JP2002506414A - High solubility sizing composition for fibers - Google Patents

Abstract

  (57) [Summary] A high solubility sizing composition is provided that can be applied to glass fibers useful for reinforcing polymeric materials. The sizing composition comprises a first film-forming agent comprising a polyether-based or polyester-based thermoplastic polyurethane derived from a saturated, non-crosslinkable polyether or polyester; at least i) a vinyl acetate glycidyl methacrylate copolymer and ii. A) a second film-forming agent containing one of components selected from a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer; a silane coupling agent; and water. The use of glass fibers coated with the present high solubility sizing composition advantageously enables the production of low-color or non-color molded articles with improved surface appearance and color uniformity.

Description

Description: FIELD OF THE INVENTION The present invention relates to a high solubility size composition used for fibers, in particular sheet molding compounds. And a high solubility sizing composition for use in glass fibers used as reinforcement for bulk molding compounds. The use of such a sizing composition gives the resulting molded article a smooth and uniform appearance. BACKGROUND OF THE INVENTION The use of glass fibers as reinforcement for polymeric materials such as sheet molding compounds (SMC) and composites formed by bulk molding compound (BMC) processes. Are well known in the art. Such composites are formed using glass fiber reinforcement, which provides the resulting composite with dimensional stability and excellent mechanical properties. For example, glass fibers provide dimensional stability because they do not shrink or stretch in response to changes in atmospheric conditions. Furthermore, glass fibers have high tensile strength, heat resistance, moisture resistance, and high thermal conductivity. Glass fibers are usually manufactured by feeding ceramic in a molten form to a bushing, drawing the fibers from the bushing, and then bundling the fibers into tows or strands. A sizing composition, or chemical treatment, is typically applied after the fibers are withdrawn from the forming furnace, which protects the fibers from breaking during subsequent processing and strengthens the matrix. Improves coexistence of resin and fiber. The sizing treated strands are typically wound on a collet, packaged, dried, and wound together into rovings. In the winding step, an antistatic coating is applied to the roving. The roving is then cut and mixed with the matrix resin in a sheet or bulk molding compound to form a molded composite. Typical sizing compositions may include coupling agents, film-forming agents, lubricants, emulsifiers, or antistatic agents, which are either dissolved in water or dispersed in water (in the form of an emulsion or dispersion). Have been. However, certain organic solvents commonly used to emulsify or disperse the film formers used in SMC sizing compositions, such as styrene and xylene, are flammable and are known to be fire and health hazardous. There's a problem. Lithium chloride is also commonly used in sizing compositions as an antistatic agent, but tends to adversely affect yield and is therefore undesirable for use. Accordingly, it would be desirable to use a sizing composition that does not use undesirable organic solvents or metal halide salts. It may also be preferable to use a sizing composition that will give a smooth surface to the resulting molded article. For example, US Pat. No. 4,338,233 to Das et al. Describes an aqueous sizing composition for glass fibers that provides a smooth surface to the molding compound. However, such sizing compositions have low solubility due to the inclusion of one or more crosslinkable film-forming polymers, which become insoluble when crosslinked. Such low solubility sizing compositions are desirably used for automotive or Class A applications where the resulting composite article is painted. However, low solubility sizing compositions are not desirable when the fibers are used in non-colored or light-colored sheet moldings that are not subsequently coated. This is because the fiber strands remain integral in the molding compound, i.e., the fibers are not sufficiently defilamentized. Thus, a fiber network is visible in the resulting molded article. In the manufacture of structured, low-colored or non-colored articles, the sizing composition must be highly soluble so that the individual fibers are well dispersed or sufficiently wetted by the matrix resin. No. This promotes better defilamentation or strand breakage of the fiber strands, thereby reducing fiber fidelity and thus improving the uniformity or smooth appearance of the resulting composite surface. The sizing composition promotes an increase in the interface between the individual fibers and the matrix resin, resulting in better mechanical properties required for structural applications. Thus, there is still a need in the art for improved sizing compositions that exhibit high solubility, are easy to manufacture and easy to apply to fibers. Further, there is a need for sizing compositions that do not use environmentally undesirable solvents or metal halide salts to improve the surface appearance of non-colored or low-colored parts formed by sheet or bulk forming methods. Exists in this field. Summary of the Invention These needs are met by the present invention, which provides improved sizing compositions for glass fibers or non-glass fibers used to reinforce polymeric materials. The sizing composition is highly soluble but dissolves slowly and aids in defilamentation of the fibers during the processing process. This in turn reduces the visibility of the fibers in the resulting molded article, giving a more uniform color and surface appearance. High solubility sizing agents also improve the flow of seed molding paste into bulk molds in injection molding applications. This will be described in detail below. Further, the sizing composition is essentially free of environmentally harmful organic solvents and metal halide salts. In accordance with one aspect of the present invention, there is provided a highly soluble sizing composition for glass fiber treatment used to reinforce the polymeric material. The sizing composition comprises: a) a first film former comprising a polyether-based or polyester-based thermoplastic polyurethane formed from a non-crosslinked saturated polyether or polyester; b) i) a vinyl acetate glycidyl methacrylate copolymer, or ii) a second film-forming agent comprising