JP2009522459A - Two-part sizing composition for reinforcing fibers - Google Patents

Abstract

A two-part sizing formulation is provided that imparts improved strength to a reinforced composite comprising a size composition and a binder composition. The size composition may include one or more coupling agents and one or more film forming agents. The binder composition comprises a high acid number copolymer and / or a high acid number polycarboxylic acid formed by polymerization of maleic anhydride or maleic acid with at least one other desired monomer. In a preferred embodiment, the binder composition comprises an ethylene-maleic acid copolymer formed by hydrolysis of an ethylene maleic anhydride copolymer. The size composition may be applied to the reinforcing fiber material prior to applying the binder size material. The two part size composition can be applied to the reinforcing fiber material to form a reinforcing fiber product and then densified or compressed to form a densified reinforcing fiber product, such as a pellet.
[Selection] Figure 1

Description

  The present invention relates generally to sizing compositions for reinforcing fiber materials, and more particularly to a two-part or two-component system that imparts improved strength to a reinforced composite, including a size composition and a binder composition ( two-part) sizing composition. A composite product formed from a reinforcing fiber material sized with a two-part sizing formulation is also provided.

Glass fibers are useful in a variety of techniques. For example, glass fiber reinforced plastics or composites are typically formed using glass fibers as reinforcement in the polymer matrix. Glass fibers are used in the form of continuous or chopped filaments, strands, rovings, woven fabrics, nonwovens, meshes, and scrims to reinforce the polymer. It is known in the art that glass fiber reinforced polymer composites have higher mechanical properties than unreinforced polymer composites if the reinforcing fiber surface is appropriately modified with a sizing composition. . Thus, better dimensional stability, tensile strength and modulus, bending strength and modulus, impact resistance, and creep resistance can be achieved with glass fiber reinforced composites.
Generally, chopped glass fibers are used as the reinforcing material in the reinforced composite. Conventionally, glass fibers are formed by thinning a stream of molten glass material from a bush or orifice. The glass fibers can be thinned by a winder that collects the collected filaments in a package or by a roller that picks up the fibers and then collected and cut. Typically, an aqueous sizing composition, or chemical treatment, is applied to the fiber after it has been drawn from the bushing. After treating the fibers with the aqueous sizing composition, they can be dried in package or chopped strand form.
The chopped strand segment can be mixed with a polymer resin and fed to a compression molding machine or injection molding machine to form a glass fiber reinforced composite. Typically, chopped strand segments are mixed with pellets of thermoplastic polymer resin in an extruder. In one conventional method, polymer pellets are fed to a first port of a twin screw extruder and chopped glass fibers are fed with molten polymer to a second port of the extruder to form a fiber / resin mixture. Alternatively, the polymer pellets and chopped strand segments are dry mixed and fed together to a single screw extruder to melt the resin, destroy the integrity of the glass fiber strands, and the fiber strands throughout the molten resin. Disperse to form a fiber / resin mixture. The fiber / resin mixture is then degassed and formed into pellets. Next, the dried fiber strand / resin dispersion pellet is supplied to a molding machine to form a molded composite product (glass fiber strands are dispersed substantially uniformly throughout the composite product).

  Unfortunately, chopped glass fibers are often bulky and do not flow well with automated equipment. As a result, the chopped fiber strands are compressed into rod-like bundles or pellets to improve their fluidity, for example, allowing the use of automated equipment to transport the pellets and mix them with the polymer resin. US Pat. No. 5,578,535 (Hill et al.) Discloses glass fiber pellets that are about 20% -30% denser and about 5-10 times larger in diameter than the individual glass strands from which the glass fiber pellets are made. This pellet is sufficient to prevent the chopped fiber strand segments from separating into individual filaments of the fiber strand segments, but insufficient hydration to aggregate the fiber strand filaments into lumps. Prepared by hydrating to level. The hydrated strand segments are then mixed for a time sufficient for the strand segments to form pellets. Suitable mixing methods include processes that keep the fibers moving up and around each other, for example, by tumbling, shaking, blending, mixing, agitation, and / or intermingling.

Sizing compositions such as those used in reinforced composites are well known in the art and typically include a polyacid polymer component, a film-forming polymer component, a coupling agent, and a lubricant. Polyacid sizing compositions are typically added to glass fibers to reduce the friction between the filaments and to make the glass fibers compatible with the polymeric material they are intended to strengthen. The sizing composition also ensures the integrity of the glass fiber strands, for example, the interconnection of the glass filaments forming the strands.
One fundamental problem associated with conventional sizing compositions used in reinforced composites is that cationic species such as metal salts of long chain carboxylic acids are present in the polymer used to form the reinforced composite. It exists. The interaction between the dicationic lubricant and the conventional sizing composition of the polyacid reduces the mechanical strength. For example, polyacid composites reinforced with conventional sizing compositions may have impact strength (e.g., Charpy or Izod, unnotched or notched) when tested on hydro-aged composite pieces. Often shows a decrease in tensile strength and a decrease in tensile strength and elongation at break. Accordingly, there is a need in the art for a sizing composition that provides improved mechanical strength to a reinforced composite containing a dicationic lubricant.

Improved to reinforced polymer composites (e.g., reinforced polyamide composites) even when the composite contains a dicationic or higher valency cationic additive such as a calcium stearate lubricant. It is to provide a two part sizing formulation that provides mechanical properties and resistance to hydrolysis in a dry-as-molded (DaM) state. The two-part sizing formulation includes a size composition and a binder composition. The size composition can be applied to the reinforcing fiber material prior to applying the binder composition. The reinforcing fiber material may be one or more glass (Advantex® glass) strands, natural fibers, carbon fibers, or one or more synthetic polymers. According to at least one exemplary embodiment of the present invention, the size composition includes one or more coupling agents and one or more film forming agents. Preferably, the coupling agent is an aminosilane or diaminosilane. In addition, the size composition can optionally include conventional additives such as lubricants, wetting agents, pH adjusters, antioxidants, antifoaming agents, processing aids, antistatic agents, and / or nonionic surfactants. May be included.
The binder composition comprises a high acid number copolymer and / or a high acid number polycarboxylic acid formed from maleic anhydride or maleic acid and at least one other desired monomer. The maleic anhydride or copolymer of maleic acid may be a pure copolymer, or may be an anhydride, acid, salt, or derivative in the form of a partial ester, partial amide, partial imide. Suitable copolymers include C ₂ -C ₅ α-olefins such as butadiene, ethylene-, propylene- or (iso) butylene-maleic acid copolymers, and methyl vinyl ether-maleic acid copolymers. In a preferred embodiment, the binder composition comprises an ethylene-maleic acid copolymer formed by hydrolysis of an ethylene-maleic anhydride copolymer. The binder composition may include a film forming agent, which may be the same as or different from the film forming agent in the size composition. The size composition may include conventional additives such as lubricants, surfactants, and antistatic agents.

Still another object of the present invention is to provide a method for producing a densified reinforcing fiber product. A method for producing a densified reinforcing fiber product includes a step of applying a two-part sizing preparation as described above to a strand of reinforcing fiber material, a step of cutting the strand of sized reinforcing fiber into segments, and a binder composition as described above. May be applied to the segment and an in-line process including pelletizing and / or densifying the segment to form a densified reinforcing fiber product. Pellet formation and densification can occur in separate tumbling devices, such as rotating drums (eg, pelletizers) and / or rotating zigzag tubes (eg, densifiers). Alternatively, pellet formation and densification can occur in separate areas within a single device, such as a “zigzag” blender commercially available from Patterson Kelly. Within the pelletizer, the size composition can be applied to the fibers as they are formed, and the binder composition can be applied to the sized fibers. By applying the binder composition in a pelletizer, application efficiencies of about 95% to 100% of the binder composition can be obtained. In addition, applying the binder composition separately from the size composition outside the fiber forming environment can result in safety, flammability, irritation, stability, poor compatibility with aminosilanes, viscosity, toxicity, cleanliness, odor, cost, and Materials that are not desirable to apply during the fiber formation process due to shear sensitivity may be included.
An advantage of the present invention is that the high loss-on-ignition (LOI) of high acid number maleic anhydride copolymers, ethylene maleic acid copolymers, or polycarboxylic acids in the sizing composition is improved molding. To provide mechanical properties and improved hydrolysis resistance when dry.
Another advantage of the present invention is that the polyurethane film former present in the sizing composition exhibits good compatibility with the polyamide matrix and helps improve the dispersion of reinforcing fiber bundles in the melt during the formation of the composite (e.g. In extrusion process or injection molding process). This improved fiber distribution reduces defects such as visual defects in the final product, reduced processing interruptions, and / or low mechanical properties of the final product.
A further advantage of the present invention is that the dispersion of the polyurethane present in the sizing composition enhances the compatibility of the sizing composition with the dicationic species-containing polymer and further fiber dispersion during processing to form a composite article. It is to improve.
Yet another advantage is that the present invention provides improved physical properties to composites formed from industrially processable and easily dispersible pellets, such as dry on molding (DaM) state or severe To provide improved mechanical properties after aging the composite part under hydrolysis conditions.
It is also an advantage of the present invention that the two-part sizing formulation has improved stability over conventional sizing formulations containing aminosilane and polyacid in the same mixture.
The above and other objects, features and advantages of the present invention will become more fully apparent in view of the following detailed description.
The advantages of the present invention will become apparent upon consideration of the following detailed description of the invention, particularly when taken in conjunction with the accompanying drawings.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. All references cited herein are presented in the cited references, including published or corresponding U.S. or foreign patent applications, issued U.S. or foreign patents and any other references. All the data, tables, figures and the whole including text are incorporated respectively. The terms “film forming agent” and “film former” are used interchangeably herein. Further, the terms “reinforcing fiber material” and “reinforcing fiber” are used interchangeably herein.
The present invention relates to a two-part sizing formulation that improves the mechanical performance of reinforced composites. In particular, the two-part sizing formulations of the present invention provide for polymer-reinforced composites such as polyamide reinforced composites, even when the composite contains a dicationic or higher ionic additive such as a calcium stearate lubricant. Provides improved mechanical properties and hydrolysis resistance in the dry state during molding. Any dication or higher cation cation can be applied to the present invention, but for ease of discussion, the dication will be discussed in detail herein. A two-part sizing formulation can be applied to a reinforcing fiber material to form a reinforcing fiber product and then densified or compressed to form a densified reinforcing fiber product such as a pellet. Densified pellets provide a convenient form for storage and handling of chopped fibers used as reinforcing materials in composite structures.
The size composition can be applied to the reinforcing fiber material prior to applying the binder composition. The reinforcing fiber material may be one or more strands of glass formed by conventional techniques such as drawing molten glass through a heated bushing to form a substantially continuous glass fiber. These fibers can then be collected into glass strands. Any type of glass can be used, for example, A-type glass, C-type glass, E-type glass, S-type glass, or ECR-type glass, such as Owens Corning's Advantex® glass fiber. . Preferably, the reinforcing fiber material is E-type glass or Advantex® glass.
Alternatively, the reinforcing fiber material may be a strand of one or more synthetic polymers such as polyester, polyamide, aramid, and mixtures thereof. Polymer strands may be used alone as the reinforcing fiber material, or glass strands and polymer strands such as those described above may be used in combination. As a further alternative, natural fibers can be used as the reinforcing fiber material. The term “natural fiber” as used in connection with the present invention refers to plant fibers extracted from any part of the plant, including but not limited to trunks, seeds, leaves, roots. Or phloem.
Examples of natural fibers suitable for use as reinforcing fiber materials include cotton, jute, bamboo, ramie, bagasse, hemp, coconut, linen, kenaf, sisal, flax, henequen, and The combination is mentioned. Carbon fiber or polyaramid fiber can also be used as the reinforcing fiber material.
The reinforcing fiber material includes fibers having a diameter of about 6 microns to about 24 microns and can be cut into segments of about 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 about 10 microns. Prior to densification of the reinforcing fiber material as described below, each strand can include from about 500 fibers to about 8,000 fibers.

