may also include one or more film-forming agents. Film builders are agents that create improved adhesion between reinforcing fibers, which results in improved yarn integrity. Suitable film formers include thermocured and thermoplastic polymers that promote adhesion of sizing compositions. Polyurethane film formers are a preferred class of film formers for use in the binder composition because they demonstrate good compatibility with polyamide arrays and help to improve the dispersion of fiberglass beams in the melt (e.g. extrusion process or injection molding process) in the formation of the composite article which causes the reduction or elimination of defects in the final article caused by poor dispersion of the reinforcing fibers (eg visual defects, process breaks and / or low mechanical properties). The polyurethane dispersions used in the two-part sizing formulation of the present invention may be part of a dispersion that is based or not on a blocked isocyanate. Furthermore, as discussed above, the film former present in the binder composition may or may not be the same film former present in the gum composition.

Examples of polyurethane film formers that are not based on blocked isocyanates that may be used in the binder composition include, but are not limited to, Baybond®XP-2602 (a nonionic polyurethane dispersion (Bayer Corp.)); Baybond®PU-401 and Baybond®PU-402 (anionic urethane polymer dispersions (Bayer Corp.)); Baybond® VP-LS-2277 (an anionic / nonionic urethane polymer dispersion (Bayer Corp.)); Aquathane 518 (a nonionic polyurethane dispersion (Dainippon, Inc)); and Witcobond 290H (polyurethane dispersion (Witco Chemical Corp.)). Other examples of suitable film-forming agents for use in the binder composition include, but are not limited to, polyvinylpyrrolidone homo- and copolymers and other polymers having amide-like functionality such as polyamide, polyvinylformamide or polyacrylamide. In at least one exemplary embodiment, the film-forming agent is an aqueous polyurethane dispersion that is not part of a dispersion that includes a blocked polyurethane and isocyanate.

Examples of suitable blocked isocyanate-based urethane film formers that may be used in the binder composition include, but are not limited to, BaybondOXW-Il6; Baybond®XP-055; Baybond® PU-330; Baybond® PU-400-S; Baybond® PU-401 (blocked isocyanate-based polyurethane dispersions (available from Bayer Corp.)); Bay Bond® VP-LS-2277 and Baybond® VP-LS-2297 (anionic / nonionic urethane polymer dispersions (Bayer Corp.)); Baybond® PU-130 (an anionic / nonionic urethane polymer dispersion (Bayer Corp.)); Baybond® PU-403 (a polyurethane dispersion (Bayer Corp.)); Baybond® PU-239 (a cross-linkable anionic / nonionic urethane polymer dispersion (Bayer Corp.)); Baybond® PU-2435 (an anionic / nonionic urethane polymer dispersion (Bayer Corp.)) and Witcobnd 296B (a blocked aqueous polyurethane dispersion available from Bayenden Chemicals).

The film former (s) may be present in the binder composition in an amount sufficient to provide an LOI of up to about 1.0% and preferably about 0%. , 10% to about 0.40%. It is desirable that the amount of film former present in the two-part sizing formulation is such that the two-part sizing formulation provides the desired level of compatibility for the reinforcing fibers and the polymer matrix to assist fiber dispersion. during processing to form a composite part without affecting the positive effect of polyacid fractions to improve dry molding and hydro-aged mechanical properties and without developing static and / or undesirable color in the fiber reinforcement product.

The binder composition may be formed by mixing a solution of the desired high acid number polyacid (s) (e.g. a carboxylic acid obtained by hydrolysis of the parent polyanhydride in hot water) with a solution of the forming agent Movie Optionally, the solution may be diluted with water. It may be necessary to adjust the pH of the polyacid solution with a base before mixing it with the film-forming solution to reduce or eliminate the occurrence of destabilization phenomena. Any suitable pH adjuster may be added to the binding composition to adjust the pH to a desired level; however it is preferred that ammonium (NH4) be added to adjust the pH. The pH of the binder composition may fall in the range of 2.5-10. The total LOI for the two-part ironing formulation in the reinforcing fiber material may be from about 0.25% to about 2.05%, preferably from about 0.60% to about 1.10%. .

An advantage of the two-part sizing formulation of the present invention is that the product resulting from the application of the two-part sizing formulation, which may contain LOI of up to about 2.0% of the high acidic maleic anhydride copolymer. , high acid number ethylene and maleic acid copolymer, or high acid number polycarboxylic acid, provides improved mechanical properties even when the polyamide matrix contains a dication additive such as calcium stearate.

In addition, the two-part sizing formulation of the present invention confers improved physical properties, such as improved dry molding mechanical properties (DaM) of the composite part after aging of the composite part under severe hydrolysis conditions, to compounds formed from industrially processable and easily dispersible sediments.

The present invention is also advantageous in that the polyurethane film formers present in the two-part sizing formulation demonstrate good compatibility with polymeric matrices (such as polyamide matrices) containing dicathonic lubricants, which help to improve the dispersion of the bundles. reinforcement fiber in the melt (eg in extrusion or injection molding) in the formation of a composite article. This increased dispersion of the reinforcing fibers causes a reduction in defects such as visual defects, processing breaks and / or low mechanical properties in the final product.

Additionally, the two-part ironing formulation of the present invention has improved stability over traditional ironing formulations containing an aminosilane and a polyacid in the same mixture. Mixtures containing both aminosilanes and polyacids may not be stable due to chemical interactions between the two compounds. By placing substantially all (if not all) aminosilane in the gum composition and polyacid in the binder composition, both the gum composition and the binder composition have increased shelf lives.

The process for making a densified reinforcement fiber product may be an in-line process that allows the application of the gum composition, the cutting of the glass fibers, the application of the binder composition and the settling of the fiber material. reinforcement. Such an inline process forms a sedimented product that exhibits superior physical properties, such as improved strength, when integrated into a compound (e.g., as compared to sedimented products produced by the process previously known in the art). While not wishing to compromise the theory, it is believed that such superior properties are due to the improved compatibility of the gum composition and binder composition, which allows for a better coating of the reinforcing fiber material.

The process for making a densified reinforcing fiber product according to the invention may employ an apparatus comprising: (a) an apparatus for applying a gum composition to a continuous fiber material; (b) an apparatus for cutting fiberglass yarns to form cut yarn segments; (c) an apparatus for transporting the cut wire segments to a first rolling apparatus; (d) an apparatus for applying a binder composition to the cut yarn segments; (e) a first rolling apparatus for imparting a rolling action to the cut wire segments to disperse the binder composition and cause the cut wire segments to align and coalesce in pellets; (f) optionally an apparatus for transporting the sediment to a second rolling apparatus; (g) optionally, a second rolling apparatus for rolling the sediment to compact them and increase their density; (h) a apparatus for transporting the densified pellets to a drying apparatus and (i) a drying apparatus adapted to receive and dry the pellets.

Initially, the gum composition may be applied to the reinforcing fiber material by any conventional means, including spray or slide applicators, kiss roll and dip-draw. Preferably, the precursor gum is applied by passing the reinforcing fiber material, e.g. glass or polymer strands, over a klss roll applicator. The gum composition is preferably applied to the yarns in an amount sufficient to provide the yarns with a moisture content of about 8% by weight to about 13% by weight, more preferably about 10% to about 11%. by weight. The starched yarns can then be cut into yarn segments. The wire segments may have a length of approximately 2 mm to approximately 50 mm. Preferably, the wires have a length of about 3 to about 4 mm. Any suitable method or apparatus known to those of ordinary skill in the art for cutting fiberglass yarns into segments may be used.