a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer; c) a silane coupling agent; and d) water. Preferably, the sizing composition has a solubility of at least 70% in styrene, toluene or acetone, and more preferably has a solubility of about 70 to about 90%. The film-forming polyurethane in the sizing composition is preferably in the form of an anionic or non-ionic dispersion. The polyurethane maintains a high solubility of the sizing composition because it is a linear polymer formed from a non-crosslinked saturated polyether or polyester. In addition, polyurethanes have elastomeric properties to impart flexibility to the fibers, reduce fiber brittleness, and improve contact between the fibers and equipment during processing. The second film forming agent in the sizing composition may be a vinyl acetate glycidyl methacrylate copolymer. The copolymer preferably has an average molecular weight (Mw) of about 50,000 to about 150,000, for example, about 90,000 or 100,000. Alternatively, the second film former may comprise a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer. Preferably, the homopolymer may replace about 0 to 80% by weight of the copolymer solids component in the composition. Either the polyurethane and copolymer or the polyurethane and copolymer / homopolymer mixture protects the glass fibers from damage during the processing step and gives the fibers compatibility with the matrix resin. The silane coupling agent is preferably selected from the group consisting of amino silanes, reaction products of amino silanes with maleic anhydride, vinyl silanes, ureido silanes, and blends thereof. The sizing composition may optionally include a pH adjusting agent such as acetic acid to adjust the pH level of the composition. Preferably, the pH of the sizing composition is from about 4 to about 6. The amounts of the components of the present sizing composition may be from 5 to 60% of the first film forming agent, from 40 to 95% of the second film forming agent, and from 1 to 10% of the coupling agent as percent by weight solids. In a preferred embodiment, the first film former (polyether-based or polyester-based thermoplastic polyurethane) is present in the sizing composition at about 10 to about 40% by weight solids, and The agent is present at about 60 to about 85% by weight solids, and the silane coupling agent is present at about 1 to about 15% by weight solids. More preferably, based on total body weight, the sizing composition comprises from about 25 to about 35% of a first film former, from about 55% to about 65% of a second film former, from about 5 to about 10%. % Silane coupling agent. Preferably, the composition is aqueous, ie, the solvent or carrier for the solid is water. The size composition may also include a sufficient amount of a pH adjuster, such as acetic acid, such that the composition has a pH of about 4 to 6. The present invention also includes a method of coating the sizing composition on a plurality of glass fibers used to reinforce the polymeric material. The method includes applying the sizing composition described above to a plurality of glass fibers to form a coated fiber and drying the sizing composition on the fibers. Preferably, the size is dried to be present at about 0.6 to about 2.0% by weight on the fiber. The sized glass fiber strands so dried can be advantageously used as reinforcing materials in polymeric materials such as sheet-forming and bulk-forming compounds. The resulting molded composite article does not show a fiber network pattern below the composite surface. This is particularly advantageous in SMC molding applications where the molded article is not painted and a uniform surface appearance is important. In addition, the sizing compositions of the present invention exhibit excellent wettability in polyester and vinyl ester resins, which allows the formulator to increase filler loading. The sizing composition also advantageously has excellent mechanical properties, enhanced mold flowability, fluff and electrostatic properties, and excellent runnability and choppability. are doing. Accordingly, an object of the present invention is to provide a composite for fibers used in reinforcement applications that has an improved surface appearance that can be easily manufactured and applied to the fiber, and that the organic solvent or metal halide It is to provide a high solubility sizing composition that does not use salts. BRIEF DESCRIPTION OF THE FIGURES This application contains at least one drawing executed in color. Copies of this patent with color drawings will be provided upon request and payment of the US Patent and Trademark Office. This figure shows the relationship between the solubility of the sizing agent and the surface appearance of the molded article reinforced with the sizing fiber according to the present invention in color. Detailed description of the invention and preferred embodiments The high solubility sizing composition of the present invention offers many advantages over conventional low and high solubility sizing compositions. The size composition of the present invention has a high solubility but dissolves slowly, thereby allowing good wet-through of the fiber strands by the matrix resin. This is explained further below. The high solubility sizing composition also enhances the compatibility of the fiber with the matrix resin being reinforced. Composite articles reinforced with the sizing fibers of the present invention have improved uniform and smooth surfaces. This is particularly advantageous for low-colored sheet molding compounds such as white compounds or non-colored (transparent) compounds. The use of high solubility sizing agents eliminates or reduces the need to add expensive dyes to the molded article to hide the fiber network and to hide the non-uniform coloration of the product. In addition, composite articles reinforced with fibers sized with the polyether-based polyurethane formulations of the present invention exhibit improved demolding character isteics. In addition, the sizing composition is environmentally safe because it is essentially free of harmful organic solvents and lithium chloride or other metal halide salts. The size has also been found to improve the flow of compound pastes in injection molding applications. This is due to the low dissolution rate of the sizing agent. Since the sizing agent dissolves slowly, the fibers stay together and stay longer, ie, the fibers are less susceptible to premature defilamentation than other high solubility sizing agents. This improves the flow of the SMC and BMC resin or paste. As a result, molding a compound comprising fibers coated