After the reinforcing fibers are formed and before the reinforcing fibers are collected into strands, they can be coated with a size composition. A suitable size composition of at least one exemplary embodiment of the present invention comprises one or more coupling agents and one or more film forming agents. Optionally, conventional additives such as lubricants, wetting agents, pH adjusting agents, antioxidants, antifoaming agents, processing aids, antistatic agents, and nonionic surfactants (including but not limited to May be present in the size composition. The size composition may be applied to the reinforcing fibers in an amount sufficient to achieve a loss on ignition (LOI) of about 0.05% to 1.0% for the dry fibers, preferably in an amount of 0.15% to about 0.40%. LOI is the percentage of organic solids deposited on the glass fiber and the weight loss experienced by the fiber after heating the fiber to a temperature sufficient to burn or pyrolyze the organic size from the fiber. Defined as the ratio measured by
The size composition includes one or more coupling agents. Preferably, the coupling agent is a silane coupling agent. In addition to its role of the coupling agent to bond the surface of the reinforcing fiber and the plastic matrix, the silane enhances the adhesion of the polycarboxylic acid component to the reinforcing fiber and flakes during subsequent processing, or It also functions to lower the level of fiber filaments that are broken. Examples of silane coupling agents that can be used in the size composition of the present invention are characterized by the functional groups amino, epoxy, vinyl, methacryloxy, ureido, isocyanato, and azamide. In preferred embodiments, the silane coupling agent has one or more functional groups such as amines (primary, secondary, tertiary, and quaternary), amino, imino, amide, imide, ureido, isocyanato, or azamide. Including silanes containing one or more nitrogen atoms.
Suitable silane coupling agents include, but are not limited to, amino silanes, silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur silanes, ureido silanes, and isocyanato silanes. Specific non-limiting examples of the silane coupling agent used in the present invention include γ-aminopropyltriethoxysilane (A-1100), n-phenyl-γ-aminopropyltrimethoxysilane (Y-9669), and n-trimethoxy. -Silyl-propyl-ethylene-diamine (A-1120), methyl-trichlorosilane (A-154), γ-chloropropyl-trimethoxy-silane (A-143), vinyl-triacetoxysilane (A-188), methyl Examples thereof include trimethoxysilane (A-1630) and γ-ureidopropyltrimethoxysilane (A-1524). Other examples of suitable silane coupling agents are shown in Table 1 below. All silane coupling agents above and in Table 1 are commercially available from GE Silicones.

  Further examples of suitable silane coupling agents include Chisso's products having the registered trademarks shown in Table 1A below.

Table 1A

The silane coupling agent used in the present invention may be replaced with an alternative coupling agent or mixture. For example, A-1387 may be replaced with a modification in which the methanol solvent is replaced with ethanol. A-1126 (GE Silicones), an aminosilane coupling agent containing a mixture of about 24% by weight diaminosilane modified with a surfactant in methanol solution, was added to trimethoxy-silyl-propyl-ethylene-diamine (Dow Corning's Z -6020). A-1120 or Z-6020 may be replaced with a prehydrolyzed variant. Z-6020 may be replaced with Z-6137, a prehydrolyzed variant lacking an alcohol solvent and containing 33% diaminosilane in water at a solids concentration of 24% (commercially available from Dow Corning). In addition, A-1100 can be replaced with its hydrolyzed Y-9244, which will reduce or eliminate ethanol excretion.
Preferably, the silane coupling agent is aminosilane or diaminosilane.
The size composition can include one or more of the above coupling agents. The coupling agent can be applied to the fiber in an amount sufficient to achieve a loss on ignition (LOI) of about 0.02% to about 0.30% for the dry fiber, preferably about 0.04% to about 0.08%.
Further, the size composition may include at least one resin film-forming agent. Any conventional film former known to those skilled in the art can be utilized in the size composition. Further, the film forming agent may be the same as or different from the film forming agent present in the binder composition described in detail later. In the size composition, the film-forming agent acts as a polymer binder to provide additional protection to the reinforcing fibers and enhance processability such as reduced flaking produced by high speed cutting. A film former may be present on the reinforcing fibers in an amount sufficient to provide a LOI of 0% to about 1.0%. Preferably, the film former is present on the fibers in an amount sufficient to provide an LOI of about 0.15% to about 0.60%.

In another embodiment of the present invention, the size composition contains a lubricant in place of or in addition to the film former to facilitate manufacture. Examples of suitable lubricants include, but are not limited to, water soluble ethylene glycol stearates (eg, polyethylene glycol monostearate, butoxyethyl stearate, polyethylene glycol monooleate, and butoxyethyl stearate), ethylene glycol These include oleates, ethoxylated fatty amines, glycerin, emulsified mineral oil, and organopolysiloxane emulsions. Other examples of lubricants include alkyl imidazoline derivatives (e.g., cationic softeners having a solids content of about 90% and commercially available from Th. Goldschmidt AG), stearinethanolamide (e.g., Lubesize K12 (AOC )), And polyethyleneimine polyamide salts which are commercially available from Cognis under the trade name Emery 6760 at 50% active solids. Lubricant may be present on the fiber in an amount sufficient to provide a LOI of up to about 0.10%.
The size composition is effective at any pH level, but the pH is preferably in the range of 7-11. The pH can be adjusted depending on the intended use or to facilitate compatibility of the components of the size composition. Any suitable pH adjusting agent (eg, a weak organic acid such as acetic acid or a base such as ammonia) can be added to the size composition in an amount sufficient to adjust the pH to the desired level.
A size composition can be prepared by dissolving each component with stirring to form a premix. The separate premix is then combined with deionized water to form a main mixture, achieving the proper concentration, and controlling the mixing of the solids. The premix may be added in any order. If necessary, the pH of the main mixture can be adjusted to the desired level. The premix may be added separately or simultaneously to form the main mixture.

As mentioned above, the two-part sizing formulation also includes a binder composition. The binder composition comprises a high acid number copolymer and / or a high acid number polyacid formed from maleic anhydride or maleic acid and at least one other desired monomer. Here, the expression “high acid number” is intended to indicate a polyacid having an acid number or acid value higher than about 300. In addition, the binder composition may contain any suitable additive recognized by those skilled in the art, such as an adhesive film-forming polymer, a lubricant, a surfactant or surfactant mixture, an antistatic agent, and a crosslinking agent. . Depending on the desired application, the binder composition can be applied to the fibers at a LOI of about 0.20% to about 2.0%.
The maleic anhydride or maleic anhydride copolymer may be a pure copolymer or a derivative in the form of an anhydride, acid, partial salt, partial ester, partial amide, or partial imide. Suitable copolymers include C ₂ -C ₅ α-olefins such as ethylene-, propylene-, (iso) butylene-, or butadiene-maleic acid copolymers, and methyl vinyl ether-maleic acid copolymers. The copolymer is not very soluble when dispersed in water at room temperature, but when heated to temperatures above about 90 degrees, hydrolysis of the anhydride group of the polymer causes the copolymer to dissolve and form the corresponding polyacid. In the reaction, 1 mole of anhydride hydrolyzes to 2 moles of diacid in an exothermic reaction. Next, a binder composition can be mix | blended using the aqueous solution produced by hydrolysis. Similar reactions can be utilized to form partial ammonium salts, partial esters, partial amides, or partial imide derivatives, respectively, using ammonia or amines in water or alcohols or amines in non-reactive solvents.
In a preferred embodiment, the binder composition comprises an ethylene-maleic acid (EMA) copolymer formed by hydrolysis of an ethylene-maleic anhydride copolymer. Ethylene-maleic anhydride copolymers can be formed by radical copolymerization of ethylene and maleic anhydride in the presence of peroxide. This copolymerization results in alternating copolymers containing high levels of maleic acid units, which impart high polyacid functionality to the ethylene-maleic acid copolymer.
In at least one exemplary embodiment, the copolymer is an aqueous solution of a polyacid, (partial) ammonium salt, partial ester, partial amide, or partial imide derivative of an alternating block copolymer of maleic anhydride, or a mixture thereof. Different ethylene maleic acid copolymers or other high acid number polycarboxylic acids such as maleic anhydride copolymers or maleic anhydride homopolymers or copolymers with acrylic acid or mixtures of derivatives thereof such as those mentioned above are used in the binder composition to achieve the desired properties. For example, improved strength or improved fiber processability of the reinforcing fiber product can be achieved, and the overall binder cost can be reduced.
As noted above, the binder composition may include a high acid number (eg, high acid number) polyacid instead of or in addition to maleic anhydride or maleic acid copolymer. Desirably, the polyacid is a polycarboxylic acid. Suitable polycarboxylic acid polymers for use in the binder composition are organic polymers that contain many pendant carboxylic acid groups and are characterized by high acid numbers. The acid number or acid number of a substance is expressed as a measure of the free acid content and can be expressed in milligrams of potassium hydroxide neutralized with the free acid present in one gram of 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.

  The polycarboxylic acid polymer may be a homopolymer or copolymer prepared from an unsaturated carboxylic acid. Unsaturated carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, and α , β-methylene glutaric acid. Alternatively, polycarboxylic acid polymers can 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 skilled in the art and are not described in detail herein. Further, the polycarboxylic acid polymer may comprise a copolymer of one or more unsaturated carboxylic acids or anhydrides and one or more vinyl compounds as described above. Examples of the vinyl compound include, but are not limited to, styrene, α-ethylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, methacrylic acid. n-butyl, isobutyl methacrylate, glycidyl methacrylate, vinyl methyl ether, vinyl acetate, 1-olefins (eg, ethylene, isobutene) vinyl and allyl alkyl ethers (eg, methyl vinyl ether, ethyl vinyl ether), substituted acrylamides, and sulfonic acids And sulfonate monomers (eg, allyl sulfonic acid, vinyl sulfonic acid). The polyacids are described in detail in US Pat. No. 5,236,982 (Cossement et al.), Which is hereby incorporated by reference in its entirety.