Next, the binder composition can be applied to the cut yarn segments. The coated cut wire segments are then sedimented by any suitable method known to those of ordinary skill in the art, such as, for example, rolling or otherwise shaking the cut wire segments in a settler. Suitable processes for cut yarn segments are disclosed in US Pat. No. 5,868,982, 5,945,134, 6,365,090 and 6,659,756 to Strait et al., And US Patent No. 5,868,378 to Hill et al., All of which are incorporated by reference in their entirety. The amount of moisture in the binder composition serves to adjust the moisture content of the wire segments to a level suitable for sediment formation when the wire segments are rolled into the sedimenter. Although the moisture content of the wire segments can be adjusted prior to introducing them into the sedimenter, it is preferred that the segments be hydrated to a moisture content suitable for sedimentation formation in the sedimenter itself.

Preferably, the moisture content of the cut yarn segments in the settler is from about 12% by weight to about 16% and more preferably from about 13% by weight to about 14% by weight. based on the total weight of the binder yarn cut segments. If the moisture content is too low, the wire segments tend not to combine in sediment and will remain in a wire formation. On the other hand, if the moisture content is too high, the strands tend to agglomerate or accumulate or form pellets that have a large diameter and an irregular, non-cylindrical shape.

The binder composition may be applied to the cut wire segments as they enter the settler, or after the cut segments are placed in the settler but prior to rolling. In an alternative embodiment, the binder composition may be sprayed on the fibers before they are cut. In this alternative embodiment, it is preferable to use a settler that is specially equipped with rolling medium as baffle plates to ensure proper rolling and settling.

To ensure good recovery of the cut segments, the binder composition is preferably applied to the cut wire segments as they enter the settler, but before they begin to coalesce into settlers. If the binder composition is applied at other locations in the seeder, pellets may form before the yarn segments are completely coated with the binder composition, which results in pellets containing fibers that are not coated with the binder composition. When such sediments are used in the manufacture of fiber-reinforced composite articles, the uncoated fibers lack the interfacial coating required to provide good reinforcing characteristics and the resulting composite article will have less than optimal properties. Preferably, the settler is equipped with a spray nozzle, located adjacent to the wire segment opening, to spray the binder gum on the wire segments as they enter the settler.

The settler may be any apparatus capable of rolling the yarn segments such that: (1) they become considerably uniformly coated with the binder composition and (2) multiple yarn segments align and coalesce on pellets having a desired dimension. Such a rolling apparatus should have a sufficient sufficient average residence time to ensure that the yarn segments become considerably coated with gum binder and form pellet but not sufficient for pellet to be damaged or degraded by abrasion (eg , by rubbing against each other). Preferably, the residence time in the rolling apparatus is from about 1 minute to about 10 minutes. Most preferably, the residence time in the rolling apparatus is from about 1 minute to about 3 minutes.

A preferred settler is a rotary drum, such as that disclosed in US Patent No. 5,868,982, as referenced hereinabove. US Patent No. 5,868,982 discloses an apparatus for making fiber reinforced pellets, which are preferably provided with a system for monitoring and / or adjusting various process parameters. Moisture content of the spent yarn segment can be monitored and controlled using appropriate method. In one embodiment wherein the binder composition is applied to the yarn segments before being placed in the settler, the rotary drum is adapted to accommodate a spray head for applying the binder composition to the yarn segments as they enter. on the drum The binder composition and a solvent, such as water, may be combined into a fluid stream and dispersed through a nozzle orifice. This current can be combined with two air jets positioned approximately 180 degrees apart and at a 60 degree angle of current flow direction. Mixing the binder composition with the forced air currents effectively creates a mist that is propelled on the surface of the rolling wire segments in the drum.

Rotation of the drum causes damp yarn segments to roll around each other while surface tension created by wet sizing or coating causes yarn segments to contact each other in a considerable portion of them. lengths to align with each other and coalesce into a cylindrical pellet. By such action, any single or thin fibers created during the shearing operation are recombined and incorporated into the pellets formed to essentially eliminate individual fine fibers from the resulting pellets. Preferably, the drum is angled slightly so that the end of the drum from which the sediment exits is lower than the end at which it enters to ensure that the sediment formed in the drum does not remain in the drum for a period of time. excessive time.

The size of the sediment formed in the drum is controlled primarily by the moisture content of the wire segments. If the moisture content is kept at a high level, a large number of wire segments will coalesce into a sediment and the sediment will have a larger diameter. On the other hand, if moisture is kept at a lower level, few strands of wire will coalesce in a sediment and the sediment will have a smaller diameter. The amount of binder composition that is discharged into the wires can be controlled by a computer that monitors the weight of wet glass entering the sedimenter and adjusts the amount of the binder composition to obtain a final cut wire having a content of yarn solids from about 0.25% to about 2.05% by weight.

Preferably the sedimented ones have a diameter of from about 20% to about 65% of their lengths. Such seeds are typically formed by combining from about 70 yarn segments to about 175 yarn segments, each containing from about 500 individual filaments per yarn to about 8000 individual filaments per yarn.

Sediment size may also be affected by drum yield. For example, the higher the drum yield, the shorter the residence time of the wire segments in the drum. As a result, smaller pellets may be formed because the binder composition is not adequately dispersed in the yarns which may cause the yarns not to coalesce into a pellet. In addition, pellets formed on the drum for a shorter period of time are less compacted than pellets formed on the drum for a longer period of time.

Although some compaction of the sediment formed formed invariably occurs in the sedimenter, it is typically insufficient to increase the density of the sediment to a level that provides optimal flowability. For this reason, after their formation in the sedimenter, the sedimented ones can optionally be fed into a second rolling apparatus or densifier, in which the sedimented ones are further compacted and densified. Any low impact bearing apparatus that compresses the sediment without degrading them by abrasion or otherwise damaging the sediment can be used. Preferably, the densifier is a zigzag tube adapted to be rotated about its longitudinal axes as described in US Patent No. 5,868,982, 5,945,134, 6,365,090 and 6,659,756 to Strait et al.

Preferably, the densifier has a less vigorous rolling action, softer than that of the sedimenter to minimize sedimentation degradation. As the zigzag tube is rotated, the pellets placed there are gently rolled by rotating the tube as they are pulled through the gravity of the tube. As with the rotating drum described above, the zigzag tube densifier is preferably angled at a slight angle to ensure that the pellets flow through the apparatus without excessive residence times. In addition, the densifier preferably has an average residence time of less than approximately 5 minutes to reduce any embrace that may occur. Preferably the average residence time in the densifier is from about 1 minute to about 2 minutes.