with the sizing agent of the present invention will require less pressure to fill the mold. In addition, by improving the flow of the paste, the sizings of the present invention allow for thinner wall molding and more complex molding configurations using the same pressure. The sizing agent is preferably in styrene, toluene or acetone, as measured by the Soxhlet acetone solubility test described in Dana et al., "Sheet Molding Compound Glass Fibers", PPG Industries, page 130. It has a solubility of, for example, 70% to 90%. The disclosure of this document is incorporated herein. As mentioned above, high solubility sizing agents dissolve slowly, which facilitates excellent wet-out and wet-through of glass fiber bundles or strands. Wet out refers to the degree to which the strand bundle is coated or encapsulated in the polymer matrix resin. Wet-through refers to the rate at which the polymer matrix resin can flow through a glass bundle or strand as a result of the compression that occurs during compounding of the molding compound. Typically, conventional high solubility sizing compositions had low wet-through. Because the sizing agent dissolves quickly, the fiber bundles break apart and the resin becomes too fine to flow through. However, the sizing agents of the present invention dissolve slowly, the fiber bundles are kept together for a longer period of time, and the resin can flow through the space between the individual fiber bundles. However, due to the chemical compatibility of the sizing agents, rapid wetting of the strands also occurs, which is desirable. The sizing composition of the present invention preferably comprises a polyester-based thermoplastic polyurethane present in the form of an anionic dispersion or a polyether-based polyurethane preferably present in the form of a non-ionic dispersion. Preferably, the polyurethane is formed from the reaction product of a polyether or polyester diol and a diisocyanate. Preferred diisocyanates are aliphatic diisocyanates, such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate or blends thereof. Other suitable diisocyanates include, for example, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate, 1,6-hexamethylene diisocyanate, 4,6'-xylene diisocyanate, para-phenylene Includes diisocyanate, cyclohexyl diisocyanate, 3,3'-tolidene 4,4'-diisocyanate, and 3,3'-dimethyl-diphenylmethane 4,4'-diisocyanate. More particularly, preferred polyester-based polyurethanes are polyurethane ionomers containing pendant ionic groups such as sulfonate or carboxylate groups. The ionic groups allow the polyester-based polyurethane to form a stable dispersion in water. A specific polyester-based polyurethane that is preferred for use in the present invention is Impranil DLS. ^TM ). It comprises about 50% by weight of solids and is an aliphatic polyester-based polyurethane available from Bayer AG. Aliphatic-cycloaliphatic poly in nonionic water emulsion form available from Savid Terurethane polymer dispersions, both available from Bayer, and Baybond MWH 0949 (prepared from IPDI and HDI, containing anionic carboxylate groups (sodium salt), containing 40% solids, pH 8. 7, polyester polyurethane anionic dispersion with a viscosity of 13S according to DIN 53211) and Baybond MWH 0948 (prepared from IPDI and HDI, with anionic sulfonate groups (sodium salt), containing 39% solids, pH 7. 7, polyester polyurethane anionic dispersions of viscosity 12S according to DIN 53211, which do not contain organic solvents or crosslinkable blocked isocyanate groups, which are also available from Bayer. A preferred polyether-based polyurethane is RET 11266 (a nonionic polyether polyurethane dispersion available from Bayer, containing about 35% by weight solids). As a second film former, the sizing composition may comprise a random copolymer of vinyl acetate and glycidyl methacrylate. Preferably, the copolymer contains about 1 to 5 parts of glycidyl methacrylate per 100 parts of vinyl acetate (all parts are by weight unless otherwise specified). More preferably, the copolymer contains 2 parts of glycidyl methacrylate per 100 parts of vinyl acetate. Low glycidyl methacrylate content may inhibit binding to glass. Conversely, if the glycidyl methacrylate content is high, many reactions may occur in the chain, resulting in increased solubility or insolubility. On the other hand, the preferred ratio increases the molecular weight and gives sufficient binding to the glass, while maintaining high solubility. Suitable copolymers for the second film former include Fulatex PD-0166 and Fu1atex PN-6019, both available from Fuller. Fu1atex PN-601 9 is a modified vinyl acetate copolymer in an anionic / nonionic surfactant system with the following typical properties: solids content 53.5 to 55.5 wt%; viscosity 100 to 600 cps; pH 3. 5 to 4.5; and a residual monomer content of 0.5% or less. A particularly preferred copolymer is Vinamul ^TM 88127, which is available from Vinamul UK or product number NS25-1971 from National Starch. The copolymer typically contains 53.5 to 55.5% by weight of solids, has a pH of 4 to 5, and a viscosity of 100 to 400 mPas. Analysis of Vinamul 88127 and Fulatex PN-6019 gave the following results: Alternatively, the second film forming agent may be a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer. Homopolymers may or may not be plasticized. Suitable homopolymers include Vinamul 88154 (Vinamul UK) or Fulatex PD366 (Fuller). The homopolymer can replace about 0 to about 80% by weight of the solids content of the copolymer in the sizing composition. Polyurethane and copolymer or polyurethane and copolymer / homopolymer mixtures maintain high solubility of the sizing agent and at the same time regulate the dissolution rate. The solubility and dissolution rate of the sizing agent are directly affected by the molecular weight of the copolymer, the molecular weight of the homopolymer, and the mass ratio of homopolymer to copolymer. For example, a copolymer having a high molecular weight will reduce the dissolution rate of the sizing agent. The dissolution rate also decreases as the molecular weight of the homopolymer increases. Vinyl acetate glycyl methacrylate copolymer has a high dissolution rate. However, when the copolymer is mixed with a polyurethane having a low dissolution rate or with a higher molecular weight homopolymer, the dissolution rate is reduced without affecting the solubility of the final sizing agent. This provides an improvement over conventional sizing compositions that include a crosslinkable coating former. The crosslinking reaction reduces the dissolution rate, but also reduces the