  The high acid number maleic anhydride copolymer, high acid number ethylene maleic acid copolymer, or high acid number polycarboxylic acid in the binder composition is up to about 2.0%, preferably about 0.10% to about 2.0%, and still more preferably about It can be present on the fiber in an amount sufficient to provide a LOI of 0.40% to about 1.0%. When a high acid number maleic anhydride copolymer, a high acid number ethylene maleic acid copolymer, or a high acid number polycarboxylic acid is contacted with a polymer containing a dication, an interaction occurs between the carboxylic acid component and the dication, and the carboxylic acid component is It can be seen that it is consumed or otherwise cannot interact advantageously with the polymer premix. Although not wishing to be bound by theory, it is believed that ratios higher than 2: 1 (respectively carboxylic acid equivalents of polyacids: dicationic equivalents) retain the presence of carboxylic acid components after the interaction between the polyacid component and the dication. Therefore, the excess carboxylic acid component present in the size / binder composition supplements the polyacid consumed by the dication to achieve improved dry state mechanical properties and improved hydrolysis resistance. It is desirable to do. However, the specific amount of carboxylic acid component necessary to achieve the excess (and improved physical properties) present in the binder composition depends on the amount of dication present in the polymer. It is equivalent to the number of equivalents of carboxylic acid component present on the reinforcing fiber and the equivalent of dicationic additive present in the polymer, targeting LOI% of maleic anhydride copolymer, ethylene maleic acid copolymer, or high acid number polycarboxylic acid. This is considered to be a difference from the number. It should be noted that the use of high LOI polyacids does not change the efficacy of calcium stearate in its main role as a lubricant / release agent.

In addition to the maleic anhydride copolymer, ethylene maleic acid copolymer, or high acid number polycarboxylic acid, the binder composition may include one or more film formers. A film-forming agent is an agent that increases the adhesion between reinforcing fibers and consequently improves the integrity of the strands. Suitable film formers include thermosetting and thermoplastic polymers that promote the adhesion of the sizing composition. Polyurethane film formers exhibit good compatibility with polyamide matrices when forming composite articles and help improve the dispersion of glass fiber bundles in the melt (e.g., extrusion or injection molding processes), in the final product. A preferred class of film formers for use in binder compositions because they reduce or eliminate defects (eg, visual defects, processing interruptions, and / or poor mechanical properties) caused by insufficient dispersion of reinforcing fibers. The polyurethane dispersion utilized in the two-part sizing formulation of the present invention may be part of a dispersion that is based on blocked isocyanate or not. Further, as described above, the film forming agent present in the binder composition may be the same as or different from the film forming agent present in the size composition.
Non-limiting examples of suitable urethane film formers based on blocked isocyanate that can be used in the binder composition include, but are not limited to, Baybond® XP-2602 (nonionic polyurethane dispersion (Bayer Corp. .)); Baybond® PU-401 and Baybond® PU-402 (anionic urethane polymer dispersion (Bayer Corp.)); Baybond® VP-LS-2277 (anionic / non-ionic) Ionic urethane polymer dispersions (Bayer Corp.)); Aquathane 518 (nonionic polyurethane dispersions (Dainippon, Inc.)); and Witcobond 290H (polyurethane dispersions (Witco Chemical Corp.)). Other examples of suitable film formers for use in the binder composition include, but are not limited to, polyvinylpyrrolidone homopolymers and copolymers and other polymers with amide-like functionality such as polyamide, polyvinylformamide, or polyacrylamide. Can be mentioned. In at least one exemplary embodiment, the film former is an aqueous polyurethane dispersion that is not part of a dispersion comprising polyurethane and blocked isocyanate.
Examples of suitable urethane film formers based on blocked isocyanates that may be used in the binder composition include, but are not limited to, Baybond® XW-116; Baybond® XP-055; Baybond (Registered trademark) PU-330; Baybond® PU-400-S; Baybond® PU-401 (polyurethane dispersion based on blocked isocyanate (available from Bayer Corp.)); VP-LS-2277 and Baybond VP-LS-2297 (anionic / nonionic urethane polymer dispersion (Bayer Corp.)); Baybond® PU-130 (anionic / non-ionic) Ionic Urethane Polymer Dispersion (Bayer Corp.)); Baybond® PU-403 (Polyurethane Dispersion (Bayer Corp.)); Baybond® PU-239 (Crosslinkable Anionic / Nonionic Urethane) Polymer dispersion (Bayer Corp.); Baybond® PU-2435 (anionic / nonionic urethane polymer dispersion (Bayer Corp.)) Corp.)); and Witcobond 296B (aqueous blocked polyurethane dispersion, available from Baxenden Chemicals).
The film former may be present in the binder composition in an amount sufficient to provide an LOI of up to about 1.0%, preferably from about 0.10% to about 0.40%. The amount of film-forming agent present in the two-part sizing formulation helps the fiber dispersal during processing by the two-part sizing formulation providing the desired level of compatibility to the reinforcing fibers and polymer matrix, and the positive effect of the polyacid component The amount should be such that it improves the mechanical properties of the dry and hydro-aged state during molding without affecting and forms a composite part without generating static electricity and / or undesired color in the reinforcing fiber product. desirable.

The binder composition can be prepared by mixing a solution of the desired high acid number polyacid (e.g., a polycarboxylic acid obtained by hydrolysis of the parent polyanhydride in hot water) with a solution of the film forming agent. it can. Optionally, the solution may be diluted with water. Prior to mixing the polyacid solution with the film former solution, it may be necessary to adjust the pH of the polyacid solution with a base to reduce or eliminate the occurrence of destabilization phenomena. Although any pH adjuster can be added to the binder composition, the pH can be adjusted to a desired level, but it is preferable to adjust the pH by adding ammonia (NH ₄ ).
The total LOI of the two-part sizing formulation on the reinforcing fiber material may be from about 0.25% to about 2.05%, preferably from about 0.60% to about 1.10%.
One advantage of the two-part sizing formulation of the present invention is that a two-part, which can contain a high acid number maleic anhydride copolymer, a high acid number ethylene maleic acid copolymer, or a high acid number polycarboxylic acid with a LOI of up to about 2.0%. The product resulting from application of the sizing formulation is to provide improved mechanical properties even when the polyamide matrix contains a dicationic additive such as calcium stearate.
In addition, the two-part sizing formulation of the present invention provides improved physical properties to composites formed from pellets that can be processed industrially and easily dispersed, such as aging of composite parts within severe hydrolysis conditions. Gives the improved dry state (DaM) mechanical properties of the composite part later.
The present invention provides that the polyurethane film former present in the two-part sizing formulation exhibits good compatibility with a polymer matrix containing a dicationic lubricant (e.g., a polyamide matrix), and the reinforcing fiber bundle in the melt during the formation of the composite article. To increase the dispersion (eg, in an extrusion or injection molding process). This high dispersion of reinforcing fibers reduces defects such as visual defects, processing interruptions, and / or low mechanical properties of the final product.
In addition, the two-part sizing formulation of the present invention has improved stability over conventional sizing formulations containing aminosilane and polyacid in the same mixture. A mixture containing both aminosilane and polyacid will not be stable due to the chemical interaction between the two compounds. By placing substantially all (if not all) aminosilanes in the size composition and polyacid in the binder composition, the shelf life of both the size composition and the binder composition is increased.

The method for producing the densified reinforcing fiber product may be an in-line method that allows for the application of a size composition, the cutting of glass fibers, the application of a binder composition, and the pelletization of reinforcing fiber material. The in-line method forms pellet products that exhibit superior physical properties (eg, compared to pellets produced by methods known in the art), for example when integrated into a composite. While not wishing to be bound by theory, it is believed that such superior properties are due to the improved compatibility of the size composition and binder composition allowing better coating of the reinforcing fiber material.
The method for producing a densified reinforcing fiber product of the present invention may utilize an apparatus including the following apparatuses: (a) an apparatus for applying a continuous fiber material to a size composition; (b) a glass fiber strand. An apparatus for cutting to form a chopped strand segment; (c) an apparatus for transporting the chopped strand segment to a first tumbling apparatus; and (d) for applying a binder composition to the chopped strand segment. An apparatus; (e) a first tumbling apparatus for imparting a tumbling action to the chopped strand segments to disperse the binder composition and aligning and fusing the chopped strand segments into pellets; (f) optionally pellets (G) Optionally, the pellet is tumbled to compress the pellet to increase its density. Second tumbling apparatus order; (h) a device for conveying the densified pellets drying apparatus; and (i) drying apparatus adapted to dry it receives the pellets.