Although sedimentation and densification may occur in separate apparatus, such as a separate rotary drum and a rotary zigzag tube connected by a conveyor, the sedimentation process may be performed using any suitable apparatus. For example, sedimentation and densification may occur in separate rolling regions or zones in a single apparatus. A preferred example of such an apparatus is a zigzag blender commercially available from Patterson Kelly. In a preferred embodiment of this device, a drum is equipped as an inner baffle plate to reduce the free fall distance of the sedimented glass and wire segments during rotation of the drum. By reducing this distance, less deterioration of glass and sedimented fibers occurs through impact and abrasion, resulting in improved physical properties in fiberglass-reinforced molded articles manufactured in this way.

After densification, the sediment can be distributed on a drive belt and dried, for example, using a sealed furnace supplied with hot and chilled air or any other suitable drying apparatus easily identified by one of ordinary skill in the art. To reduce the drying time to an acceptable level for commercial mass production, it is preferred that the fibers be dried at elevated temperatures to approximately 260 ° C in a fluid bed oven. After drying, the densified sediment can be sorted by size using a screen or other suitable device.

By varying the yield and moisture content of fiberglass sedimented yarn segments can be made 13% to 60% denser than the corresponding unsettled yarn segments and about 10 times to about 65 times larger in diameter. For example, 4 mm (length) segments cut from a 2000 micron 14-filament (diameter) fiber yarn typically have a bulk density of about 33 lb / ft3 (528, 66 kg / m3) to 36 lb / ft3 (576.72 kg / m3). After being hydrated to a moisture content of from about 13% to about 14% and formed into densified sediment as described above according to the process of the invention, the resulting dry sediment typically has a density of volume from about 40 lb / ft3 (640.8 kg / m3) to about 55 lb / ft3 (881.1 kg / m3). As a result of their increased diameter-to-length ratio and increased density, the resultant pellets exhibit significantly improved flowability compared to the non-pelleted cut yarn product.

The gum composition and binder composition make it easy to treat reinforcing fiber materials, for example glass, during a continuous process which includes forming the fibers as well as subsequent processing and handling. By applying the binder composition to the settler, an application efficiency of from about 95% to about 100% for the binder composition can be obtained. This high application efficiency reduces wastewater contamination at the factory. Additionally, because the binder composition can be applied efficiently, the binder composition can be applied with a cost reduction.

In addition, applying the binder composition separately from the fiber-forming off-environment sizing composition allows materials which are not desirably applied during the fiber forming process due to toxicity, safety, flammability, irritation, stability. , low aminosilane compatibility, viscosity, toxicity, cleanliness, odor, cost and / or shearing sensitivity can be applied to glass fibers. In addition, because the polyacid in the binder composition can be applied to glass fibers in a more concentrated form in the settler than if it were applied directly to the glass strands as they are being formed, there is reduced fiber residue and logging when compared. to conventional inline processes.

Although the invention is highly suitable for inline manufacturing processes as described above, it can also be used in an offline process where the gum composition and binder composition are applied to previously reinforced fiber materials. formed and packaged, or wherein the gum composition and the binding composition are applied to the reinforcing fiber material at different times. For example, the gum composition may be applied to a formed fiber yarn, after which the yarn may be vented and stored prior to subsequent unwinding, segment cutting and application of the binder composition.

Having described this invention generally, an additional understanding may be obtained by reference to certain specific examples illustrated below which are provided for illustration purposes only and are not intended to be all inclusive or limiting unless otherwise specified.

EXAMPLES

Two-part ironing formulations

TABLE 2

<table> table see original document page 41 </column> </row> <table> <table> table see original document page 42 </column> </row> <table> <table> table see original document page 43 < / column> </row> <table>

<a> AX-1100 silane γ-aminopropyltrieoxysilane (GE Silicones)

(b) K12 Lubricate stearic acid-reacted tetraethylenepentamine (AOC) (c) Zonyl FS-300 fluoralkyl alcohol substituted polyethylene glycol (DuPont)

(d) Baybond PU-403 blocked isocyanate polyurethane dispersion (Bayer Corp.)

(e) Witcobond 296B blocked polyurethane dispersion (Baxenden Chemicals)

(f) Baybnd XP-2602 Nonionic Polyurethane Dispersion (Bayer Corp.)

(g) Glascol E5 low PM acrylic acid homopolymer solution (Ciba)

(h) Glascol C95 Low PM partially ammonia-neutralized acrylic acid homopolymer solution (Ciba)

(i) ZeMac E400 alternating copolymer of ethylene and maleic anhydride with a PM of approx. 400,000 (Zeeland Chemicals)

(j) ZeMac E60 alternating copolymer of ethylene and maleic anhydride with a MW of approximately 60,000 '(Zeeland Chemicals)

(k) Aquathane 518 polyurethane dispersion (D.I.C.)

(l) Jeffamine ED2003 Water-soluble aliphatic diamine derived from a propylene oxide capped poly (ethylenoxide) (Hunstsman Corp.)

(m) Pluronic F-yl oxirane (EO-PO copolymer) (BASF)

(n) Pluronic PE-103 oxirane (EO-PO copolymer) (BASF)

(o) Pluronic L-101 oxirane (EO-PO copolymer) (BASF)

(p) Triton X-100 octylphenoxy polyethoxyethanol (Union Carbide Corp.)

The two-part ironing compositions shown in Table 2 were prepared as described below.

Preparation of Examples 1 - 3 from Table 2

In Examples 1-3, the components of Table 3 were mixed to prepare the gum composition. Gum composition was applied to 1Ομm Advantex® glass fibers to obtain a 0.60% Yarn Ignition Loss (LOI) on the glass fibers. A conventional ignition loss (LOI) method, ASTM 2854, was used to determine how much of the gum composition applied was to the glass fibers. The glass fibers were then collected on a string and cut damp in line by a cutter in segments of approximately 4 mm in length.

TABLE 3

<table> table see original document page 45 </column> </row> <table>

(a) blocked polyurethane dispersion (Baxenden Chemicals)

(b) γ-aminopropyltrieoxysilane (GE Silicones)

The cut segments were then collected and approximately 1-2 days after rotation treated in a laboratory settler where the corresponding binder exposed in Table 2 was sprayed on the cut segments. In Example 1, no binder was applied during sedimentation. In Example 2, Glascol E5, a 25% solids solution of a low molecular weight acrylic acid homopolymer available from Ciba, was diluted to 15% solids with deionized water and used as the binder. In Example 3, the binder composition was prepared by dispersing 132 g of ZeMac 400, an alternating ethylene-maleic anhydride copolymer available from Zeeland Chemicals, in 870 g of deionized water and dissolved by heating to approximately 95 ° C under stirring. . The various binder compositions were applied to obtain the corresponding% LOI exposed in Table 2. The densified glass pellets were collected and dried in a moving belt laboratory oven for approximately 16 minutes at a mean temperature. - max. 220 ° C.

Preparation of Examples 4 - 7 of Table 2

In Examples 4-7, the components of Table 4 were mixed to prepare the gum composition. Gum composition was applied to 10μm Advantex® glass fibers to obtain a 0.35% Yarn Ignition Loss (LOI) on the glass fibers. A conventional ignition loss (LOI) method, ASTM 2854, was used to determine how much of the gum composition applied was to the glass fibers. The glass fibers were then collected on a string and cut damp in line by a cutter in segments about 4 mm long.