solubility, which is undesirable. The sizing composition may preferably include a silane coupling agent. The silane coupling agent acts to enhance the adhesion of the film-forming copolymer to the glass fibers and reduce fuzzing or fiber filament breakage during the process. It is believed that this enhanced attachment is due to a reaction between the coupling agent and the epoxy groups in the copolymer. Suitable coupling agents include, but are not limited to, aminosilanes, the reaction product of aminosilanes with maleic anhydride, vinylsilanes, ureidosilanes, and blends thereof. A preferred coupling agent is A1100, which is commercially available from OSI Specialties and contains 52% by weight of solid active silane after hydrolysis. Also, hydrolyzed A1100 aqueous solution is suitable for use. Commercially available under the name 51 (40% solution). The sizing composition further comprises an amount of water sufficient to dissolve or disperse the active solid for coating. Preferably, the weight percent of the first film forming agent, the second film forming agent, and the coupling agent in the composition as total solids is from about 4 to about 16% by weight. The sizing composition may optionally include a pH adjusting agent, such as an organic acid, in an amount sufficient to provide the sizing composition with a pH of about 4 to 6. The preferred organic acid is acetic acid. The size composition may optionally include processing aids such as lubricants for ease of manufacture. For example, small amounts of conventional water-based lubricants may be used, preferably up to 0.14% by weight of the sizing composition. Examples of lubricants that may be used for addition to the size composition include one or more of the following: a nonionic surfactant, such as Pluronic L101 (available from BASF) or Synperonic PE / Block copolymers of ethylene oxide and propylene oxide, such as L101 (available from ICI) or octylphenoxypolyethoxyethanol, such as Triton X100 (available from Rohm and Hass); polyvinylpyrrolidone, e.g. Luviskol K grade ( Available from BASF); imidazolines, for example alkyl imidazoline derivatives such as Tego cationic softener (available from Th. Goldshmidt); alternatively, polyethyleneimine polyamide salts, for example Emery 6760 (available from Henkel) . The size composition is preferably prepared by diluting and mixing each of the polyurethane, copolymer and coupling agent separately with water to form a pre-mix, before combining with the other ingredients in the main mixing tank. You. Acetic acid is optionally added to the coupling agent pre-mix or the combined mixture to bring the final pH to 4-5. After all of the pre-mixed ingredients have been added to the main mixing vessel, sufficient water is added so that the total solids content of the composition is from about 4 to about 16% by weight. The sizing composition may be prepared by any suitable equipment and technique known in the art. As noted above, the sizing is preferably applied to the fiber and dried such that the sizing is present on the fiber in an amount of about 0.6 to about 2.0% by weight of the fiber. This is measured by the loss on ignition (LOI) of the roving. Ignition loss means the loss of mass after heating due to combustion or high temperature decomposition to remove the organic sizing agent from the fibers. To achieve the desired solids content on the fibers, the amount of water used to dilute the sizing mixture will vary. For example, to obtain a LOI of 1.2% on the fibers, the following sizing composition may be used (% based on the total weight of the composition): 4.8 as the first film former Wt% (6,675 g) Impranil DLS; 17.5 wt% (24,483 g) Vinamul 88127 as the second film former; 1.2 wt% (1,691 g) A1100 as the silane coupling agent; 0.6 wt% (829 g). Acetic acid; and 75.9% by weight (106,322 g) water. Examples of compositions having a LOI value of 0.6% are as follows: 1.50% (6,675g) Impranil DLS; 5.50% (24,483g) Vinamul 88127; 0.38% (1,691g) A1100; 0.19% by weight (829g) acetic acid; and 92.43% by weight (411,322g) water. To obtain a LOI of 2.0%, 6.1% (6,675 g) of Impranil DLS; 22.3% (24,483 g) of Vinamul 88127; 1.5% (1,691 g) of A1100; 0.8% (829 g) A composition may be prepared which contains acetic acid; and 69.4% by weight (76,322 g) water. The sizing composition is preferably applied to fibers having a diameter of about 9 to 20 micrometers, with fibers having a diameter of about 14 to about 16 micrometers being more preferred. The preferred roving yield or tex for a bundle of sized fibers is between 15 and 500 tex, especially 75 tex. Tex is the value of the mass per unit length of roving expressed in g / km. Texturing is used to verify that a constant glass load has been achieved during the compounding process and involves breaking the strands using a comb as the strands are wound. The number of strand bundles divided by the comb is equal to the number of splits. For example, a strand showing a 300 tex bush divided into four splits creates a strand consisting of four bundles of 75 tex each. The 400 tex strand is divided into 6 splits, giving a bundle of 67 tex per bundle. The text of the strand formed from the bush naturally depends on the type of bush and the fiber diameter. Text values from 1200 to 9600 are preferred for aggregate strands, and 2400 to 4800 tex are more preferred. Such a tex value allows sufficient glass redistribution on the SMC line. Larger strands of text are difficult to cut, causing non-uniform redistribution of the glass. Smaller tex strands have better fiber dispersion, but are more expensive to manufacture and handle (requires more cake per SMC line, including creels and feed tubes). Values of 2400 and 4800 tex are standard values. In some cases, such as in BMC preparation, 9600 tex can be used. The smaller (thinner) the bundle tex, the better the glass redistribution in SMC molding. Thinner bundle tex also improves mechanical properties. The most common tex ranges from 37.5 to 75 tex. Although the sizing composition is described as applied to glass fibers, Naturally, it can be applied to synthetic fibers (non-glass fibers), carbon fibers or graphite fibers, silicon carbide (SiC) fibers, polymer fibers (preformed or continuously formed), and other non-glass fibers. is there. The sizing composition may be applied to the fibers by conventional methods known in the art. Generally, the sizing composition is applied to the fibers as they exit the bush using an applicator roller, as described in U.S. Patent Application No. 08 / 311,817, filed September 26, 1994. You. The disclosure of this patent application is incorporated