Initially, the size composition can be applied to the reinforcing fiber material by any conventional means such as kiss rolls, dip-draws, and slide or spray applicators. Preferably, the precursor size is applied by passing a reinforcing fiber material such as glass or polymer strands over the kiss roll applicator. Preferably, the size composition is applied to the strand in an amount sufficient to provide the strand with a moisture content of from about 8% to about 13%, more preferably from about 10% to about 11% by weight.
The sized strand can then be cut into strand segments. The strand segment can have a length of about 2 mm to about 50 mm. Preferably, the strand has a length of about 3 mm to about 4 mm. Any suitable method or apparatus known to those skilled in the art for cutting glass fiber strands can be used.
The binder composition can then be applied to the chopped strand segment. The coated chopped strand segments are then pelletized by any suitable method known to those skilled in the art, such as by tumbling or otherwise agitating the chopped strand segments in a pelletizer. Suitable methods for pelletizing chopped strand segments are disclosed in U.S. Patent Nos. 5,868,982, 5,945,134, 6,365,090, and 6,659,756 to Strait et al. And U.S. Patent No. 5,693,378 to Hill et al. (All these patents are incorporated herein in their entirety). The amount of moisture in the binder composition helps to adjust the moisture content of the strand segments to a level suitable for pellet formulation when the strand segments are tumbled in the pelletizer. Although the moisture content of the strand segment can be adjusted before introducing the strand segment into the pelletizer, it is preferable to hydrate the segment to a moisture content suitable for the pellet formulation within the pelletizer itself.
Preferably, the moisture content of the chopped strand segment in the pelletizer is from about 12% to about 16%, more preferably from about 13% to about 14%, based on the total weight of the binder-sized chopped strand segment. % By mass. If the moisture content is too low, the strand segments will not be tied together into pellets and will remain in the strand structure. On the other hand, if the moisture content is too high, the strands agglomerate or aggregate to form pellets with large diameters and irregular non-cylindrical shapes.
When the chopped strand segment is placed in the pelletizer, or the chopped segment is placed in the pelletizer, the binder composition can be applied to the chopped strand segment prior to tumbling. In an alternative embodiment, the binder composition may be sprayed onto the strands before cutting the strands. In this alternative embodiment, it is preferred to use a pelletizer specially provided with tumbling means such as baffles to ensure sufficient tumbling and formation of the pellets.
In order to ensure good coverage of the chopped segments, it is preferable to apply the binder composition to the chopped strand segments, when the chopped strand segments are introduced, but before the strand segments begin to coalesce into pellets. Application of the binder composition at other locations within the pelletizer can produce pellets before the strand segments are completely coated with the binder composition. The result is a pellet containing fibers that are not coated with the binder composition. If such pellets are used in the manufacture of fiber reinforced composites, the uncoated fibers will lack the interfacial coating necessary to provide good reinforcing properties and the resulting composite properties will be less than optimal. Preferably, the pelletizer comprises a spray nozzle disposed adjacent to the strand segment inlet for spraying a binder size onto the strand segment as the strand segment enters the pelletizer.
The pelletizer may be any device that can tumble the strand segments as follows: (1) the strand segments are uniformly coated with the binder composition, and (2) multiple chopped strand segments are aligned and fused to the desired dimensions. It becomes the pellet which has. Such a tumbling device is sufficient to ensure that the strand segments are substantially coated with the binder size to form the pellets, but the pellets are rubbed through friction (e.g. by rubbing each other). It must have an average residence time that is insufficient to damage or decompose. Preferably, the residence time in the tumbling apparatus is from about 1 minute to about 10 minutes. More preferably, the residence time in the tumbling apparatus is from about 1 minute to about 3 minutes.
A preferred pelletizer is a rotating drum as disclosed in US Pat. No. 5,868,982, as described above. US Pat. No. 5,868,982 discloses an apparatus for producing reinforcing fiber pellets, preferably equipped with a system for monitoring and / or adjusting various process parameters. Appropriate methods can be used to monitor and control the moisture content of the strand segment input. In one embodiment where the binder composition is applied to the strand segment prior to placing the strand segment into the pelletizer, rotating to provide a spray head for applying the binder composition to the strand segment as it enters the drum. Adapt the drum. The binder composition and a solvent, such as water, can be combined into a single fluid stream and dispersed through the nozzle orifice. This stream may be combined with two air jets positioned approximately 180 degrees apart and at an angle of 60 degrees with the direction of flow of the stream. This mixing of the forced air stream with the binder composition effectively produces a mist that is sprayed onto the surface of the tumbling strand segments in the drum.
The rotation of the drum causes the surface tension produced by the wet sizing or coating to tumble the wet strand segments around each other, causing the strand segments to contact each other beyond a substantial length of the strand segments and align with each other. Fused into a cylindrical pellet. By this action, any fine fibers or single fibers produced during the cutting operation recombine with the formed pellets and are incorporated into the formed pellets, essentially eliminating individual fine fibers from the resulting pellets. Preferably, the drum is tilted slightly so that the end of the drum where the pellets exit is lower than the end where the pellets enter so that the pellets formed in the drum do not stay in the drum for an excessive period of time.
The size of the pellets formed in the drum is mainly controlled by the moisture content of the strand segments. If the moisture content is maintained at a high level, more strand segments will coalesce into pellets that will have a larger diameter. On the other hand, if moisture is maintained at lower levels, fewer strand segments will coalesce into pellets, which will have a smaller diameter. Monitor the mass of wet glass entering the pelletizer and adjust the amount of binder composition on the strand by a computer that adjusts the amount of binder composition to obtain a final chopped strand having a strand solids of about 0.25 wt% to about 2.05 wt%. The amount of binder composition that flows out can be controlled.
Preferably, the pellet formed has a diameter of about 20% to about 65% of the length of the pellet. Such pellets are typically formed by combining about 70 strand segments to about 175 strand segments, each containing about 500 individual filaments per strand to about 8000 individual filaments per strand.
The size of the pellets can also be affected by the throughput of the drum. For example, the higher the throughput of the drum, the shorter the residence time of the strand segment in the drum. As a result, smaller binder pellets are formed because the binder composition is not well dispersed on the strands and does not fuse the strands into the pellets. Furthermore, pellets formed in the drum in a shorter time are less dense than the pellets formed in the drum for a longer time.
Some compression of the formed pellets always occurs in the pelletizer, but this is generally insufficient to increase the density of the pellets to a level that provides optimum flowability. For this reason, after forming the pellets in the pelletizer, the pellets can optionally be fed to a second tumbling device or densifier. Here, the pellets are further compressed and densified. Any low impact tumbling device that compresses the pellets without rubbing or otherwise breaking the pellets may be used. Preferably, the densifier is a zigzag tube adapted to rotate about its longitudinal axis, as disclosed, for example, in U.S. Pat.Nos. 5,868,982, 5,945,134, 6,365,090, and 6,659,756 to Strait et al. ing.
Preferably, the densifier has a tumbling action that is milder and less severe than the pelletizer's tumbling action to minimize pellet degradation. As the zigzag tube rotates, the pellets in it are pulled through the tube by gravity and are therefore gently tumbled around by the rotation of the tube. As with the rotating drum described above, the zigzag tube densifier is preferably tilted at a slight angle so that excess residence time pellets do not flow through the apparatus. Further, the densifier preferably has an average residence time of less than about 5 minutes to reduce any friction that may occur. Preferably, the average residence time in the densifier is from about 1 minute to about 2 minutes.

Pellet formation and densification may be performed on separate devices, such as separate rotating drums and rotating zigzag tubes connected by a conveyor, although pelletizing can be achieved using either device. For example, pellet formation and densification may occur in separate tumbling regions or zones within a single device. A preferred example of such a device is a “zigzag” blender commercially available from Patterson Kelly. In a preferred embodiment of this apparatus, the drum comprises an internal baffle to reduce the natural fall distance of glass pellets and strand segments during drum rotation. By reducing this distance, glass fiber and pellet degradation through impact and friction is reduced, resulting in improved physical properties of the glass fiber reinforced moldings produced therefrom.
After densification, the pellets can be fed onto a conveyor belt and dried using, for example, a hooded dryer with hot and cold air or any drying device readily identifiable by those skilled in the art. In order to reduce the drying time to a level acceptable for commercial mass production, it is preferred to dry the fibers at a high temperature up to about 260 ° C. in a fluid bed dryer. After drying, the densified pellets can be sorted by size using a screen or other suitable device.
By varying the throughput capacity and moisture content of the strand segments, glass fiber pellets can be made that are about 13% to about 60% denser and about 10 to about 65 times larger in diameter than the corresponding non-pelletized strand segments. For example, a chopped 4 mm (length) segment of 2000 filament strands composed of 14 micron (diameter) fibers typically ranges from about 528.66 kg / m ³ (33 lb / ft ³ ) to 576.72 kg / m ³ (36 lb / It has a bulk density of ft ³ ). After forming the hydrated and densified pellets to a moisture content of about 13% to about 14% as described above by the method of the present invention, the resulting dry pellets are typically about 640.8 kg / m ³ (40 lbs). / ft ³ ) to a bulk density of about 881.1 kg / m ³ (55 lb / ft ³ ). As a result of its high diameter-to-length ratio and high density, the resulting pellets exhibit significantly improved flow properties compared to non-pelleted chopped strand products.
The size composition and binder composition facilitate the treatment of reinforcing fiber materials, such as glass, during a continuous process that includes fiber forming and subsequent processing or handling steps. By applying the binder composition in a pelletizer, an application efficiency of about 95% to about 100% is obtained for the binder composition. This high application efficiency reduces wastewater contamination in the plant. Furthermore, since the binder composition can be applied efficiently, the binder composition can be applied at low cost.
In addition, by applying the binder composition separately from the sizing composition outside the fiber forming environment, toxicity, safety, flammability, irritation, stability, low compatibility with aminosiloxanes, viscosity, toxicity, cleanliness, fouling. It allows glass fibers to be applied with materials that are undesirable to apply during the fiber forming process due to odor, cost, or shear sensitivity. In addition, when the glass fiber is formed, the polyacid in the binder composition can be applied to the glass fiber in a concentrated form in the pelletizer rather than directly to the glass fiber. And waste is reduced.
The present invention is very suitable for in-line manufacturing processes as described above, but the size composition and binder composition are applied to a pre-formed and packaged reinforcing fiber material, or the size composition and binder composition are reinforced fiber. The invention can also be used in off-line processes applied at different times to the material. For example, after applying the size composition to the formed fiber strands, the strands may be wound and stored, and then subsequently unwound and cut into segments to apply the binder composition.
Having generally described the invention, a further understanding can be obtained by reference to the specific embodiments shown below. The following specific examples are provided for illustrative purposes only, and are not intended to be comprehensive or limiting unless otherwise specified.

  [2-part sizing preparation]

^(a) AX-1100 シラン γ-アミノプロピルトリエトキシシラン(GE Silicones)
^(b) K12 Lubesize テトラエチレンペンタミン(ステアリン酸と反応した)(AOC)
^(c) Zonyl FS-300 フルオロアルキルアルコール置換ポリエチレングリコール (DuPont)
^(d) Baybond PU-403 ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)
^(e) Witcobond 296B ブロックトポリウレタン分散系(Baxenden Chemicals)
^(f) Baybond XP-2602 非イオン性ポリウレタン分散系(Bayer Corp.)
^(g) Glascol E5溶液(低Mwアクリル酸ホモポリマーの)(Ciba)
^(h) Glascol C95溶液(アンモニアで部分的に中和した低Mwアクリル酸ホモポリマーの)(Ciba)
⁽ⁱ⁾ ZeMac E400(約400,000のMwエチレンと無水マレイン酸の交互コポリマー)(Zeeland Chemicals)
^(j) ZeMac E60(約60,000のMwを有する、エチレンと無水マレイン酸の交互コポリマー)(Zeeland Chemicals)
^(k) Aquathane 518ポリウレタン分散系(D.I.C.)
^(l) Jeffamine ED2003 水溶性脂肪族ジアミン(プロピレオキシド-キャップドポリ(エチレンオキシドから誘導) (Huntsman Corp.)
^(m) Pluronic F-77 オキシラン(EO-POコポリマー) (BASF)
⁽ⁿ⁾ Pluronic PE-103 オキシラン(EO-POコポリマー) (BASF)
^(o) Pluronic L-101 オキシラン(EO-POコポリマー) (BASF)
^(p) Triton X-100 オクチルフェノキシポリエトキシエタノール(Union Carbide Corp.) Table 2

^(a) AX-1100 Silane γ-Aminopropyltriethoxysilane (GE Silicones)
^(b) K12 Lubesize Tetraethylenepentamine (reacted with stearic acid) (AOC)
^(c) Zonyl FS-300 fluoroalkyl alcohol substituted polyethylene glycol (DuPont)
^(d) Baybond PU-403 blocked isocyanate polyurethane dispersion (Bayer Corp.)
^(e) Witcobond 296B blocked polyurethane dispersion (Baxenden Chemicals)
^(f) Baybond XP-2602 nonionic polyurethane dispersion (Bayer Corp.)
^(g) Glascol E5 solution (low Mw acrylic acid homopolymer) (Ciba)
^(h) Glascol C95 solution (of low Mw acrylic acid homopolymer partially neutralized with ammonia) (Ciba)
⁽ⁱ⁾ ZeMac E400 (alternate copolymer of about 400,000 Mw ethylene and maleic anhydride) (Zeeland Chemicals)
^(j) ZeMac E60 (alternate copolymer of ethylene and maleic anhydride having a Mw of about 60,000) (Zeeland Chemicals)
^(k) Aquathane 518 polyurethane dispersion (DIC)
^(l) Jeffamine ED2003 Water-soluble Aliphatic Diamine (Propylene oxide-capped poly (derived from ethylene oxide) (Huntsman Corp.)
^(m) Pluronic F-77 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 Octylphenoxypolyethoxyethanol (Union Carbide Corp.)