TABLE 4

<table> table see original document page 46 </column> </row> <table>

<a> blocked isocyanate polyurethane dispersion (Bayer Corp.)

(b) γ-aminopropyltrieoxysilane (GE Silicones) The cut segments were then collected and approximately 1-2 days after rotation treatment in a laboratory settler where the corresponding binder exposed in Table 2 was sprayed on the cut segments. In Example 4, Baybond PU-403, a 39% solids blocked isocyanate polyurethane dispersion available from Bayer Corp., was diluted to 15% solids with deionized water and used as the binder. In Examples 5-7, the binder was prepared by diluting Glascol E5, a solids solution in 25% of an available low molecular weight acrylic acid homopolymer, to 15% solids with deionized water. The various binder compositions were applied to obtain the corresponding% LOI exposed in Table 2. The densified glass pellets were collected and dried in a moving belt laboratory oven for approximately 16 minutes at a maximum temperature of 220 ° C. ° C.

Preparation of Examples 8 of Table 2 The gum composition of Example 8 was prepared according to the description of Table 7 set forth in US Patent Publication No. 2004/0209991 A1 to Piret et al., Which is hereby incorporated by reference in its entirety. In particular, the gum composition as set forth in Table 5 was prepared and applied to 10μm Advantex® glass fibers as they were produced in a continuous line process. The glass fibers were then formed into wires and cut into wire segments that were approximately 4.0 mm long. The molten glass was fed through the bushing at approximately 2.71 χ 10-2 kg / s. The gum composition was applied with a kiss roll applicator turning in the direction of the wire and 0.25 meters per second. The gum composition was applied at a concentration of 0.69% to obtain a LOI of 0.06% solid yarn in the glass.

TABLE 5

<table> table see original document page 48 </column> </row> <table>

(a) γ-aminopropyltrieoxysilane (GE Silicones)

(b) stearic acid (AOC) reacted tetraethylenepentamine

(c) fluoralkyl alcohol substituted polyethylene glycol (DuPont)

The cut segments were then transported to a settler where the binder composition according to Table 6 was sprayed onto the cut segments. The binder composition was applied to obtain a LOI of 0.59% solid yarn in the glass fibers. The total ignition loss (LOI) of the glass was 0.65%. The densified glass pellets were transported to a fluid bed or conveyor type kiln for drying.

TABLE 6

<table> table see original document page 48 </column> </row> <table> <table> table see original document page 49 </column> </row> <table>

(a) alternating copolymer of ethylene and malic acid with a PM of approx. 400,000 (Zeeland Chemicals)

(b) water soluble aliphatic diamine derived from a propylene oxide capped poly (ethylene oxide) (Hunstsman Corp.)

(c) partially ammonia-neutralized low PM acrylic acid homopolymer solution

(d) γ-aminopropyltrieoxysilane (GE Silicones)

(e) polyurethane dispersion (D.I.C.)

(f) oxirane (EO-PO copolymer) (BASF)

(g) oxirane (EO-PO copolymer) (BASF)

(h) oxirane (EO-PO copolymer) (BASF)

(i) octylphenoxy polyethoxyethanol (Union Carbide Corp.) Preparation of Example 9 of Table 2

In Example 9, the components of Table 7 were mixed to prepare the gum composition. The gum composition was applied to IOpm Advantex® glass fibers to obtain a 0.25% Yarn Ignition Loss (LOI) on the glass fibers. A conventional ignition loss (LOI) method, ASTM 2854, was used to determine how much of the gum composition applied was to the glass fibers. The glass fibers were then collected on a wire and cut damp in line by a cutter in segments of approximately 4 mm in length.

TABLE 7

<table> table see original document page 50 </column> </row> <table>

(a) blocked isocyanate polyurethane dispersion (Bayer Corp.)

(b) γ-aminopropyltrieoxysilane (GE Silicones)

The cut segments were then collected and approximately 1-2 days after rotation treated in a laboratory settler where the binder was sprayed on the cut segments. The binder composition was prepared by dispersing 13.43 kg of ZeMac 400 EMA powder in 47.85 kg of deionized water and dissolving the powder by heating the water to approximately 95 ° C while stirring. After the ZeMac 400 EMA powder was dissolved, the solution was further diluted by the addition of 19 kg of deionized water. Eighteen sixty-one-tenths kg of Glascol E5, a solution of a partially ammonia-neutralized low molecular weight acrylic acid homopolymer which is available in Ciiba, was then added with stirring at a lower temperature than 60 ° C. The binder composition was applied to obtain a 0.61% solid yarn LOI on the glass fibers. The total ignition loss (LOI) of the glass was 0.86%. The densified glass sediments were collected and dried in a moving belt conveyor laboratory oven for approximately 16 minutes at a maximum temperature of 220 ° C.

Preparation of Example 10 from Table 2

In Example 10, the components of Table 8 were mixed to prepare the gum composition. The gum composition was applied to IOpm Advantex® glass fibers to obtain a 0.22% Yarn Ignition Loss (LOI) on the glass fibers. A conventional ignition loss (LOI) method, ASTM 2854, was used to determine how much of the gum composition applied was to the glass fibers. The glass fibers were then collected on a wire and cut damp in line by a cutter in segments of approximately 4 mm in length.

TABLE 8 <table> table see original document page 52 </column> </row> <table>

(a) nonionic polyurethane dispersion (Bayer Corp.)

(b) γ-aminopropyltrieoxysilane (GE Silicones)

The cut segments were then transported to a settler where the binder was sprayed on the cut segments as they passed through the settler inlet chamber. The binder composition was prepared by dispersing 32.00 kg of ZeMac 60 EMA powder in 80.80 kg of deionized water and dissolving the powder by heating the water to approximately 95 ° C while stirring. After the ZeMac 60 EMA powder was dissolved, the solution was cooled to 25 ° C and the pH adjusted to about 3.5 by the addition of approximately 9.10 kg of a 25% ammonia solution. Fifty-two and thirty-one-tenths of a kilogram of Baybond XP-2602, a nonionic polyurethane dispersion available from Bayer Corp., was then added slowly with stirring. The densified glass pellets were transported to a fluidized bed or conveyor type conveyor or oven for drying. The binder composition was applied to obtain a 0.61% solid yarn LOI on the glass fibers. The total ignition loss (LOI) of the glass fibers was 0.83%.

Preparation of Example 11 from Table 2 In Example 11, the components of Table 9 were mixed to prepare the gum composition. The gum composition was applied to IOym Advantex® glass fibers to obtain a 0.22% Yarn Ignition Loss (LOI) on the glass fibers. A conventional ignition loss (LOI) method, ASTM 2854, was used to determine how much of the gum composition applied was to the glass fibers. The glass fibers were then collected on a wire and cut damp in line by a cutter in segments of approximately 4 mm in length. TABLE 9

<table> table see original document page 53 </column> </row> <table>

(a) nonionic polyurethane dispersion (Bayer Corp.)

(b) γ-aminopropyltrieoxysilane (GE Silicones) The cut segments were then transported to a settler where the binder was sprayed on the cut segments as they passed through the settler inlet chamber. The binder composition was prepared by dispersing 13.43 kg of ZeMac 400 EMA powder in 47.85 kg of deionized water and dissolving the powder by heating the water to approximately 95 ° C while stirring. After the Ze- Mac 400 EMA powder was dissolved, the solution was further diluted by the addition of 19 kg of deionized water. Eighteen sixty-one tenths of a kg of Glascol C95, a solution of a partially ammonium-neutralized low molecular weight acrylic acid homopolymer which is available in Ciba, was then added with stirring at a lower temperature than 60 ° C. The densified glass pellets were then transported to a fluidized bed or conveyor type conveyor or drying oven. The binder composition was applied to obtain a 0.50% solid yarn LOI in the glass fibers. The total ignition loss (LOI) of the glass fibers was 0.72%.

Comparative test

Fiberglass pellets were composed of polyamide 6 modeling pellets (BASF Ultramid B3 with or without added calcium stearate) using a co-rotating twin-screw interreticulating expeller (ZKK30 Werner-Pfleiderer (Coperion)) while introducing the sedimented in the melt of the second expeller door. The fiber / resin mixture was then degassed and formed into composite glass / resin pellets.

The composite glass / resin pellets were then dried for 12 hours at 95 ° C by a molecular sieve circulating hot air dryer. After drying, the pellets were injection molded by an injection molding machine (Demag DC80 or Arburg 420C) into Axxicon ISO molds to form standard composite samples. The modeled samples were placed in metal containers containing silica gel to keep them dry.

A portion of the composite samples were mixed crosswise between different autoclaves to stimulate the same aging for each composite sample.

During hydrolysis (hydro-aging) testing, the compounds were completely immersed in a 50/50 ethylene glycol / water mixture and pressurized for 500 hours at a temperature of 120 ° C. When each hydrolysis test was completed, the vessel was cooled to room temperature before the tensile strengths and uncharged impact forces of Charpy were determined. Dry molding properties such as tensile strength, Charpy non-fixed impact force and Izod fixed and non-fixed impact force were measured in the dry, modeled samples. Results are shown below.

Tests to determine tensile strength were conducted according to the procedures set out in ISO 527-4 / 1B-10. Charpy non-fixed impact strength was measured according to the procedures set out in ISO 179-1 / 1 Eu. Izod's fixed and non-fixed impact strengths (2mm fixed) were measured according to ISO 180 / A. Laboratory conditions were adjusted as described in this 291.

Example 1: Loss of properties of polyacid-based glass fibers in the presence of calcium stearate Table 10

Molding dry properties of pieces composed of (polyamide 6) X (polyamide 6 + 0.35% calcium stearate)

<table> table see original document page 56 </column> </row> <table> <table> table see original document page 57 </column> </row> <table>

(a) blocked polyurethane dispersion (Baxenden Chemicals / Y-aminopropyltrieoxysilane (GE Silicones)

(b) blocked polyurethane dispersion (Baxenden Chemicals / Y-aminopropyltrieoxysilane (GE Silicones) + polyacrylic acid (low polyacid content)

(c) blocked polyurethane dispersion (Baxenden Chemicals / Y-aminopropyltrieoxysilane (GE Silicones) + EMA (low polyacid content)

(d) property value in (polyamide 6 + calcium stearate) minus property value in polyamide 6 / property value in polyamide 6

In Table 10, the overall negative effects of the presence of calcium stearate on physical properties such as tensile strength, Izod fixed and non-fixed impact forces of Charpy can be seen. As shown in Table 10, when calcium stearate is present in polyamide 6, as in Examples 2 and 3, tensile, Charpy and Izod properties are significantly lower compared to when there is no calcium stearate present. in polyamide. For example, in Examples 2 and 3, Izod's non-fixed impact forces decreased from 87.8 KJ / m2 to 55.4 KJ / m2 (Example 2) and from 90.1 KJ / m2 to 72.7 KJ / m2. m2 (Example 3) when calcium stearate was present. Similar decreases in Izod-labeled and Charpy-unlabeled impact forces were obtained when calcium stearate was present. As indicated by the strongly negative delta values for Examples 2 and 3, the losses were more severe in Example 2. Although the negative delta values for Example 3 were less severe, they are still significant when compared to the values. negative results obtained for the polyacid-free compound of Example 1. It is to be noted that although Examples 2 and 3 contain a polyacid, the amount of polyacid fractions present in the two-part sizing formulation is not enough to overcome the negative effects of polyamide dications 6.

It can also be seen from Table 10 that when no calcium stearate is present in polyamide 6, Examples 2 and 3, which contain a polyacid, they perform as well as and sometimes better than the polyacid-free compound. Example 1. For example, the results of Charpy impact strength in Examples 2 and 3 and Izod's fixed and fixed impact tests were higher than the corresponding results obtained for Example 1. The improved performance of the Examples 2 and 3 in polyamide 6 without calcium stearate with respect to Izod's non-fixed impact force can be seen graphically in FIG. 1, as well as the strong losses of the same properties when calcium stearate is present in polyamide 6.

Example 2: Influence of Polyacid Level on Performance of Calcium Stearate-containing Polyamide 6 Compounds

TABLE 11

Molding dry properties of pieces composed of (polyamide 6) X (polyamide 6 + 0.35% calcium stearate)

<table> table see original document page 59 </column> </row> <table> <formula> formula see original document page 60 </formula> <table> table see original document page 61 </column> </row> <table>

(a) γ-aminopropyltrieoxysilane (GE Silicones) + blocked polyurethane dispersion (Bayer Corp.)

(b) γ-aminopropyltrieoxysilane (GE Silicones) + blocked polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) (low polyacid content)

(c) γ-aminopropyltrieoxysilane (GE Silicones) + blocked polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) (medium polyacid content)

(d) γ-aminopropyltrieoxysilane (GE Silicones) + blocked polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) (high polyacid content)

(e) property value in (polyamide 6 + calcium stearate) minus property value in polyamide 6 / property value in polyamide 6 TABLE 12

Properties of (polyamide 6) X (polyamide 6 + 0.35% calcium stearate) composite pieces after aging in water / glycol mixture for 500 hours at 120 ° C

<table> table see original document page 62 </column> </row> <table> <table> table see original document page 63 </column> </row> <table>

(a) γ-aminopropyltrieoxysilane (GE Silicon

nes) / blocked isocyanate polyurethane dispersion (Bayer Corp.)

(b) γ-aminopropyltrieoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) (low polyacid content)

(c) γ-aminopropyltrieoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) (medium polyacid content)

(d) γ-aminopropyltrieoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) (high polyacid content)

(e) property value in (polyamide 6 + calcium stearate) minus property value in polyamide 6 / property value in polyamide 6

It can be seen from the data obtained and illustrated in Tables 11 and 12 that the negative effects caused by the presence of calcium stearate in polyamide 6 on tensile strength, uncharged and fixed and non-fixed impact forces of Charpy. Izod are reduced by the presence of a suitable amount of polyacid in the inventive ironing composition in two parts. It is to be noted that Examples 5, 6 and 7 differ only in the amount of polyacid content and increase in polyacid content from Example 5 (low acid content) to Example 6 (medium acid content) to Example 7 (high content). acid) respectively. Referring to Table 11, an example of the reduction of the negative effects caused by the presence of calcium stearate in polyamide is shown by Example 6. Although Charpy's unfixed impact forces decreased from 101.3 KJ / m2 to 94.8 KJ / m2 when calcium stearate was present, these data show an improvement on the Charpy non-fixed impact strength of the polyacid-free compound of Example 4 where Charpy's non-fixed impact strength decreased. from 98.4 KJ / m2 to 90.1 KJ / m2 when calcium stearate was present. By including an appropriate amount of polyacid in the two-part sizing formulation of the invention, Charpy's non-fixed impact strength was greater (98.4 KJ / m2) than the Charpy impact strength of the polyacid-free compound of the invention. Example 4 (90.1 KJ / m2) in the presence of calcium stearate. The reduction in negative effects of the presence of calcium stearate is also demonstrated by Example 7, where Charpy's non-fixed impact force decreases from 104.0 KJ / m2 to 94.7 KJ / m2 in the presence of calcium stearate. . The data obtained from Examples 6 and 7 show a slight difference in Charpy's non-fixed impact force (94.8 KJ / m2 for Example 6 and 94.7 KJ / m2 for Example 7), indicating that there may be a plateau for the number of polyacid fractions required to obtain dry-conformed-shaped mechanical properties in the composite product. Similar results demonstrating a decrease in the negative effects of calcium stearate on the polyacid were obtained in relation to tensile strength and fixed and non-fixed impact forces of Izod.

Referring to Example 5, it can be seen that the relatively low level polyacid containing compound resulted in better mechanical performance than the polyacid free polyurethane based compound formed by the two-part ironing formulation of Example 4. That is particularly noteworthy for the unfixed properties of dry molded Izod (DaM) (Table 11) and for tensile strength properties after hydro-aging when no calcium stearate is present (Table 12). However, when calcium stearate was present in polyamide 6, the polyacid-containing compound of Example 5 showed a loss of mechanical properties. For example, the polyacid containing compound of Example 5 demonstrated a loss of impact strength (fixed and unfixed) of dry Izod and Charpy as modeled (Table 11) and tensile strength and unfixed impact strength of Charpy after hydrochloride. aging (Table 12) compared to these same mechanical properties in the absence of calcium stearate. These mechanical property losses are clearly accentuated by the strongly negative delta values associated with the separate properties. While not wishing to be bound by theory, it is believed that the amount of polyacid present in the binder of the two-part sizing formulation that forms the compound product of Example 5 is not high enough to compensate for the carboxylic acid fractions consumed in the formulation. negative interaction with calcium stearate and as a result there is a decrease in the mechanical properties tested. On the other hand, as discussed above, Examples and 7 contain a higher polyacid content than Example 5 and are less sensitive to the presence of calcium stearate, as indicated by lower negative delta values for properties or drying as after hydro modeling. -aging. In Examples 6 and 7, the amount of polyacid present in the two-part ironing formulation is high enough to compensate for the negative interaction with calcium stearate. This excess in polyacid fractions results in improved and superior mechanical properties as seen in FIGS. 2 and 3.

Example 3: High X Low Polyacid Content Fiberglass Performance in Calcium Stearate-containing Polyamide 6 Compounds

TABLE 13

Molding dry properties of pieces composed of (polyamide 6) X (polyamide 6 + 0.35% calcium stearate)

<table> table see original document page 66 </column> </row> <table> <table> table see original document page 67 </column> </row> <table> <table> table see original document page 68 < / column> </row> <table>

(a) γ-aminopropyltrieoxysilane (GE Silicas) / blocked polyurethane dispersion (Baxenden Chemicals)

(b) γ-aminopropyltriexysilane (GE Silicones) + stearic acid-reacted tetramethylenopentamine (AOC) + fluoralkyl alcohol-substituted polyethylene glycol (Du-Pont) + partially ammonia-neutralized low-acrylic acid homopolymer solution ( Ciba) + alternating ethylene and maleic anhydride copolymer (Zeeland Chemicals) + polyurethane dispersion (DIC) + water soluble aliphatic diamine derived from propylene oxide-capped poly (ethylenoxide) (Hunstsman Corp.) + oxirane mixture (EO-PO copolymers) (BASF) (low polyacid content)

(c) γ-aminopropyltriexysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Ciba) + alternating ethylene and maleic anhydride copolymer (Zeeland Chemicals) ( high polyacid content)

(d) property value in (polyamide 6 + calcium stearate) minus property value in polyamide 6 / property value in polyamide 6

TABLE 14

Properties of (polyamide 6) X (polyamide 6 + 0.35% calcium stearate) composite pieces after aging in water / glycol mixture for 500 hours at 120 ° C

<table> table see original document page 69 </column> </row> <table> (a) γ-aminopropyltrieoxysilane (GE Silicas) / polyurethane dispersion (Baxenden Chemicals)

(b) γ-aminopropyltrieoxysilane (GE Silicones) + stearic acid-reacted tetraethylenepentamine (AOC) + fluoralkyl alcohol-substituted polyethylene glycol (Du-Pont) + partially ammonia-neutralized low-PM acrylic acid homopolymer solution ( Ciba) + alternating ethylene and maleic anhydride copolymer (Zeeland Chemicals) + polyurethane dispersion (DIC) + water soluble aliphatic diamine derived from propylene oxide-capped poly (ethylenoxide) (Hunstsman Corp.) + oxirane mixture (EO-PO copolymers) (BASF) (low polyacid content) (c) γ-aminopropyltrieoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low PM acrylic acid homopolymer solution (Cyba) ) + alternating ethylene-maleic anhydride copolymer (Zeeland Chemicals) (high polyacid content)

<d) property value in (polyamide 6 + calcium stearate) minus property value in polyamide 6 / property value in polyamide 6

It can be seen from the data obtained and illustrated in Tables 13 and 14 that negative effects caused by the presence of calcium stearate in polyamide 6 on tensile strength, uncharged and unchanged Charpy impacted and Izod impacted forces. are reduced by the presence of a suitable amount of polyacid in the two-part ironing composition of the invention. In the absence of calcium stearate, the polyacid-based fiberglass compound of Example 8 demonstrated an improvement in uncharged Charpy and fixed and non-fixed Izod impact properties as modeled (Table 13) and strength tensile strength and uncoupled impact strength after hydro-aging (Table 14) against the polyacetan-free, commercial polyurethane-based fiberglass of Example 1. Thus, the polyacid performed its expected function of improving mechanical properties when no calcium stearate was present.

In the presence of calcium stearate, however, the level of polyacid present in the two-part ironing formulation of Example 8 was not sufficient to compensate for the level of calcium stearate present in polyamide, as a result, the polyacid fractions were consumed. negative interaction with calcium stearate dication. The low polyacid level present in Example 8 results in lower than expected performance (eg, results that are well below the results that were observed with polyamide 6 without calcium stearate) of Charpy and (fixed) impact forces. and non-fixed) dry Izod according to the model (Table 13) and Charpy's tensile strength and non-fixed impact strength after hydro-aging (Table 14). The high sensitivity to calcium stearate of the low polyacid level of Example 8 is also clearly accentuated by the highly negative delta values for these properties. On the other hand, the compound product of Example 9 contained a higher level of polyacid in the two-part ironing formulation. This can be seen from Tables 13 and 14 that when calcium stearate was present in polyamide 6, calcium stearate-induced losses in the uncharged impact forces of Charpy and (fixed and non-fixed) Izod dried according to modeling (Table 13) and Charpy's tensile strength and non-fixed impact strength after hydro-aging (Table 14) of Example 9 were less severe compared to the composite product of Example 8. Improved impact strength Fixed Charpy dried according to Example 9 is illustrated graphically in FIG. 4. Excess polyacid present in the two-part filler formulation resulted in a high mechanical performance of the compound pieces tested both before and after hydro-aging with and without the presence of calcium stearate in polyamide 6. Such mechanical properties demonstrated by the compound product of Example 9 confirm the superior and unexpected properties of the two-part ironing formulation of the present invention.

Example 4: Influence of calcium stearate level present on polyamide 6 on polyacid based fiber reinforced polyamide 6 performance

Table 15

Molding dry properties of (polyamide 6) X polyamide 6 + 0.14% calcium stearate (1) and polyamide 6 + 0.35% calcium stearate (2) _

<table> table see original document page 72 </column> </row> <table> <table> table see original document page 73 </column> </row> <table> <table> table see original document page 74 < / column> </row> <table>

(a) γ-aminopropyltrieoxysilane (GE Silicas) / blocked polyurethane dispersion (Baxenden Chemicals)

(b) γ-aminopropyltriexysilane (GE Silicones) + stearic acid-reacted tetramethylenopentamine (AOC) + fluoralkyl alcohol-substituted polyethylene glycol (Du-Pont) + partially ammonia-neutralized low-acrylic acid homopolymer solution ( Ciba) + alternating ethylene and maleic anhydride copolymer (Zeeland Chemicals) + polyurethane dispersion (DIC) + water soluble aliphatic diamine derived from propylene oxide-capped poly (ethylenoxide) (Hunstsman Corp.) + oxirane mixture (EO-PO copolymers) (BASF) (low polyacid content)

(c) γ-aminopropyltrieoxysilane (GE Silicones) + nonionic polyurethane dispersion (Bayer Corp.) + alternating ethylene and maleic anhydride copolymer (Zeeland Chemalicals)

(d) γ-aminopropyltrieoxysilane (GE Silicones) + nonionic polyurethane dispersion (Bayer Corp.) + ammonia-partially neutralized low PM acrylic acid homopolymer solution + alternating ethylene-maleic anhydride copolymer (Zeeland Chemicals)

(e) property value in (polyamide 6 + calcium stearate) minus property value in polyamide 6 / property value in polyamide 6

Another way to exemplify the results of the high polyacid fiber content against traditional low or polyacid free polyacid-based glass fibers is to compare their performance in polyamide formulations containing increasing levels of calcium stearate. Table 15 shows the mechanical properties of pieces of polyamide 6 compound based on four different glass fibers that were produced on an industrial scale. For each example, data on the mechanical properties of the compounds were collected for polyamide 6 (without any calcium stearate), for polyamide 6 containing 0.14% by weight against calcium stearate compound (1) and for polyamide 6 containing 0.35% by weight against calcium stearate compound (2). The polyacid level (as LOI) increases from Example 1 to Example 8 to Example 10 to Example 11, respectively.

The specific LOI for each example is exposed in

Table 2

It can be seen from Table 15 that when no calcium stearate is present, all polyacid based products perform as well (eg tensile strength) or better than (eg fixed impact strength of Izod and Charpy). the polyacetane-free, fiberglass-based fiberglass of Example 1. At intermediate levels of calcium stearate, the impact properties of the low polyacid content candidate of Example 8 are noticeably affected. On the other hand, the larger polyacid content compounds of Examples 10 and 11 show acceptable impact properties at intermediate levels of calcium stearate as well as in the presence of even greater amounts of calcium stearate. These results are illustrated in FIG. 5, which shows the relative performance of glass fibers on the related Charpy unfixed property of DaM-tested polyamide 6 compounds containing different levels of calcium stearate. It is noted that the tensile strength properties are less dependent on the level of calcium stearate present in the compound.

The foregoing description of the specific embodiments will fully disclose the general nature of the invention which others may, by applying knowledge within the skill of the art (including the contents of the references cited herein), readily modify and / or adapt to various applications such as these. specific embodiments, without undue experimentation, without departing from the general concept of the present invention.

Therefore, such adaptations and modifications are intended to be within the meaning and equivalent range of the disclosed embodiments, based on the teaching and guidance set forth herein. It is to be understood that the phraseology or terminology herein is for the purpose of description and not limitation, such that the terminology or phraseology of the present specification is to be interpreted by the skilled artisan in light of the teachings and guide presented herein in combination with the above. knowledge of someone skilled in the art.

The invention of this application has been described above both generally and with respect to specific embodiments. While the invention has been set forth in what are believed to be preferred embodiments, a wide variety of alternatives known to those skilled in the art may be selected within the general disclosure. The invention is not otherwise limited except by reciting the claims set forth below.

Claims (43)