herein. In the manufacture of glass fibers, the fibers are separated into strands in a gathering shoe and wound into a collet to form a package or cake. The package is preferably cured in an oven at a temperature of 100 ° C. to 130 ° C. for 12 to 18 hours to remove water and to cure the size at the surface of the fibers. This package is then placed in a creel and the strands are combined and wound into a continuous roving. Preferably, an antistatic agent is applied to the roving in this winding step. Suitable antistatic agents include Emerstat ^TM Included are 6660, a quaternary ammonium antistatic agent available from Henkel, and FC-430, a product containing fluoroaliphatic polymer esters available from 3M. The antistatic agent is preferably applied to rovings at about 0.001 to about 0.3% by weight. In some cases, the wound rovings may be subjected to a suitable postovening treatment to improve properties without substantially affecting solubility. For example, to improve run-out, the wound antistatic treated roving is unpackaged (so that hot air can easily circulate around it) and placed on a shelf, then It is placed in a ventilated furnace and heated at a temperature of about 130 ° C for about 2 to 8 hours. The exact conditions are appropriately chosen for a particular roving bobbin size and text. Such processing is preferably performed to improve runout at the end of the bobbin. The roving is then cooled. The roving is then properly packaged and shipped to the customer for the desired SMC, BMC or other processing into the composite article. Non-colored SMC formulations or bases that can be used in the treatment with the glass fibers of the present invention are unsaturated polyester resins as a matrix, thermoplastic low-profile additives such as polyethylene to suppress resin shrinkage during polymerization, It may include fillers such as calcium carbonate, and thickeners such as magnesium oxide. The paste may also include an organic peroxide to initiate cross-linking polymerization of the matrix resin, such as tertiary butyl perbenzoate, and a demolding agent such as zinc stearate. The paste is placed on a moving carrier film and the sized glass fiber rovings are fed to a shredder and cut into various lengths from about 6 mm to about 50 mm. The chopped fibers are dropped onto the resin paste, then the second carrier film is coated with the resin paste and placed (with the resin facing down) on the chopped fibers, and the glass fibers are coated with the resin paste. Wet. The glass fibers are blended with the paste in a proportion of about 30% by weight glass and about 70% by weight paste. The SMC sheet is then picked up on a storage roll. When the SMC is ready for molding, the material is cut into pieces of the desired size and shape, and the cut pieces are assembled into a charge and pattern that fills the mold cavity and fills. This charge is placed in a mold, usually equipped with a matching pair of steel dies, and compressed. The SMC is then cured, the mold is opened, and the resulting molding is removed. SMC molded articles using the sizing fibers of the present invention as reinforcement include molded electrical cabinets containing electrical networks, bathtubs, and automotive structural components. Roving of sizing fiber is useful in a wide variety of applications of SMC, such as valve covers, semi-structured and structural applications, and household and commercial electrical equipment, and can be used in sanitary and appliance equipment. Particularly useful in lightly colorable SMC formulations such as Bulk molding compound (BMC) formulations that may be used with the sizing fibers of the present invention include polyester resins, low profile thermoplastics, pigments, crosslinkers, catalysts, thickeners, molding lubricants and powdered inorganic fillers. Agent. In the BMC process, the compound may be prepared by mixing the BMC resin matrix with the sized chopped fibers using a sigma-blet mixer. Alternatively, the rovings may be withdrawn from a BMC resin dipping bath and then chopped. The resulting material is now ready for molding. Typical bulk molding compounds are processed by compression molding, transfer molding, and injection molding. An important feature in BMC molding is the flow of BMC material into the mold. As mentioned above, the sizing composition of the present invention improves the matrix resin or paste so that less pressure is used to fill the mold. BMC molded articles using the sizing fibers of the present invention as reinforcing agents include headlight reflectors, iron cases, toasters, electrical boxes, and switch bases. The present invention preferably relates to sizing agents for SMC and BMC applications, while the sizing agents are Zanella molding compounds (ZMC), premix molding compounds (doughmolding compound) (DMC), knead molding compounds (knead molding compounds). KMC), thick molding compound (TMC), continuous impregnated compound (continuously impregnated compound) (CIC), granular molding compound (GMC), nodular molding compound (NMC), pellet molding compound (TMC) PMC), may also be used for other applications. The sizing composition may also be used in reaction injection molding (RIM) due to slow dissolution and excellent wet-through. This sizing agent may also be used in resin transfer molding applications, especially in "Industrial RTM--New Developments in Molding and Preforming Technologies" (Advanced Composite Materials: New Developments and Aplication Conference Proceedings, Detroit, Mi chigan, It may be used in the Owens Corning process (September 30, 1991 to October 3, 1991). The disclosure of this document is included in the present invention. For a better understanding of the invention, reference is made to the following examples, which are intended to illustrate the invention and are not intended to limit the scope of the invention. Example 1 The sizing composition according to the invention was prepared by diluting 6.675 kg of Impranil DLS (Bayer) with 42 liters of deionized water. The solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 2.8 liters of water. Next, 24.483 kg of Vinyl 88127 (Vin amul UK) was diluted with 42 liters of deionized water, mixed for 10 minutes, transferred to the main tank and flushed with 2.8 liters of water. Next, 1691 g of A-1100 (OSI Specialites) was diluted with 28 liters of deionized water and stirred for 15 minutes. Glacial acetic acid was then added to the coupling agent solution in progressively 28 g portions, with agitation for 10 minutes between additions until the pH of the mixture reached 4-5. When such pH was reached, the mixture was