The two-part sizing composition shown in Table 2 was prepared as described below.
Preparation of Examples 1-3 in Table 2:
In Examples 1 to 3, the components in Table 3 were mixed to prepare a size composition. The size composition was applied to 10 μm Advantex® glass fiber to achieve a 0.60% strand loss on ignition (LOI) for the glass fiber. The amount of size composition applied on the glass fiber was determined using the conventional loss on ignition (LOI) method, ASTM 2854. Next, the glass fibers were collected into strands and cut into segments having a length of about 4 mm by a wet in-line with a chopper.

^(a) ブロックトポリウレタン分散系(Baxenden Chemicals)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones) Table 3

^(a) Blocked polyurethane dispersion (Baxenden Chemicals)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones)

The chopped segments were then collected and processed after about 1-2 days under laboratory pelletizer rotation (where the corresponding binders shown in Table 2 were sprayed onto the chopped strands). In Example 1, no binder was applied during pelletization. In Example 2, Glasscol E5 (low molecular weight acrylic acid homopolymer 25% solids solution) available from Ciba was diluted to 15% solids with deionized water and used as a binder. In Example 3, a binder composition was prepared by dispersing 132 g ZeMac 400 (an alternating copolymer of ethylene and maleic anhydride available from Zeeland Chemicals) in 870 g deionized water and heated to about 95 ° C. with stirring. And melted. Various binder compositions were applied to achieve the corresponding LOI% shown in Table 2. Densified glass pellets were collected and dried at a maximum temperature of 220 ° C. for about 16 minutes in a moving belt laboratory dryer.
Preparation of Examples 4-7 in Table 2:
In Examples 4-7, the size composition was prepared by mixing the ingredients in Table 4. The size composition was applied to 10 μm Advantex® glass fiber to achieve a 0.35% strand loss on ignition (LOI) for the glass fiber. The amount of size composition applied on the glass fiber was determined using the conventional loss on ignition (LOI) method, ASTM 2854. Next, the glass fibers were collected into strands and cut into segments having a length of about 4 mm by a wet in-line with a chopper.

^(a) ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones) Table 4

^(a) Blocked isocyanate polyurethane dispersion (Bayer Corp.)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones)

The chopped segments were then collected and processed after about 1-2 days under laboratory pelletizer rotation (where the corresponding binders shown in Table 2 were sprayed onto the chopped strands). In Example 4, Baybond PU-403 (a 39% solids blocked isocyanate polyurethane dispersion available from Bayer Corp.) was diluted to 5% solids with deionized water and used as the binder. In Examples 5-7, binders were prepared by diluting Glascol E5 (25% solids solution of low molecular weight acrylic acid homopolymer) to 15% solids with deionized water. Various binder compositions were applied to achieve the corresponding LOI% shown in Table 2. Densified glass pellets were collected and dried at a maximum temperature of 220 ° C. for about 16 minutes in a moving belt laboratory dryer.
Preparation of Example 8 in Table 2:
The size composition of Example 8 was prepared according to the description in Table 7 set forth in US Patent Publication No. 2004/020999 A1 (Piret et al.), Which is incorporated herein in its entirety. In 4-7, the components of Table 4 were mixed to prepare a size composition. In particular, the size compositions shown in Table 5 were prepared and applied to 10 μm Advantex® glass fibers when producing glass fibers in a continuous in-line process. Next, glass fibers were formed into strands and cut into strand land segments having a length of about 4.0 mm. Molten glass was fed through the bush at about 1.48 × 10 ⁶ Pa (215 lbs) / hour. The size composition was applied using a conventional kiss roll applicator while rotating the strand direction at 15 m / min. A size composition was applied at a concentration of 0.69% to achieve a strand LOI of 0.06% solids for the glass.

^(a) γ-アミノプロピルトリエトキシシラン(GE Silicones)
^(b) ステアリン酸と反応したテトラエチレンペンタミン(AOC)
^(c) フルオロアルキルアルコール置換ポリエチレングリコール(DuPont) Table 5

^(a) γ-Aminopropyltriethoxysilane (GE Silicones)
^(b) Tetraethylenepentamine (AOC) reacted with stearic acid
^(c) Fluoroalkyl alcohol substituted polyethylene glycol (DuPont)

  Next, the chopped segment was conveyed to a pelletizer, and the binder composition of Table 6 was sprayed onto the chopped segment. The binder composition was applied to achieve a strand LOI of 0.59% solids for the glass fiber. The total loss on ignition (LOI) of the glass was 0.65%. The densified glass pellets were transported to a conveyor type or fluid bed dryer and dried.

^(a) 約400,000のMwを有する、エチレンと無水マレイン酸の交互コポリマー
(Zeeland Chemicals)
^(b) 水溶性脂肪族ジアミン(プロピレンオキシド-キャップドポリ(エチレンオキシド)
(Huntsman Corp.)
^(c) 部分的にアンモニアで中和した低Mwアクリル酸ホモポリマーの溶液
^(d) γ-アミノプロピルトリエトキシシラン(GE Silicones)
^(e) ポリウレタン分散系(D.I.C.)
^(f) オキシラン(EO-POコポリマー) (BASF)
^(g) オキシラン(EO-POコポリマー) (BASF)
^(h) オキシラン(EO-POコポリマー) (BASF)
⁽ⁱ⁾ オクチルフェノキシポリエトキシエタノール(Union Carbide Corp.) Table 6

^(a) an alternating copolymer of ethylene and maleic anhydride having a Mw of about 400,000
(Zeeland Chemicals)
^(b) Water-soluble aliphatic diamine (propylene oxide-capped poly (ethylene oxide)
(Huntsman Corp.)
^(c) Low Mw acrylic acid homopolymer solution partially neutralized with ammonia
^(d) γ-Aminopropyltriethoxysilane (GE Silicones)
^(e) Polyurethane dispersion (DIC)
^(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 in Table 2:
In Example 9, a size composition was prepared by mixing the ingredients in Table 7. The size composition was applied to 10 μm Advantex® glass fiber to achieve a 0.25% strand loss on ignition (LOI) for the glass fiber. The amount of size composition applied on the glass fibers was determined using the conventional loss on ignition (LOI) method, ASTM 2854. Next, the glass fibers were collected into strands and cut into segments having a length of about 4 mm in a wet in-line using a chopper.

^(a) ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones) Table 7

^(a) Blocked isocyanate polyurethane dispersion (Bayer Corp.)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones)

  The chopped segments were then collected and processed after about 1-2 days under laboratory pelletizer rotation (where the binder was sprayed onto the chopped strands). 13.43 kg of ZeMac 400 EMA powder was dispersed in 47.85 kg of deionized water, and the powder was dissolved by heating the water to about 95 ° C. with stirring. After the ZeMac 400 EMA powder was dissolved, 19 kg of deionized water was added to further dilute the solution. 18.61 kg of Glascol C95 (partial ammonia neutralized low molecular weight acrylic acid homopolymer solution available from Ciba) was then added at a temperature below 60 ° C. with stirring. This binder composition was applied to achieve a 0.61% solids strand LOI for the glass. The total loss on ignition (LOI) of the glass fiber was 0.86%. Densified glass pellets were collected and dried at a maximum temperature of 220 ° C. for about 16 minutes in a moving belt laboratory dryer.

Preparation of Example 10 in Table 2:
In Example 10, a size composition was prepared by mixing the ingredients in Table 8. The size composition was applied to 10 μm Advantex® glass fiber to achieve a 0.22% strand loss on ignition (LOI) for the glass fiber. The amount of size composition applied on the glass fibers was determined using the conventional loss on ignition (LOI) method, ASTM 2854. Next, the glass fibers were collected into strands and cut into segments having a length of about 4 mm in a wet in-line using a chopper.

^(a) 非イオン性ポリウレタン分散系(Bayer Corp.)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones) Table 8

^(a) Nonionic polyurethane dispersion (Bayer Corp.)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones)

  The chopped segment was then transported to the pelletizer and the binder was sprayed onto the chopped segment as it passed through the inlet chamber of the pelletizer. 32.00 kg of ZeMac 60 EMA powder was dispersed in 80.80 kg of deionized water, and the powder was dissolved by heating the water to about 95 ° C. with stirring. After the ZeMac 60 EMA powder was dissolved, the solution was cooled to 25 ° C. and about 9.10 kg of 25% ammonia solution was added to adjust the pH to about 3.5. Next, 52.37 kg Baybond XP-2602 (a nonionic polyurethane dispersion available from Bayer Corp.) was added slowly with stirring. The densified glass pellets were transported to a conveyor or conveyor type or fluid bed dryer and dried. The binder composition was applied to achieve a 0.61% solids strand LOI for the glass fiber. The total loss on ignition (LOI) of the glass fiber was 0.83%.

Preparation of Example 11 in Table 2:
In Example 11, a size composition was prepared by mixing the ingredients in Table 9. The size composition was applied to 10 μm Advantex® glass fiber to achieve a 0.22% strand loss on ignition (LOI) for the glass fiber. The amount of size composition applied on the glass fibers was determined using the conventional loss on ignition (LOI) method, ASTM 2854. Next, the glass fibers were collected into strands and cut into segments having a length of about 4 mm in a wet in-line using a chopper.