1. Two-part ironing formulation for filling a reinforcing fiber, characterized by the fact that it comprises: a gum composition; and a binder composition comprising at least one polyacid having an acid number greater than about 300 and containing acid fractions, wherein said two-part sizing formulation is used to form a product compound when combined with a polymer which includes a higher valence dication or cation, said acid fractions being present in said polyacid in an amount that is greater than the amount of said higher valence cation or cation present in said polymer. Two-part ironing formulation according to claim 1, characterized in that the said amount of said acidic fractions is sufficient to retain at least a portion of said acidic fractions after interacting with said dication or said cation of higher valence when forming said composite material. Two-part ironing formulation according to claim 1, characterized in that said at least one polyacid is present in said reinforcing fiber in an amount sufficient to provide an ignition weight loss. up to about 2.0%. A two-part ironing formulation according to claim 1, characterized in that said at least one polyacid is a polyacid selected from a copolymer formed from the polymerization of maleic anhydride and at least one other monomer. copolymerized therewith, a copolymer formed from the maleic acid polymerization and at least one other copolymerized monomer thereof and a polycarboxylic acid. Two-part ironing formulation according to claim 4, characterized in that said at least one polyacid is an ethylene-maleic acid copolymer. Two-part ironing formulation according to claim 1, characterized in that said polymer has an acid number of from about 300 to about 950. Two-part sizing formulation according to claim 1, characterized in that said gum composition comprises a coupling agent and a first film-forming agent. A two-part sizing composition as defined in claim 7, characterized in that said binder composition further comprises a second film-forming agent, said first and second film-forming agents being the same or different from each other. A two-part ironing formulation as defined in claim 8, characterized in that at least one of said first and second film-forming agents is a non-isocyanate-based polyurethane film-forming agent. blocked. 10. Two-part ironing formulation for the sizing of a reinforcing fiber used to form a composite material when combined with a polymer which includes a higher valence dication or cation, the above two-sizing ironing formulation. parts being characterized by the fact that it comprises: a gum composition containing a first film former; and a binder composition comprising at least one high acid number polyacid selected from a copolymer formed from the maleic anhydride polymerization and at least one other monomer copolymerized therewith, a copolymer formed from the maleic acid polymerization and at least one other copolymerized monomer thereof, and a polycarboxylic acid and a second film former, said first and second film former being the same or different from each other, wherein said high acid number is greater. that about 300. Two-part ironing formulation according to claim 10, characterized in that said high acid number is from about 300 to about -950. A two-part ironing formulation according to claim 10, characterized in that the high acid number polyacid cited in the said reinforcing fiber is sufficient to provide a loss of ignition up to about 2.0%. A two-part ironing formulation according to claim 10, characterized in that at least one of said first and second film-forming agents is an isocyanate-based polyurethane film-forming agent. not blocked. 14. Reinforced product compound, characterized in that it comprises: a polymeric matrix containing a dication or cation of greater valence; and a plurality of yarns of a reinforcing fiber, the yarns including: an inner coating of a gum composition; and an outer coating of a binder composition including at least one high acid polyacid containing acid fractions, said acid fractions being present in an amount that is greater than the amount of said higher valence dication or cation present in said matrix polymeric. A reinforced product compound according to claim 14, characterized in that said at least one high acid number polyacid is a polyacid selected from a copolymer formed from the maleic anhydride polymerization and at least one. another copolymerized monomer thereof, a copolymer formed from the maleic acid polymerization and at least one other copolymerized monomer thereof is a polycarboxylic acid. Reinforced product compound according to claim 15, characterized in that said at least a high acid number polyacid is present in said reinforcing fiber in an amount sufficient to provide a loss of ignition of up to about 2.0%. A reinforced product compound according to claim 16, characterized in that said at least one high acid number polyacid is an ethylene maleic acid copolymer. Reinforced product compound according to claim 14, characterized in that said at least a high acid number is from about 300 to about -950. A reinforced product compound according to claim 14, characterized in that said gum composition comprises a first film-forming agent. A reinforced product compound according to claim 19, characterized in that said binder composition further comprises a second film-forming agent, said second film-forming agent being the same or different from said first film-forming agent. movie pain. Reinforced product compound according to claim 20, characterized in that at least one of said first and second film-forming agents is a non-blocked isocyanate-based polyurethane film-forming agent. 22. Starched reinforcing fiber used to form a product compound, characterized in that it comprises: a reinforcing fiber at least partially coated with a two-part sizing formulation, said reinforcing fiber being combined with a polymer which includes a dication or cation of greater valence to form said product compound, wherein said two-part sizing formulation includes: a gum composition; and a binder composition comprising at least one high acid number polyacid containing acid fractions, said acid fractions being present in an amount that is greater than the amount of said higher valence cation or cation present in said polymer, said ci. - high acid number being greater than about 300. A starched reinforcing fiber according to claim 22, characterized in that said amount of said acidic fractions is sufficient to retain at least a portion of said acidic fractions after interacting with said dication or cation of cation. greater valence when forming said composite material. A starched reinforcing fiber according to claim 22, wherein said at least a high acid number polyacid is present in said reinforcing fiber in an amount sufficient to provide a loss of ignition of up to about 2.0%. Starched reinforcing fiber according to claim 22, characterized in that said high acid number is from about 300 to 950. A starched reinforcing fiber according to claim 22, characterized in that said gum composition comprises a coupling agent and a first film-forming agent. A starched reinforcing fiber according to claim 27, characterized in that said binder composition further comprises a second film-forming agent, said first and second film-forming agents being the same or different from one another. tro. Starched reinforcing fiber according to claim 26, characterized in that at least one of said first and second film-forming agents is a non-blocked isocyanate-based polyurethane film-forming agent. A starched reinforcing fiber according to claim 22 wherein said at least a high acid number polyacid is a polyacid selected from a high acid number copolymer formed from the maleic anhydride polymerization and by at least one other copolymerized monomer thereof, a copolymer formed from maleic acid polymerization and at least one other copolymerized monomer thereof and a high acid number polycarboxylic acid. 30. Starched reinforcing fiber, characterized in that it comprises: a reinforcing fiber at least partially coated with a two-part sizing formulation, said two-part sizing formulation including: a gum composition containing a first form. - film pain; and a binder composition comprising at least one high acid number polyacid containing acid fractions capable of interacting with higher valence dications or cations, said high acid number polyacid being selected from a copolymer formed from polymerization of maleic anhydride and at least one other copolymerized monomer thereof, a copolymer formed from the polymerization of maleic acid and at least one other copolymerized monomer thereof and a polycarboxylic acid, wherein said high acid number is greater than about 300. Starched reinforcing fiber according to Claim 30, characterized in that said high acid number is from about 300 to 950. A starched reinforcing fiber according to claim 30, characterized in that said high acid number polyacid is present in said reinforcing fiber in an amount sufficient to provide an ignition loss of up to about 2.0. %. A starched reinforcing fiber according to claim 30, wherein said binder composition further comprises a second film forming agent, said first and second film forming agents being the same or different from one another. tro. A starched reinforcing fiber according to claim 30, characterized in that at least one of said first and second film-forming agents is a non-blocked isocyanate-based polyurethane film-forming agent. 35. A method of preparing a reinforced fiber reinforced to reinforce an article compound containing a higher valence dikation or cation, characterized in that it comprises: applying a gum composition to at least a portion of a dye fiber. reinforcement to form a coated reinforcement fiber material; and applying a binder composition to said coated reinforcing fiber material, said binder composition comprising at least one high acid number polyacid containing acid fractions capable of interacting with a higher valence dication or cation, said high acid number polyacid having an acid number of at least about -300. A method according to claim 35 wherein said gum composition comprises a film-forming agent. A method according to claim 35, characterized in that said amount of said acidic fractions is sufficient to retain at least a portion of said acidic fractions after interacting with said higher valence cation or cation. 38. The method of claim 35 wherein said at least one high acid number polyacid is present in said reinforcing fiber in an amount sufficient to provide an ignition loss of up to about 2.0. %. 39. [Claim missing on original document] 40. A method of forming reinforced fiber pellets, characterized in that it comprises: at least partially coating reinforcing fibers with a gum composition to form coated reinforcing fibers, said gum composition including a first film-forming agent. ; cutting coated reinforcing fibers to produce short length coated reinforcing fibers; at least partially coating said short-length coated reinforcement fibers with a binder composition to form binder-coated short-length reinforcement fibers, said binder composition comprising at least one high acid number polyacid containing acid fractions capable of interacting with higher valence dications or cations, said high acid number polyacid selected from a copolymer formed from maleic anhydride polymerization and at least one other copolymerized monomer therewith, a copolymer formed from maleic acid polymerization and at least another monomer copolymerized therewith and a polycarboxylic acid, said high acid number being greater than 300; and pelleting the reduced length binder-coated reinforcement fibers to form pellets of reinforcement fiber. A method according to claim 39, characterized in that it further comprises densifying said reinforced fiber pellets. 41. The method of claim 39 wherein said at least one high acid number polyacid is present in said binder-coated short length reinforcement fibers in an amount sufficient to provide an ignition loss of up to about 2.0%. 42. The method of claim 41 wherein said binder composition further comprises a second film forming agent, said first and second film forming agents being the same or different from each other. 43. The method of claim 42, wherein at least one of said first and second film-forming agents is an unblocked isocyanate-based polyurethane film-forming agent.