transferred to the main mixing tank and flushed with 2.8 liters of water. The prepared sizing composition was applied as it exited the bush to several samples of 16 μm diameter using a conventional in-line graphite applicator roller. The resulting 400 tex fiber strand was then split into six strands and wound into a collet into a single molded cake. The molded cake was then cured at 130 ° C. for 17 hours in a conventional ventilated oven. Six such cakes were then placed on the creel and the strands were wound together into a 2400-tex continuous roving. An antistatic agent was applied as an aqueous solution to the roving at a concentration of 0.09% solids on the strand. The antistatic agent was prepared according to the following composition: The rovings were then tested for tex, loss on ignition (LOI) and solubility. The results are shown in Table I below. Example 2 A sizing composition was prepared as in Example 1. Next, the prepared sizing composition was applied to fibers having a diameter of 14 μm by a conventional method when it came out of the bush without separating. In this sample, 300 tex strands were not split to increase the size of the bundle (and thus enhance its effect on the appearance of the molded panel) and to make the coloring test easier. Eight molded cakes were assembled into 2400 tex rovings. The 2400 tex rovings were then fed by polyethylene tubing spaced 50 mm apart into a conventional SMC impregnator, a commercially available Finn & Fram shredder. The shred length was set to 25 mm. The glass was compounded with an uncolored general purpose SMC paste of the following composition: The shredding speed and the carrier speed were adjusted so that the glass and the paste were mixed at a ratio of 30% by mass of glass and 70% by mass of the paste. The obtained prepreg has a surface mass of 5 kg / m. ^Two And aged at 30 ° C. for 3 days. The panel was then formed by overlaying three layers of prepreg material in a 500T Battenfeld press so that 70% of the mold surface projection was covered. 40 to 60 kg / cm box-shaped product with dimensions of 40 cm x 60 cm x 9 cm and thickness of 3.5 mm ^Two At a pressure of 3 times. The bottom of the box was cut and used for mechanical testing and surface quality measurements as described below. Each panel was measured for color uniformity using a visible spectrophotometer using the color parameters L, a, b (CIEL ^* a ^* b ^* Adjusted based on system; ASTM method E308). For each molded specimen, 20 measurements were recorded at random on the specimen surface. Next, the variation ranges of the three color parameters L, a, b were statistically calculated. The variation range was small when the panel had a uniform surface appearance, and large when the panel did not have a uniform surface appearance. Next, the variation ranges of the color parameters were integrated into one value by the sum of the three color parameter variation ranges represented by the sum R = L variation range + a variation range + b variation range. The graph shown shows the dependence of color uniformity on strand size and solubility (measured by Soxhlet extraction). As can be seen, higher solubility corresponds to a more uniform surface of the resulting molded article. Example 3 A sizing composition was prepared as in Example 1 and coated on glass fibers having an average diameter of 16 μm. The properties of this fiber were measured and compared to those of other fibers coated with a commercially available sizing composition. The results of the comparison are shown in Table II below. The fluff run-out refers to the weight of the fluff collected when the bobbin is run out. This is done to simulate the fluff that the strand will exit the customer's creel before entering the guide tube. Fluff severity refers to fluff produced when a strand passes through a series of tensioning bars in a closed box. This simulates the fluff generated in the shredding step of the customer's line. It will be seen that the sizings of the present invention achieve the lowest fuzz levels. This has been achieved without the aid of lubricants or other processing aids that are usually applied to the fibers during manufacture and compounding to reduce fluff. Example 4 Another embodiment of the size composition according to the invention was prepared by diluting 4.918 kg of Impranil DLS with 30 liters of deionized water. The solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 3 liters of water. Next, 18.907 kg of Vinamul 88127 was diluted with 30 liters of water, stirred for 10 minutes, transferred to the main tank and flushed with 3 liters of water. Next, 1246 g of A-1100 was diluted with 20 liters of deionized water and stirred for 15 minutes. Next, 551 g of maleic anhydride was added to the coupling agent and stirred for 15 minutes. Glacial acetic acid was then added gradually to the coupling agent solution in 28 g increments, with stirring between the additions for 10 minutes until the pH of the mixture reached 4-5. When such pH was reached, the premix was transferred to the main mixing tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the volume of the mixture to 140 liters. As described in Example 1, the prepared sizing composition was applied to 16 μm fibers and the resulting 400 tex fiber strand was divided into 6 strands to form 2400 tex rovings. Three samples of roving were so prepared and tested. The following results were obtained (value is the average of three samples): LOI = 1.22%; Solubility = 86% Example 5 A further embodiment of the sizing according to the invention was prepared by diluting 4.918 kg of Impranil DLS with 20 liters of deionized water. This solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 3 liters of water. Next, 18.040 kg of Vinamul 88 127 was diluted with 20 liters of deionized water, mixed for 10 minutes, transferred to the main tank and flushed with 3 liters of water. Next, 415 g of A-1100 was diluted with 20 liters of deionized water and stirred for 15 minutes. Next, 203 g of glacial acetic acid was added to the coupling agent solution and stirred for 15 minutes. Next, a further 28 g of glacial acetic acid was gradually added to the coupling agent, during which time stirring was continued for 10 minutes until the pH of the mixture reached 4-5. After reaching such pH, the mixture was transferred to the main mixing tank and flushed with 3 liters of water. Next, 332 g of glacial acetic acid was diluted with 30 liters of deionized water. Next, 830 g of A174 (γ-methacryloxypropyltrimethoxysilane, available from OSI Specialties) was added and stirred for 30 minutes. When the solution became clear, it