^(a) 非イオン性ポリウレタン分散系(Bayer Corp.)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones) Table 9

^(a) Nonionic polyurethane dispersion (Bayer Corp.)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones)

  The chopped segment was then transported to the pelletizer and the binder was sprayed onto the chopped segment as it passed through the inlet chamber of the pelletizer. 13.43 kg of ZeMac 400 EMA powder was dispersed in 47.85 kg of deionized water, and the powder was dissolved by heating the water to about 95 ° C. with stirring. After the ZeMac 400 EMA powder was dissolved, 19 kg of deionized water was added to further dilute the solution. Next, 18.61 kg of Glascol C95 (a solution of low molecular weight acrylic acid homopolymer partially available with ammonia, available from Ciba) was added at a temperature below 60 ° C. with stirring. The densified glass pellets were transported to a conveyor or conveyor type or fluid bed dryer and dried. The binder composition was applied to achieve a strand LOI of 0.50% solids on the glass fiber. The total loss on ignition (LOI) of the glass fiber was 0.72%.

[Comparative test]
Using a twin-screw simultaneous rotary meshing extruder (ZSK30 Werner-Pfleiderer (Coperion)), the glass fiber pellets were extruded with amide 6 molded pellets (Ultramid B3 available from BASF, with or without calcium stearate), Compounding while feeding the pellets to the melt at the second port of the machine. The fiber / resin mixture was then degassed and formed into compounded glass / fiber pellets.
The compounded glass / resin pellets were then dried at 95 ° C. for 12 hours in a molecular sieve circulating hot air dryer. After drying, the pellets were injection molded into Axxicon ISO molds with an injection molding machine (Demag DC80 or Arburg 420C) to form standard composite specimens. The molded specimen was placed in a metal container containing silica gel and kept dry.
A portion of the composite specimen was cross-mixed between different autoclaves to simulate the same aging for each composite specimen. During the hydrolysis (hydroaging) test, the composite was completely immersed in an ethylene glycol / water (50/50) mixture and placed under pressure at a temperature of 120 ° C. for 500 hours. When each hydrolysis test was completed, the tensile strength and Charpy notch impact strength were determined after the container was cooled to room temperature. The dry state during molding (DaM) characteristics such as tensile strength, impact strength without Charpy notch, and impact strength without Izod notch were measured on the dried molded specimens. The results are shown below.
A test was performed to determine the tensile strength according to the procedure shown in ISO 527-4 / 1B / 10. The Charpy notch impact strength was measured according to the procedure shown in ISO 179-1 / 1 Eu. Izod notched and notched (2 mm notch) were measured according to ISO 180 / A. Laboratory conditions were as described in ISO 291.

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

^(a) ブロックトポリウレタン分散系(Baxenden Chemicals)/γ-アミノプロピルトリエトキシシラン(GE Silicones)
^(b) ブロックトポリウレタン分散系(Baxenden Chemicals)/γ-アミノプロピルトリエトキシシラン(GE Silicones)+ポリアクリル酸(低ポリ酸含量)
^(c) ブロックトポリウレタン分散系(Baxenden Chemicals)/γ-アミノプロピルトリエトキシシラン(GE Silicones)+EMA(低ポリ酸含量)
^(d) {(ポリアミド6+ステアリン酸カルシウム)の特性値−ポリアミド6の特性値}／ポリアミド6の特性値 Table 10
(Polyamide 6) vs. (Polyamide 6 + 0.35% calcium stearate) composite piece when dried

^(a) Blocked polyurethane dispersion (Baxenden Chemicals) / γ-aminopropyltriethoxysilane (GE Silicones)
^(b) Blocked polyurethane dispersion (Baxenden Chemicals) / γ-aminopropyltriethoxysilane (GE Silicones) + polyacrylic acid (low polyacid content)
^(c) Blocked polyurethane dispersion (Baxenden Chemicals) / γ-aminopropyltriethoxysilane (GE Silicones) + EMA (low polyacid content)
^(d) {characteristic value of (polyamide 6 + calcium stearate) −characteristic value of polyamide 6} / characteristic value of polyamide 6

In Table 10, there is a general negative effect of the presence of calcium stearate on physical properties such as tensile strength, Charpy notch and Izod notched and unnotched impact strength. As shown in Table 10, when calcium stearate is present in polyamide 6 (e.g., Examples 2 and 3), tensile strength, Charpy and Izod properties are significantly reduced compared to when no calcium stearate is present in the polyamide. To do. For example, in Example 2 and 3, the calcium stearate is present, Izod notched impact 55.4 strength from ^{87.8KJ / m 2 KJ / m 2} ( Example 2), 72.7KJ / m from 90.1KJ / m ² Reduced to ² (Example 3). In the presence of calcium stearate, similar reductions in Charpy notched and Izod notched impact strength were obtained. The loss was the worst in Example 2, as shown by the large negative value delta in Examples 2 and 3. The negative delta value of Example 3 is not very severe but is still significant compared to the smaller negative value obtained with the polyacid-free composite of Example 1. Examples 2 and 3 contain polyacids, but note that the amount of polyacid component present in the two-part sizing formulation is insufficient to overcome the negative effects of the dication present in polyamide 6. Should.
From Table 10 it can also be seen that in Examples 2 and 3 containing polyacids, when no calcium stearate is present in polyamide 6, it functions similarly to the polyacid-free composite of Example 1 and sometimes better. . For example, the Charpy impact strengths of Examples 2 and 3 and the results of Izod notched and notched impact tests were superior to the corresponding results obtained in Example 1. The improved performance of Examples 2 and 3 in polyamide 6 without calcium stearate for Izod notched impact strength, and the strong loss of the same properties when calcium stearate is present in the polyamide can be seen from the graph of FIG.

  Example 2: Effect of polyacid level on performance of polyamide 6 composites containing calcium stearate

^(a) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)(低ポリ酸含量)
^(c) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)(中ポリ酸含量)
^(d) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)(高ポリ酸含量)
^(e) {(ポリアミド6+ステアリン酸カルシウム)の特性値−ポリアミド6の特性値}／ポリアミド6の特性値 Table 11
(Polyamide 6) vs. (Polyamide 6 + 0.35% calcium stearate) composite piece when dried

^(a) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.)
^(b) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) (low polyacid content)
^(c) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) (medium polyacid content)
^(d) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) (high polyacid content)
^(e) {characteristic value of (polyamide 6 + calcium stearate) −characteristic value of polyamide 6} / characteristic value of polyamide 6

^(a) γ-アミノプロピルトリエトキシシラン(GE Silicones)/ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)(低ポリ酸含量)
^(c) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)(中ポリ酸含量)
^(d) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)(高ポリ酸含量)
^(e) {(ポリアミド6+ステアリン酸カルシウム)の特性値−ポリアミド6の特性値}／ポリアミド6の特性値 Table 12
After aging for 500 hours at 120 ° C in water / glycol mixture
Properties of (polyamide 6) vs. (polyamide 6 + 0.35% calcium stearate) composite pieces

^(a) γ-aminopropyltriethoxysilane (GE Silicones) / blocked isocyanate polyurethane dispersion (Bayer Corp.)
^(b) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) (low polyacid content)
^(c) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) (medium polyacid content)
^(d) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) (high polyacid content)
^(e) {characteristic value of (polyamide 6 + calcium stearate) −characteristic value of polyamide 6} / characteristic value of polyamide 6

From the data obtained and shown in Tables 11 and 12, the negative values caused by the presence of calcium stearate in polyamide 6 for tensile strength, Charpy notch, and Izod notched and unnotched impact strength. It can be seen that the effect is mitigated by the presence of the appropriate amount of polyacid in the two-part sizing formulation of the present invention. Examples 5, 6 and 7 differ only in the polyacid content, and the polyacid content increases in the following manner: Example 5 (low acid content) → Example 6 (medium acid content) → Example 7 (high acid content). It should be noted. Referring to Table 11, an example of the reduction in negative effects caused by the presence of calcium stearate in the polyamide is shown in Example 6. In the presence of calcium stearate, the Charpy notch impact strength decreased from 101.3 KJ / m ² to 94.8 KJ / m ² , but this data is similar to Example 4 (in the presence of calcium stearate, Charpy notch impact strength was reduced. Demonstrate the improvement over the Charpy notch impact strength of polyacid-free composites (reduced from 98.4 KJ / m ² to 90.1 KJ / m ² ). By including an appropriate amount of polyacid in the two-part sizing formulation of the present invention, the Charpy notch impact strength in the presence of calcium stearate is the Charpy impact strength of the polyacid composite of Example 4 (90.1 KJ / m ² ) (94.8 KJ / m ² ). Reduction of the negative effect of calcium stearate present is demonstrated by Example 7, Charpy notched impact strength was reduced to 94.7KJ / m ² in the presence of stearic acid from 104.0KJ / m ^2. The data obtained from Examples 6 and 7 show a small difference of Charpy notched impact strength (94.7KJ / m ² of 94.8KJ / m ² and Example 7 Example 6), during molding of the composite product dried It suggests that there may be a plateau in the number of polyacid components required to achieve improved state mechanical properties. Similar results were obtained demonstrating reduced negative effects of calcium stearate in polyacids for tensile strength and Izod notched and unnotched impact strength.

  For Example 5, it can be seen that the relatively low level of polyacid-containing composite provides better mechanical performance than the polyacid-free polyurethane-based composite formed by the two-part sizing formulation of Example 4. This is particularly noticeable in the dry state during molding (DaM) Izod notched properties (Table 11) and tensile strength properties after hydroaging (Table 12) in the absence of calcium stearate. However, when calcium stearate was present in polyamide 6, the polyacid-containing composite of Example 5 showed a loss of mechanical properties. For example, the polyacid-containing composite of Example 5 has a dry state Charpy and Izod (notched and unnotched) impact strength (Table 11) and a tensile strength after hydroaging and a Charpy unnotched impact strength ( Table 12) showed losses compared to these same mechanical properties in the absence of calcium stearate. These mechanical property losses are clearly emphasized by the strong negative delta associated with the individual properties. Although not wishing to be bound by theory, the amount of polyacid present in the binder of the two-part sizing formulation that forms the composite product of Example 5 compensates for the carboxylic acid component consumed by negative interaction with calcium stearate. It is not high enough to do so, and as a result, the tested mechanical properties are believed to be reduced. On the other hand, as mentioned above, Examples 6 and 7 have a higher polyacid content than Example 5, and calcium stearate, as suggested by a small negative delta value for dry state during molding or properties after hydroaging. Low sensitivity to the presence of In Examples 6 and 7, the amount of polyacid present in the two-part sizing formulation is high enough to compensate for negative interactions with calcium stearate. This excess of polyacid component results in improved excellent mechanical properties, as can be seen in FIGS.

  Example 3: Performance of high polyacid content glass fibers versus low polyacid content glass fibers in a polyamide 6 composite containing calcium stearate

^(a) γ-アミノプロピルトリエトキシシラン(GE Silicones)/ブロックトポリウレタン分散系(Baxenden Chemicals)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ステアリン酸と反応したテトラエチレンペンタミン(AOC)+フルオロアルキルアルコール置換ポリエチレングリコール(DuPont)+部分的にアンモニアで中和した低Mwアクリル酸ホモポリマーの溶液(Ciba)+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)+ポリウレタン分散系(D.I.C.)+プロピレンオキシド-キャップドポリ(エチレンオキシド)から誘導された水溶性脂肪族ジアミン(Huntsman Corp.)+オキシランの混合物(EO-POコポリマー)(BASF)(低ポリ酸含量)
^(c) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)(高ポリ酸含量)
^(d) {(ポリアミド6+ステアリン酸カルシウム)の特性値−ポリアミド6の特性値}／ポリアミド6の特性値 Table 13
(Polyamide 6) vs. (Polyamide 6 + 0.35% calcium stearate) composite piece when dried

^(a) γ-aminopropyltriethoxysilane (GE Silicones) / blocked polyurethane dispersion (Baxenden Chemicals)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones) + tetraethylenepentamine (AOC) reacted with stearic acid + fluoroalkyl alcohol substituted polyethylene glycol (DuPont) + partially ammonia neutralized low Mw acrylic acid Solution of homopolymer (Ciba) + alternating copolymer of ethylene and maleic anhydride (Zeeland Chemicals) + polyurethane dispersion (DIC) + water-soluble aliphatic diamine derived from propylene oxide-capped poly (ethylene oxide) (Huntsman Corp. ) + Oxirane mixture (EO-PO copolymer) (BASF) (low polyacid content)
^(c) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) + alternating copolymer of ethylene and maleic anhydride (Zeeland Chemicals) (High polyacid content)
^(d) {characteristic value of (polyamide 6 + calcium stearate) −characteristic value of polyamide 6} / characteristic value of polyamide 6

^(a) γ-アミノプロピルトリエトキシシラン(GE Silicones)/ブロックトポリウレタン分散系(Baxenden Chemicals)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ステアリン酸と反応したテトラエチレンペンタミン(AOC)+フルオロアルキルアルコール置換ポリエチレングリコール(DuPont)+部分的にアンモニアで中和した低Mwアクリル酸ホモポリマーの溶液(Ciba)+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)+ポリウレタン分散系(D.I.C.)+プロピレンオキシド-キャップドポリ(エチレンオキシド)から誘導された水溶性脂肪族ジアミン(Huntsman Corp.)+オキシランの混合物(EO-POコポリマー)(BASF)(低ポリ酸含量)
^(c) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ブロックトイソシアネートポリウレタン分散系(Bayer Corp.)+低Mwアクリル酸ホモポリマーの溶液(Ciba)+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)(高ポリ酸含量)
^(d) {(ポリアミド6+ステアリン酸カルシウム)の特性値−ポリアミド6の特性値}／ポリアミド6の特性値 Table 14
After aging for 500 hours at 120 ° C in water / glycol mixture
Properties of (polyamide 6) vs. (polyamide 6 + 0.35% calcium stearate) composite pieces

^(a) γ-aminopropyltriethoxysilane (GE Silicones) / blocked polyurethane dispersion (Baxenden Chemicals)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones) + tetraethylenepentamine (AOC) reacted with stearic acid + fluoroalkyl alcohol substituted polyethylene glycol (DuPont) + partially ammonia neutralized low Mw acrylic acid Solution of homopolymer (Ciba) + alternating copolymer of ethylene and maleic anhydride (Zeeland Chemicals) + polyurethane dispersion (DIC) + water-soluble aliphatic diamine derived from propylene oxide-capped poly (ethylene oxide) (Huntsman Corp. ) + Oxirane mixture (EO-PO copolymer) (BASF) (low polyacid content)
^(c) γ-aminopropyltriethoxysilane (GE Silicones) + blocked isocyanate polyurethane dispersion (Bayer Corp.) + low Mw acrylic acid homopolymer solution (Ciba) + alternating copolymer of ethylene and maleic anhydride (Zeeland Chemicals) (High polyacid content)
^(d) {characteristic value of (polyamide 6 + calcium stearate) −characteristic value of polyamide 6} / characteristic value of polyamide 6

From the data obtained and shown in Tables 13 and 14, the negative values caused by the presence of calcium stearate in polyamide 6 for tensile strength, Charpy notch, and Izod notched and unnotched impact strength. It can be seen that the effect is mitigated by the presence of the appropriate amount of polyacid in the two-part sizing formulation of the present invention. In the absence of calcium stearate, the polyacid-based glass fiber composite of Example 8 is a modified dry-on-mold Charpy notch as compared to the polyacid-free polyurethane-based commercial glass fiber of Example 1 as well as Izod Notched and unnotched impact properties (Table 13), tensile strength after hydroaging and Charpy unnotched impact strength (Table 14) are shown. Thus, the polyacid performed its expected function of improving mechanical properties in the absence of calcium stearate.
However, in the presence of calcium stearate, the level of polyacid present in the two-part sizing formulation of Example 8 is not sufficient to compensate for the level of calcium stearate present in the polyamide, resulting in calcium stearate. The polyacid component was consumed by negative interaction with the dication. The low levels of polyacid present in Example 8 are as-formed dry state Charpy notched and Izod (notched and unnotched) impact strength (Table 13) and tensile strength and hydropy notched impact after hydroaging. It results in performance that is lower than the predicted performance of strength (Table 14), for example, results much lower than those observed with polyamides without calcium stearate. The high sensitivity to low polyacid level calcium stearate of Example 8 is also accentuated by these high negative delta values. On the other hand, the composite product of Example 9 contained a high level of polyacid in a two-part sizing formulation. From Tables 13 and 14, when calcium stearate is present in polyamide 6, the dry state during molding of Example 9 without Charpy notch and Izod (notched and unnotched) impact strength (Table 13) and tensile after hydroaging It can be seen that the loss induced by calcium stearate in strength and Charpy notch impact strength (Table 14) is less severe than the composite product of Example 8. The improvement in impact strength without dry Charpy notch in Example 9 is shown in the graph of FIG. Excess polyacid present in the two-part sizing formulation resulted in high mechanical performance of the composite pieces tested both before and after hydroaging, both in the presence and absence of calcium stearate in polyamide 6. . Such improved mechanical properties demonstrated in the composite product of Example 9 confirm the excellent unexpected properties of the two-part sizing formulation of the present invention.

  Example 4: Effect of calcium stearate present in polyamide 6 on the performance of polyamide 6 reinforced with polyacid-based fibers

^(a) γ-アミノプロピルトリエトキシシラン(GE Silicones)/ブロックトポリウレタン分散系(Baxenden Chemicals)
^(b) γ-アミノプロピルトリエトキシシラン(GE Silicones)+ステアリン酸と反応したテトラエチレンペンタミン(AOC)+フルオロアルキルアルコール置換ポリエチレングリコール(DuPont)+部分的にアンモニアで中和した低Mwアクリル酸ホモポリマーの溶液(Ciba)+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)+ポリウレタン分散系(D.I.C.)+プロピレンオキシド-キャップドポリ(エチレンオキシド)から誘導された水溶性脂肪族ジアミン(Huntsman Corp.)+オキシランの混合物(EO-POコポリマー)(BASF)(低ポリ酸含量)
^(c) γ-アミノプロピルトリエトキシシラン(GE Silicones)+非イオン性ポリウレタン分散系(Bayer Corp.)+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)
^(d) γ-アミノプロピルトリエトキシシラン(GE Silicones)+非イオン性ポリウレタン分散系(Bayer Corp.)+部分的にアンモニアで中和した低Mwアクリル酸ホモポリマーの溶液+エチレンと無水マレイン酸の交互コポリマー(Zeeland Chemicals)
^(e) {(ポリアミド6+ステアリン酸カルシウム(2))の特性値−ポリアミド6の特性値}／ポリアミド6の特性値 Table 15
(Polyamide 6) vs. polyamide 6 + 0.14% calcium stearate (1) and polyamide 6 + 0.35% calcium stearate (2) Drying properties during molding

^(a) γ-aminopropyltriethoxysilane (GE Silicones) / blocked polyurethane dispersion (Baxenden Chemicals)
^(b) γ-Aminopropyltriethoxysilane (GE Silicones) + tetraethylenepentamine (AOC) reacted with stearic acid + fluoroalkyl alcohol substituted polyethylene glycol (DuPont) + partially ammonia neutralized low Mw acrylic acid Solution of homopolymer (Ciba) + alternating copolymer of ethylene and maleic anhydride (Zeeland Chemicals) + polyurethane dispersion (DIC) + water-soluble aliphatic diamine derived from propylene oxide-capped poly (ethylene oxide) (Huntsman Corp. ) + Oxirane mixture (EO-PO copolymer) (BASF) (low polyacid content)
^(c) γ-aminopropyltriethoxysilane (GE Silicones) + nonionic polyurethane dispersion (Bayer Corp.) + alternating copolymer of ethylene and maleic anhydride (Zeeland Chemicals)
^(d) γ-Aminopropyltriethoxysilane (GE Silicones) + nonionic polyurethane dispersion (Bayer Corp.) + partially ammonia neutralized low Mw acrylic acid homopolymer solution + ethylene and maleic anhydride Alternating copolymers (Zeeland Chemicals)
^(e) {(characteristic value of polyamide 6 + calcium stearate (2)) − characteristic value of polyamide 6} / characteristic value of polyamide 6

Another method for demonstrating the results of high polyacid content glass fibers over traditional polyacid-free or low polyacid-based glass fibers is to perform its performance in polyamide formulations containing increasing levels of magnesium stearate. To compare. Table 15 shows the mechanical properties of polyamide 6 composite pieces based on two different glass fibers produced on an industrial scale. In each example, for polyamide 6 (no calcium stearate), for polyamide 6 containing 0.14% calcium stearate (1) to the compound, and for polyamide containing 0.35% calcium stearate (2) to the compound For 6, data on the mechanical properties of the composite were collected. The level of polyacid (as LOI) increases from Example 1 → Example 8 → Example 10 → Example 11. The specific LOI for each example is shown in Table 2.
In Table 15, in the absence of calcium stearate, the polyacid-based product functions similarly to the polyacid-free polyurethane-based glass fiber of Example 1 (e.g., tensile strength) or performs better (e.g., It can be seen that Charpy and Izod notched impact strength). At intermediate levels of calcium stearate, the impact properties of the low polyacid content candidate of Example 8 are significantly affected. On the other hand, the composites of Examples 10 and 11 with higher polyacid content show acceptable impact properties not only under intermediate levels of calcium stearate but also in the presence of higher amounts of calcium stearate. These results are shown in FIG. FIG. 5 shows the relative performance of glass fibers in the relevant Charpy notch properties of DaM tested polyamide 6 composites containing different levels of calcium stearate. It should be noted that the tensile strength properties are not very dependent on the level of calcium stearate present in the compound.

The foregoing description of specific embodiments fully clarifies the general nature of the present invention, so that by applying knowledge within the skill of the art, including what is cited herein, the generality of the invention The specific embodiments can be easily modified and / or adapted to various applications without departing from the concept and without undue experimentation. Accordingly, such adaptations and modifications are intended to be within the equivalent meaning and scope of the disclosed embodiments, based on the teachings and guidance presented herein. The terminology or terminology used herein is for the purpose of explanation and not the purpose of limitation, so the terminology or terminology used herein is presented herein in conjunction with the knowledge of those skilled in the art. It should be understood by those skilled in the art in light of the teachings and guidance provided.
The invention of this application has been generally described and specific embodiments have been described. While this invention has been shown to be considered a preferred embodiment, a wide variety of alternatives known to those skilled in the art can be selected within the general disclosure. The invention is not limited in any other manner except as set forth in the appended claims.

Graph of polyamide 6 and polyamide 6 / calcium stearate composite pieces in the dry state during molding (DaM) Izod notched impact test. Graph of Charpy notch impact test in the dry state when molding (DaM) for polyamide 6 and polyamide 6 / calcium stearate composite pieces. Graph of Charpy notch impact test after hydroaging polyamide 6 and polyamide 6 / calcium stearate composite pieces. Graph of Charpy notch impact test in the dry state when molding (DaM) for polyamide 6 and polyamide 6 / calcium stearate composite pieces. Graph of Charpy notch impact test in the dry state when molding (DaM) for polyamide 6 and polyamide 6 / calcium stearate composite pieces.

Claims (45)

A two-part sizing formulation for sizing of reinforcing fibers used to form composite products when used in combination with polymers containing dications or higher ionic cations,
A binder composition comprising at least one high acid number polyacid containing an acid component, wherein the acid component is more than the amount of the dication or higher ionic cation present in the polymer. Said two-part sizing formulation, present in large quantities.   The amount of the acid component is sufficient to retain at least a portion of the acid component after interaction with the dication or higher cation cations during formation of the composite material. 2 part sizing formulation.   The two-part sizing formulation of claim 1, wherein the at least one high acid number polyacid is present on the reinforcing fibers in an amount sufficient to provide a loss on ignition of up to about 2.0%.   The at least one high acid number polyacid is formed by polymerization of maleic anhydride and at least one other monomer copolymerized with maleic anhydride, maleic acid, maleic acid and 2. The two-part sizing formulation of claim 1, which is a copolymer formed by polymerization with at least one other monomer that copolymerizes, and a polyacid selected from high acid number polycarboxylic acids.   5. The two-part sizing formulation of claim 4, wherein the at least one high acid number polyacid is an ethylene-maleic acid copolymer.   The two-part sizing formulation of claim 1, wherein the high acid number is from about 300 to about 950.   The two-part sizing formulation of claim 1, wherein the size composition comprises a coupling agent and a first film-forming agent.   2. The two-part sizing formulation according to claim 1, wherein the binder composition further comprises a second film forming agent, and the first and second film forming agents are the same or different from each other.   9. The two-part sizing formulation of claim 8, wherein at least one of the first and second film formers is a non-blocked isocyanate based polyurethane film former. A two-part sizing formulation for sizing of reinforcing fibers used to form a composite when used in combination with a polymer containing a dication or a higher ionic cation,
A size composition containing a first film-forming agent; and a binder composition, wherein the binder composition is formed by polymerization of maleic anhydride and at least one other monomer copolymerized with maleic anhydride Copolymer, a copolymer formed by polymerization of maleic acid with at least one other monomer copolymerizable with maleic acid, and at least one high acid number polyacid selected from high acid number polycarboxylic acids Said two-part sizing formulation.   The at least one high acid number polyacid contains an acid component, and the acid component is present in an amount greater than the amount of the dication or higher ionic cation present in the polymer. 10 two-part sizing formulations.   12. The two-part sizing formulation of claim 11, wherein the high acid number is from about 300 to about 950.   11. The two-part sizing formulation of claim 10, wherein the high acid number polyacid is present on the reinforcing fiber in an amount sufficient to provide a loss on ignition of up to about 2.0%.   14. The two-part sizing formulation of claim 13, wherein the binder composition further comprises a second film-forming agent, and the first and second film-forming agents are the same or different from each other.   15. The two-part sizing formulation of claim 14, wherein at least one of the first and second film formers is a non-blocked isocyanate based polyurethane film former. A reinforced composite product,
A polymer matrix containing a dication or a higher ionic cation; and a plurality of strands of reinforcing fibers, the strand comprising:
An inner coating of a size composition; and an outer coating of a binder composition comprising at least one high acid number polyacid containing an acid component, wherein the acid component is present in the polymer matrix Said reinforced composite product present in an amount greater than the amount of high ionic cation.   The at least one high acid number polyacid is copolymerized with maleic anhydride and at least one other monomer copolymerized with maleic anhydride, maleic acid and maleic acid. 17. The reinforced composite product of claim 16, which is a copolymer formed by polymerization with at least one other monomer, and a polyacid selected from polycarboxylic acids.   18. The reinforced composite product of claim 17, wherein the high acid number polyacid is present on the reinforced fiber in an amount sufficient to provide a loss on ignition of up to about 2.0%.   19. The reinforced composite product of claim 18, wherein the at least one high acid number polyacid is an ethylene-maleic acid copolymer.   The reinforced composite product of claim 16, wherein the at least one high acid number is from about 300 to about 950.   The reinforced composite product of claim 16, wherein the size composition comprises a first film-forming agent.   The reinforced composite product according to claim 21, wherein the binder composition further comprises a second film-forming agent, and the second film-forming agent is the same as or different from the first film-forming agent.   23. The reinforced composite product of claim 22, wherein at least one of the first and second film formers is a non-blocked isocyanate based polyurethane film former. A sized reinforcing fiber used to form a composite product when used in combination with a polymer containing a dication or a higher ionic cation,
Comprising a reinforcing fiber at least partially coated with a two-part sizing formulation, wherein the two-part sizing formulation comprises:
A binder composition comprising a size composition, and at least one high acid number polyacid containing an acid component,
The sized reinforcing fiber, wherein the acid component is present in an amount greater than the amount of the dication or higher ionic cation present in the polymer.   25. The amount of the acid component is sufficient to retain at least a portion of the acid component after interaction with the dication or higher cation cations during formation of the composite material. Sized reinforcing fiber.   25. The sized reinforcing fiber of claim 24, wherein the at least one high acid number polyacid is present on the reinforcing fiber in an amount sufficient to provide a loss on ignition of up to about 2.0%.   25. The sized reinforcing fiber of claim 24, wherein the high acid number is from about 300 to about 950.   25. The sized reinforcing fiber of claim 24, wherein the size composition comprises a coupling agent and a first film forming agent.   29. The sized reinforcing fiber according to claim 28, wherein the binder composition further comprises a second film forming agent, and the first and second film forming agents are the same or different from each other.   29. The sized reinforcing fiber of claim 28, wherein at least one of the first and second film formers is a non-blocked isocyanate based polyurethane film former.   The at least one high acid number polyacid is formed by polymerization of maleic anhydride and at least one other monomer copolymerized with maleic anhydride, maleic acid, maleic acid and 25. The sized reinforcing fiber of claim 24, wherein the sized reinforcing fiber is a copolymer formed by polymerization with at least one other monomer to be copolymerized and a polyacid selected from high acid number polycarboxylic acids. A sized reinforcing fiber comprising reinforcing fibers at least partially coated with a two-part sizing formulation, wherein the two-part sizing formulation comprises:
A size composition containing a first film-forming agent; and a copolymer formed by polymerization of maleic anhydride and at least one other monomer copolymerizable with maleic anhydride, maleic acid and maleic acid. Said sized reinforcing fiber comprising a copolymer formed by polymerization with at least one other monomer to be polymerized and a binder composition comprising at least one high acid number polyacid selected from high acid number polycarboxylic acids .   33. The sized reinforcing fiber of claim 32, wherein the high acid number is from about 300 to about 950.   35. The sized reinforcing fiber of claim 32, wherein the high acid number polyacid is present on the reinforcing fiber in an amount sufficient to provide a loss on ignition of up to about 2.0%.   33. The sized reinforcing fiber according to claim 32, wherein the binder composition further comprises a second film forming agent, and the first and second film forming agents are the same or different from each other.   33. The sized reinforcing fiber of claim 32, wherein at least one of the first and second film formers is a non-blocked isocyanate based polyurethane film former. A method for producing a sized reinforcing fiber for reinforcing a composite product containing a dication or a higher ionic cation, comprising the following steps:
Applying a size composition to at least a portion of the reinforcing fibers to form a coated reinforcing fiber material; and applying a binder composition to the coated reinforcing fiber material;
And the binder composition comprises at least one high acid number polyacid containing an acid component, wherein the acid component is greater than the amount of the dication or higher ionic cation in the composite article. Said method, present in an amount.   38. The method of claim 37, wherein the size composition comprises a film forming agent.   39. The method of claim 38, wherein the amount of the acid component is sufficient to retain at least a portion of the acid component after interaction with the dication or the higher ionic cation.   38. The method of claim 37, wherein the at least one high acid number polyacid is present on the reinforcing fiber in an amount sufficient to provide a loss on ignition of up to about 2.0%. A method for producing reinforcing fiber pellets, comprising the following steps:
Forming a coated reinforcing fiber by at least partially coating the reinforcing fiber with a size composition comprising a first film-forming agent;
Cutting the coated reinforcing fiber to produce a shortened long coated reinforcing fiber,
Coating the shortened long coated reinforcing fiber at least partially with a binder composition to form a binder coated shortened long reinforcing fiber (the binder composition is at least one copolymerized with maleic anhydride and maleic anhydride). A copolymer formed by polymerization with other monomers, a copolymer formed by polymerization with maleic acid and at least one other monomer copolymerized with maleic acid, and at least one selected from high acid number polycarboxylic acids Including a high acid number polyacid of a seed), and pelletizing the binder-coated shortened long reinforcing fibers to form reinforcing fiber pellets,
A method comprising the steps of:   42. The method of claim 41, further comprising densifying the reinforcing fiber pellets.   43. The method of claim 42, wherein the at least one high acid number polyacid is present on the binder-coated shortened length reinforcing fibers in an amount sufficient to provide a loss on ignition of up to about 2.0%.   44. The method of claim 43, wherein the binder composition further comprises a second film forming agent, and the first and second film forming agents are the same or different from each other.   45. The method of claim 44, wherein at least one of the first and second film formers is a non-blocked isocyanate based polyurethane film former.

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