was transferred to the main tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the mixture to a total volume of 140 liters. As described in Example 1, the prepared sizing composition was applied to 16 μm fibers, and the resulting 400 tex fiber strand was divided into 6 strands, which were formed into 2400 tex rovings. Three samples of roving were so prepared and tested. The following results were obtained (value is the average of three samples): LOI = 1.28%; solubility 80%. Example 6 A further embodiment of the sizing composition according to the invention was prepared by diluting 4.918 kg of Impranil DLS with 30 liters of deionized water. The solution was mixed for 10 minutes, mixed for 10 minutes, transferred to the main mixing tank and flushed with 3 liters of water. Next, 6.013 kg of Vinamul 88127 and 12.367 kg of Fulatex PD-8000 (Fuller) were subsequently diluted together with 30 liters of deionized water, mixed for 10 minutes, transferred to the main tank and flushed with 3 liters of water. did. Next, 1246 g of A-1100 was diluted with 20 liters of deionized water and stirred for 15 minutes. Next, 611 g of glacial acetic acid was added to the coupling agent solution and stirred for 15 minutes. An additional 28 g of glacial acetic acid was then gradually added to the coupling agent solution, during which time stirring was continued for 10 minutes until the pH of the mixture reached 4-5. When such pH was reached, the mixture was transferred to the main mixing tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the mixture to 140 liters. Example 7 Another embodiment of the sizing composition of the present invention was prepared by diluting 4.918 kg of Impranil DLS with 30 liters of deionized water. This solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 3 liters of water. Next, 6.013 kg of Vinamul 881 27 and 12.367 kg of Fulatex PD-366 (Fuller) were serially diluted together with 30 liters of deionized water, mixed for 10 minutes, transferred to the main tank and transferred to 3 liters of water. Flashed. Next, 1246 g of A-1100 was diluted with 20 liters of deionized water and stirred for 15 minutes. Next, 611 g of glacial acetic acid was added to the coupling agent solution and stirred for 15 minutes. Next, 28 g of glacial acetic acid was gradually added to the coupling agent solution, and the mixture was stirred for 10 minutes, until the pH of the mixture reached 4 to 5. After reaching such pH, the mixture was transferred to the main mixing tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the mixture to a total volume of 140 liters. Example 8 A further embodiment of the sizing composition of the present invention was prepared by diluting 6.148 kg of Baybond MWH0949 (Bayer) with 30 liters of deionized water. The solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 3 liters of water. Next, 18.040 kg of Vinamul 88127 was diluted with 30 liters of deionized water, mixed for 10 minutes, transferred to the main tank and flushed with 3 liters of water. Next, 1246 g of A-1100 was diluted with 20 liters of deionized water and stirred for 15 minutes. Next, 28 g of glacial acetic acid was gradually added to the A-1100 premix, and the mixture was stirred for 10 minutes, until the pH of the mixture reached 4 to 5. After reaching such pH, the premix was transferred to the main mixing tank and diluted with 3 liters of water. Finally, water was added to the main tank, bringing the total volume of the mixture to 140 liters. In the manner described in Example 1, the prepared sizing composition was applied to 16 μm fibers and the resulting 400 tex fiber strand was divided into 6 strands which were formed into 2400 tex rovings. Three samples of roving were so prepared and tested, with the following results (values are the average of the three samples): LOI = 1.17%; solubility = 82%. Example 9 A further embodiment of the sizing composition of the present invention was prepared by diluting 6.305 kg of Baybond MWH 0948 (Bayer) with 30 liters of deionized water. The solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 3 liters of water. Next, 18.0 40 kg of Vinamul 88127 was diluted with 30 liters of deionized water, mixed for 10 minutes, transferred to the main tank and flushed with 3 liters of water. Next, 1246 g of A-1100 was diluted with 20 liters of deionized water and stirred for 15 minutes. Next, 28 g of glacial acetic acid was gradually added to the A-1100 premix, and the mixture was stirred for 10 minutes, until the pH of the mixture reached 4 to 5. When such pH was reached, the premix was transferred to the main mixing tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the total volume of the mixture to 140 liters. In the manner described in Example 1, the prepared sizing composition was applied to 16 μm fibers, and the resulting 400 tex fiber strand was divided into 6 strands, which were formed into 2400 tex rovings. Three samples of roving were so prepared and tested and the following results were obtained (values are the average of the three samples): LOI = 1.19%; Solubility = 79%. Example 10 A further embodiment of the sizing composition of the present invention was prepared by diluting 10.150 kg of RET 11266 (Bayer) with 20 liters of deionized water. The solution was mixed for 10 minutes, transferred to the main mixing tank and flushed with 2.8 liters of water. Next, 3.673 kg of Vi namul 88127 was diluted with 21 liters of deionized water, mixed for 10 minutes, transferred to the main mixing tank and flushed with 2.8 liters of water. Next, 8.984 kg of Vinamul 88154 was diluted with 21 liters of deionized water, mixed for 10 minutes, transferred to the main mixing tank and flushed with 2.8 liters of water. Next, 1,549 kg of A-1100 was diluted with 28 liters of deionized water and stirred for 15 minutes. Next, 28 g of glacial acetic acid was gradually added to the A-1100 premix while stirring for 10 minutes until the pH of the mixture reached 4-5. When such pH was reached, the A-1100 premix was transferred to the main mixing tank and flushed with 2.8 liters of water. Finally, water was added to the main mixing tank to bring the total volume of the mixture to 140 liters. The prepared sizing composition was applied to 14 μm fibers as described in Example 1 and the resulting 300 tex fiber strand was divided into four strands, rolled into a collet to form a molded cake and allowed to rise. Cured in an oven at the temperature set to form 2400 tex rovings. Two molded cakes were prepared, three cured samples of roving from each molded cake were prepared, their surface water content, sizing composition on fiber (represented by loss on ignition or "LOI"), and acetone A test was performed to determine the solubility of the sizing agent after solvent extraction. The results of these tests are listed in Table II. Example 11 A sizing composition was prepared as in Example 10 and coated on glass fibers having an average diameter of 16 μm. The resulting 400 tex fiber strand was divided into 6 strands to form 2400 tex rovings. The roving was chopped into segments, compounded with a typical low profile formulation for electrical applications, including black pigment, and formed into composite panels in the manner described in Example 2. Table V shows the physical property measurement results of a molded composite made from these fibers (Sample A) and a molded composite made from commercially available fibers (Sample B). The value reported is the average of the measurements parallel to the direction of flow and those perpendicular to the direction of flow. The foregoing description of the present invention has been set forth to illustrate preferred features and embodiments of the present invention. Other embodiments and modifications of the invention will be apparent through the routine operation of those skilled in the art. Accordingly, the invention is not intended to be limited to the features and embodiments described above, but is to be defined by the appended claims and equivalents thereof.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // C08J 5/08 C03C 25/02 B (81) Designated country EP (AT, BE, CH, CY, DE) , DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR) , NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE , GH, GM, GW, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW

Claims (1)

[Claims] 1. A sizing composition for treating glass fiber, which is useful for reinforcing a polymer material.   ,   a) Polyether-based thermoplastics formed from non-crosslinked saturated polyethers   A first film forming agent comprising a conductive polyurethane;   b) i) vinyl acetate glycidyl methacrylate copolymer, or ii.   ) Vinyl acetate glycidyl methacrylate copolymer and vinyl acetate   A second film-forming agent comprising a mixture of a salt homopolymer;   c) a silane coupling agent; and   d) water   The composition comprising: 2. Has at least about 70% solubility in styrene, toluene or acetone   The sizing composition according to claim 1. 3. Claims wherein the polyurethane comprises a reaction product of a polyether and a diisocyanate.   Item 4. The sizing composition according to Item 1. 4. From about 50,000 to about 15 vinyl acetate glycidyl methacrylate copolymer   2. The sizing composition according to claim 1, having an average molecular weight of 0,000. 5. The sizing set according to claim 1, wherein the polyurethane is in the form of a non-ionic dispersion.   Adult. 6. When the silane coupling agent is aminosilane, the reaction between aminosilane and maleic anhydride   A group consisting of reaction products, vinyl silanes, ureido silanes, and their compounds.   The sizing composition according to claim 1, which is selected. 7. The sizing composition of claim 1, wherein the pH is from about 4 to about 6. 8. The composition of claim 7, further comprising acetic acid. 9. The first film former is present in an amount of about 10 to about 40% by weight, based on total solids.   Wherein the second film former is present in an amount of about 60 to about 85% by weight, based on total solids.   The silane coupling agent is present in an amount of about 1 to about 15% by weight, based on the total solids.   The sizing composition according to claim 1, which is present. Ten. 9. At least one gas coated with the sizing composition of claim 1 which has been dried.   Textile products containing lath fiber. 11． A plurality of glass fibers coated with the sizing composition of claim 1 which has been dried.   Articles comprising polymer materials reinforced with: 12． a) Based on total solids, including polyether-based thermoplastic polyurethanes   From about 10 to about 40% by weight of a first film former;   b) i) vinyl acetate glycidyl methacrylate copolymer, or ii)   Vinyl acetate glycidyl methacrylate copolymer and vinyl acetate resin   From about 60 to about 85% by weight of a secondary polymer, including a mixture of   Film-forming agent;   c) about 1 to about 15% by weight, based on total solids, of a silane coupling agent;   Aqueous size for glass fiber treatment, useful for reinforcing polymer materials, including   Composition comprising at least 70% in styrene, toluene, or acetone   The sizing composition having a solubility of: 13. The composition further comprising an organic acid in an amount such that the composition has a pH of about 4 to about 6.   3. The sizing composition according to item 1. 14. Polyether-based thermoplastic polyurethane formed from saturated polyether   13. The sizing composition according to claim 12, which is prepared. 15． 13. The sizing composition according to claim 12, further comprising a lubricant. 16． A glass fiber coated with the sizing composition according to claim 12 which has been dried.   Fiber products. 17． A plurality of glass fibers coated with the dried sizing composition according to claim 12.   Articles comprising polymer materials reinforced with: 18． A method of preparing a sizing fiber for polymer material reinforcement, comprising:   a) Polyether-based thermoplastics formed from non-crosslinked saturated polyethers   A first film forming agent comprising a conductive polyurethane,   b) i) vinyl acetate glycidyl methacrylate copolymer or ii) vinyl acetate   Nyl acetate glycidyl methacrylate copolymer and vinyl acetate homo   A second film former comprising a mixture of polymers,   c) a silane coupling agent, and   d) water   Applying a sizing composition comprising a plurality of glass fibers to form coated fibers;   Drying the sizing agent on the fibers to form sizing coated fibers.   , Said method. 19. The sizing composition is coated fiber in an amount of about 0.6 to about 2.0% by mass as measured by loss on ignition.   20. The method of claim 18, wherein the method is on a fiber. 20. 19. The method of claim 18, further comprising applying an antistatic coating to the sizing coated fibers.   the method of. 21. The fiber of claim 20, wherein the antistatic coating is applied to the fiber in an amount from about 0.001 to about 0.3% by weight.   The described method. twenty two. further,   a) winding the sizing treated fibers into rovings;   b) applying an antistatic agent to the roving in the winding step;   c) heating the rolled rovings in a furnace   19. The method of claim 18, comprising: