AU714552B2

AU714552B2 – High solubility size composition for fibers
– Google Patents

AU714552B2 – High solubility size composition for fibers
– Google Patents
High solubility size composition for fibers

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Info

Publication number
AU714552B2

AU714552B2
AU29537/97A
AU2953797A
AU714552B2
AU 714552 B2
AU714552 B2
AU 714552B2
AU 29537/97 A
AU29537/97 A
AU 29537/97A
AU 2953797 A
AU2953797 A
AU 2953797A
AU 714552 B2
AU714552 B2
AU 714552B2
Authority
AU
Australia
Prior art keywords
size composition
fibers
size
weight
vinyl acetate
Prior art date
1996-05-08
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Ceased

Application number
AU29537/97A
Other versions

AU2953797A
(en

Inventor
Willy Henri Piret
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

3B Fibreglass SRL

Original Assignee
Owens Corning NV SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1996-05-08
Filing date
1997-05-06
Publication date
2000-01-06
Family has litigation

First worldwide family litigation filed
litigation
Critical
https://patents.darts-ip.com/?family=24593731&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=AU714552(B2)
“Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

1997-05-06
Application filed by Owens Corning NV SA
filed
Critical
Owens Corning NV SA

1997-11-26
Publication of AU2953797A
publication
Critical
patent/AU2953797A/en

2000-01-06
Application granted
granted
Critical

2000-01-06
Publication of AU714552B2
publication
Critical
patent/AU714552B2/en

2000-10-12
Assigned to OWENS CORNING COMPOSITES S.P.R.L.
reassignment
OWENS CORNING COMPOSITES S.P.R.L.
Request to Amend Deed and Register
Assignors: N.V. OWENS-CORNING S.A.

2017-05-06
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

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HBMJWWWQQXIZIP-UHFFFAOYSA-N
silicon carbide
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[Si+]#[C-]
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238000009751
slip forming
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starch
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235000019698
starch
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synthetic fiber
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229920001169
thermoplastic
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229920005992
thermoplastic resin
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vinyl ester resin
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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H

C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material

C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials

C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres

C—CHEMISTRY; METALLURGY

C03—GLASS; MINERAL OR SLAG WOOL

C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS

C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags

C03C25/10—Coating

C03C25/24—Coatings containing organic materials

C03C25/26—Macromolecular compounds or prepolymers

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2913—Rod, strand, filament or fiber

Y10T428/2933—Coated or with bond, impregnation or core

Y10T428/2938—Coating on discrete and individual rods, strands or filaments

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2913—Rod, strand, filament or fiber

Y10T428/2933—Coated or with bond, impregnation or core

Y10T428/2962—Silane, silicone or siloxane in coating

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

Y10T428/00—Stock material or miscellaneous articles

Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof

Y10T428/2913—Rod, strand, filament or fiber

Y10T428/2933—Coated or with bond, impregnation or core

Y10T428/2964—Artificial fiber or filament

Abstract

A high solubility size composition is provided which may be applied to glass fibers useful for reinforcing polymeric materials. The size composition includes: a first film former comprising a polyester-based thermoplastic polyurethane derived from a saturated, non-crosslinkable polyester; a second film former comprising at least one ingredient selected from i) a vinyl acetate glycidyl methacrylate copolymer and ii) a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer; a silane coupling agent; and water. Using glass fibers coated with the high solubility size composition allows the advantageous production of low-pigmented or non-pigmented molded parts having enhanced surface appearance and color uniformity.

Description

WO 97/42129 PCT/EP97/02432 HIGH SOLUBILITY SIZE COMPOSITION FOR FIBERS FIELD OF INVENTION The present invention relates to a high solubility size composition for use on fibers, in particular, on glass fibers that are used as reinforcements in sheet molding compound and bulk molding compound applications. The use of such a size composition provides a smooth, uniform appearance to the resulting molded part.
BACKGROUND OF INVENTION It is well known in the art to use glass fibers as reinforcements for polymeric materials such as composites formed by sheet molding compound (SMC) and bulk molding compound (BMC) processes. Such composites are formed using glass fiber reinforcements which provide dimensional stability and excellent mechanical properties to the resulting composites. For example, glass fibers provide dimensional stability as they do not shrink or stretch in response to changes in atmospheric conditions. Further, glass fibers have high tensile strength, heat resistance, moisture resistance, and high thermal conductivity.
Glass fibers are commonly manufactured by supplying ceramic in molten form to a bushing, drawing fibers from the bushing, and then gathering the fibers into a tow or strand. A sizing composition, or chemical treatment, is typically applied to the fibers after they are drawn from the bushing, which protects the fibers from breakage during subsequent processing and improves the compatibility of the fibers with the matrix resins that are to be reinforced. The sized strands are typically wound onto a collet, packaged, dried, and then wound together into a continuous roving. An antistatic overcoating is applied to the roving during the winding step. The roving is then subsequently chopped and contacted with a matrix resin in the sheet molding or bulk molding compound to form molded composites.
Typical sizing compositions may include coupling agents, film formers, lubricants, emulsifiers, or antistatic agents that are dissolved or dispersed (in the form of an emulsion or dispersion) in water. However, some organic solvents commonly used to emulsify or disperse film formers used in SMC size compositions, such as styrene and xylene, are flammable and pose a fire and health hazard. Lithium chloride is also commonly used in sizing compositions as an antistatic agent, but tends to adversely affect WO 97/42129 PCT/EP97/02432 yield and is therefore undesirable for use. Accordingly, it would be desirable to use a sizing composition which does not utilize undesirable organic solvents or metal halide salts.
It would also be desirable to use a size composition which provides a smooth surface to the resulting molded part. For example, Das et al., in U. S. Patent No.
4,338,233, describe aqueous sizing compositions for glass fibers which provide a smooth surface to molded compounds. However, such sizing compositions have a low solubility as they comprise one or more crosslinkable film forming polymers which, when crosslinked, become insoluble. Such low solubility size compositions are desirable for use in automotive or Class A applications where the resulting composite parts are painted.
However, a low solubility size composition is undesirable for applications where the fibers are utilized in non-pigmented or light-pigmented sheet molded parts which are not subsequently painted because the fiber strands remain integral in the molding compound, the fibers do not sufficiently defilamentize. Thus, the fiber network is visible within the resulting molded part.
In the production of structural, low-pigmented or non-pigmented parts, the sizing composition should be highly soluble so that the individual fibers are sufficiently dispersed or wetted by the matrix resin. This promotes better fiber strand defilamentization, or strand breakup, which reduces fiber prominence and thus improves the uniformity or smooth appearance of the surface of the resulting composite. This also promotes an increased interface between the individual fibers and the matrix resin and results in better mechanical properties which are needed in structural applications.
Accordingly, a need still exists in the art for an improved size composition which exhibits high solubility, and is easy to manufacture and apply to fibers. There is a further need in the art for a size composition which improves the surface appearance of non-pigmented or low-pigmented parts formed by sheet molding and bulk molding processes, and which does not use include environmentally undesirable solvents or metal halide salts.
SUMMARY OF INVENTION These needs are met by the present invention in which an improved size composition is provided for glass or non-glass fibers used to reinforce polymeric materials.
The size composition is highly soluble, but dissolves slowly, which aids in
I
WO 97/42129 PCT/EP97/02432 defilamentization of the fibers during processing. This in turn reduces the visibility of fibers in the resulting molded part, providing a more homogeneous color and surface appearance. The high solubility size also improves the flow of sheet molding paste into bulk molds in injection molding applications, as will be explained in further detail below.
Further, the size composition is essentially free of environmentally unfriendly organic solvents and metal halide salts.
According to one aspect of the invention, a high solubility size composition is provided for treating glass fibers used to reinforce polymeric materials. The size composition comprises: a first film former comprising a polyester-based thermoplastic polyurethane formed from a saturated polyester which does not crosslink; a second film former comprising a vinyl acetate glycidyl methacrylate copolymer or (ii) a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer; a silane coupling agent; and water. Preferably, the size composition has a solubility of at least 70 more particularly, of from about 70 to about 90 in styrene, toluene or acetone.
The film forming polyurethane in the size composition is preferably in the form of an anionic dispersion. The polyurethane maintains the high solubility of the size composition as it is a linear polymer formed from a saturated polyester which does not crosslink. Further, the polyurethane has elastomeric properties such that it imparts softness to the fibers, making them less brittle and improving the contact of the fibers with machinery during processing.
The second film former in the size composition may be a vinyl acetate glycidyl methacrylate copolymer. The copolymer preferably has a weight average molecular weight (Mv) of from about 50,000 to about 150,000, for example, of about 90,000 or 100,000. Alternatively, the second film former may comprise a mixture of the vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer.
Preferably, the homopolymer may replace from about 0 to about 80 by weight of the copolymer solids content in the composition. Both the polyurethane and copolymer or polyurethane and copolymer/homopolymer mixture function to protect the glass fibers from damage during processing and impart compatibility of the fibers with the matrix resin.
The silane coupling agent is preferably selected from the group consisting of aminosilanes, the reaction products of an aminosilane and maleic anhydride, vinylsilanes,
I
WO 97/42129 PCT/EP97/02432 ureidosilanes, and blends thereof The size composition may also optionally include a pH adjusting agent, such as acetic acid, to adjust the pH level of the composition. Preferably, the size composition has a pH of from about 4 to about 6.
The amounts of the ingredients of the size composition, on a solids basis with percentages given in weight, may be 5 to 60 of a first film former, 40 to 95 of a second film former, and 1 to 10 of a coupling agent. In a preferred embodiment, the first film former (polyester-based thermoplastic polyurethane) is present in the sizing composition in a solids weight percent of from about 10 to about 30 the second film former is present in a solids weight percent of from about 60 to about 85 and the silane coupling agent is present in a solids weight percent of from about 1 to about 10 More preferably, on the basis of total solids, the size composition comprises from about 15 to about 25 of the first film former, from about 67 to about 78 of the second film former, and from about 3 to about 7 of the silane coupling agent.
Preferably, the composition is aqueous–i.e., the solvent or carrier for the solids is water. The size composition may also optionally include a sufficient amount of a pH adjusting agent, such as acetic acid, such that the composition has a pH of from about 4 to about 6.
The present invention also includes a method of coating a size composition on a plurality of glass fibers used to reinforce polymeric materials. The method comprises the steps of applying a size composition as described above to a plurality of glass fibers to form coated fibers, and drying the size composition on the fibers.
The size is preferably dried on the fibers such that the size is present on the fibers in an amount of from about 0.6 to about 2.0 by weight. Such dried sized glass fiber strands can be advantageously used as reinforcements in polymeric materials such as sheet molding compounds and bulk molding compounds.
The resulting molded composite parts do not show the fiber pattern or network under the composite surface. This is particularly advantageous in SMC molding applications where the parts are not painted and a uniform surface appearance is important.
Furthermore, the size composition of the invention has excellent wetting characteristics in polyester and vinyl ester resins, which allows compounders to increase filler loadings. The size composition also advantageously has excellent mechanical WO 97/42129 PCT/EP97/02432 properties, enhanced mold flowability, reduced fuzz and static electricity, and excellent runnability and choppability.
Accordingly, it is an object of the present invention to provide a high solubility sizing composition for fibers used in reinforcement applications that may be easily manufactured and applied to fibers, results in a composite having an improved surface appearance, and does not utilize organic solvents or metal halide salts.
DETAILED DESCRIPTION
AND
PREFERRED EMBODIMENTS OF INVENTION The high solubility size composition of the present invention provides many advantages over prior low and high solubility size compositions. The size composition of the present invention is highly soluble, but dissolves slowly, which allows good wetthrough of the fiber strands by the matrix resin, as will be explained in further detail below.
The high solubility size composition also enhances the compatibility of the fibers with the matrix resin which is to be reinforced.
Composite articles reinforced with the sized fibers of the present invention have an improved uniform, smooth surface, which is particularly advantageous for lowpigmented sheet molding compounds, such as white compounds, or non-pigmented (clear) compounds. The use of the high solubility size eliminates or reduces the need to add expensive pigments to the articles to hide the fiber network and the non-uniform color of the article.
Further, the size composition is environmentally safe as 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 paste in injection molding applications. This is due to the low dissolution speed of the size.
Because the size dissolves slowly, the fibers stay together longer, they are less subject to premature defilamentization than other high solubility sizes. This improves the flow of SMC and BMC resin or paste. Consequently, the molding of a compound containing fibers coated with the size of the present invention will require less pressure to fill the mold. In addition, by improving the flow of paste, the size of the present invention allows the molding of thinner walls and more complex mold shapes using the same amount of pressure.
WO 97/42129 PCT/EP97/02432 The size preferably has a solubility of from 70% to 90% in styrene, toluene or acetone as determined by the Soxhlet acetone solubility test as described in Dana et al., “Sheet Molding Compound Glass Fibers”, PPG Industries, p. 130, the disclosure of which is hereby incorporated by reference.
As mentioned previously, the highly soluble size dissolves very slowly, which facilitates good wet-out and wet-through of the glass bundles or strands. By wetout, it is meant the extent to which strand bundles are coated or encapsulated by the polymer matrix resin. By wet-through, it is meant the rate at which the polymer matrix resin can flow through the sized glass bundles or strands as a result of the compaction which occurs during compounding of the molding compound.
Typically, prior high solubility size compositions have had low wet-through because the size dissolves very quickly and the fiber bundles break apart and become too fine for the resin to flow through. However, the size of the present invention dissolves slowly, so the fiber bundles hold together longer, allowing the resin to flow through the spaces between individual fiber bundles. However, because of the chemical compatibility of the size, a fast wetting of the strands also occurs, which is desirable.
The size composition of the present invention comprises a polyester-based thermoplastic polyurethane, which is preferably present in the form of an anionic dispersion. Preferably, the polyurethane is formed from the reaction product of a 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-naphthalene diisocyanate, 1, 6 -hexamethylene diisocyanate, 4,6′-xylene diisocyanate, para-phenylene diisocyanate, cyclohexyl diisocyanate, 3,3′-tolidene 4,4’diisocyanate, and 3,3’-dimethyl-diphenylmethane 4 4 ‘-diisocyanate.
More particularly, the preferred polyurethane is a polyurethane ionomer which includes pendant ionic groups such as sulfonate or carboxylate groups. The ionic groups allow the polyurethane to form a stable dispersion in water.
A specific polyurethane preferred for use in the present invention is Impranil
DLS
T
an aliphatic polyester-based polyurethane available from Bayer AG, which contains about 50 by weight solids. Other suitable polyurethanes include Neoxil® 9851, an aliphatic-cycloaliphatic polyurethane resin in the form of a nonionic WO 97/42129 PCT/EP97/02432 water emulsion available from DSM Savid, Baybond® PU 402 and Baybond® PU 401 (anionic polyester urethane polymer dispersions), both available from Bayer, and Baybond MWH 0949 (a polyester polyurethane anionic dispersion prepared from IPDI and HDI with anionic carboxylate groups (sodium salt), having 40% solids, a pH of 8.7, and a viscosity according to DIN 53211 of 13 S) and Baybond MWH 0948 (a polyester polyurethane anionic dispersion prepared from IPDI and HDI with anionic sulfonate groups (sodium salt), having 39% solids, a pH of 7.7, and a viscosity according to DIN 53211 of 12 which do not contain organic solvent or blocked isocyanate groups capable of crosslinking and are also available from Bayer.
As the second film former, the size composition may include a random copolymer of vinyl acetate and glycidyl methacrylate. Preferably, the copolymer contains about 1 part to about 5 parts glycidyl methacrylate to 100 parts vinyl acetate (unless indicated otherwise, all parts herein are by weight). More preferably, the copolymer contains 2 parts glycidyl methacrylate to 100 parts vinyl acetate. When the glycidyl methacrylate content is low, bonding to the glass may be inhibited. Conversely, when the glycidyl methacrylate content is high, many reactions may occur in the chain resulting in decreased solubility or in insolubility. On the other hand, the preferred ratios increase the molecular weight and provide sufficient bonding to the glass while maintaining high solubility.
Copolymers suitable for the second film former include Fulatex PD-0166 and Fulatex PN-6019, which are both available from Fuller. Fulatex PN-6019 is a modified vinyl acetate copolymer in an anionic/nonionic surfactant system with the following typical properties: solids content of 53.5 to 55.5 weight viscosity of 100 to 600 cps (0.1 to 0.6 Pa-s); pH of 3.5 to 4.5; and a residual monomer content of 0.5 or below. An especially preferred copolymer is Vinamul T 88127, which is available from Vinamul U.K. or from National Starch under the product code N.S. 25-1971. This copolymer typically contains from 53.5 to 55.5 by weight solids, has a pH of 4 to 5, and a viscosity of from 100 to 400 mPa s. Analysis of Vinamul 88127 and Fulatex PN-6019 gave the following results: Prert Vinamul 88127 Fulatex PN-60 19 pH 4.5 4.3 Viscosity 306 286 Percent solids, by wt. 54.1 54.5 Particle size, nm (BI-90) 223 234 Percent insoluble in acetone 0 0 GPC data: Mw 90,725 97,800 M, 34,458 29,300 polydispersity 2.63 3.33 Percent soluble in THF 94.7 99.0 Tg (degrees Celsius) 25 24 Alternatively, the second film former may be a mixture of a vinyl acetate Sglycidyl methacrylate copolymer and a vinyl acetate homopolymer. The homopolymer S may or may not be plastified. Suitable homopolymers include Vinamul 88154 (Vinamul or Fulatex PD 366 (Fuller). The homopolymer can replace from about 0 to about 80 by weight of the copolymer solids content in the size composition.
20 The polyurethane and the copolymer or the polyurethane and the copolymer/homopolymer mixture maintains the high solubility of the size while regulating the speed of dissolution of the size. The solubility of the size and the rate of dissolution are directly affected by the molecular weight of the copolymer, the molecular weight of the homopolymer, and the weight ratio of homopolymer to copolymer. For example, a 25 copolymer having a high molecular weight will slow the dissolution rate of the size. The speed of dissolution is also reduced when the molecular weight of the homopolymer is increased.
The vinyl acetate glycidyl methacrylate copolymer has a high dissolution speed. However, when the copolymer is mixed with a polyurethane having a lower dissolution speed or when mixed with a higher molecular weight homopolymer, the dissolution speed is reduced without affecting the final solubility of the size. This provides SR a improvement over prior size compositions which include crosslinkable film formers.
WO 97/42129 PCT/EP97/02432 While the crosslinking reaction reduces the dissolution speed, the solubility is also reduced, which is undesirable.
The size composition also preferably includes a silane coupling agent. The silane coupling agent functions to enhance the adhesion of the film forming copolymer to the glass fibers and to reduce the level of fuzz, or broken fiber filaments, during processing. This enhanced adhesion is believed to occur due to a reaction between the coupling agent and epoxy groups in the copolymer. Suitable coupling agents include, but are not limited to, aminosilanes, the reaction product of an aminosilane and maleic anhydride, vinylsilanes, ureidosilanes, and blends thereof. A preferred coupling agent is Al 100, which is commercially available from OSI Specialties and contains 52% by weight active silane solids after hydrolysis. Also suitable for use is a hydrolyzed A1100 solution in water, which is commercially available from OSI Specialties under the designation VS 142 (40% solution) or from Hils under the designation Al 151 (40% solution).
The size composition further comprises an amount of water sufficient to dissolve or disperse the active solids for coating. Preferably, the weight percentage as total solids of the first film former, second film former, and coupling agent in the composition is from about 4 to about 16 weight percent.
The size composition may optionally include a pH adjusting agent, such as an organic acid, in an amount sufficient to provide the size composition with a pH of from about 4 to about 6. A preferred organic acid is acetic acid.
The size composition may also optionally include a processing aid, such as a lubricant, to facilitate manufacturing. For example, a small amount, preferably no more than about 0.14 by weight of the size composition, of a conventional water-based lubricant may be employed. Exemplary lubricants that may be optionally added to the size compositions of the invention include one or more of the following: a nonionic surfactant, a block copolymer of ethylene oxide and propylene oxide such as Pluronic L101 (available from BASF) or Synperonic PE/L101 (available from ICI), or octylphenoxypolyethoxyethanol such as Triton X100 (available from Rohm and Haas); a polyvinyl pyrrolidone, a Luviskol K grade (available from BASF); an imidazoline, an alkylimidazoline derivative such as Tego cationic softener (available from Th.Goldschmidt AG); or a polyethyleneimine polyamide salt, Emery 6760 (available from Henkel Corp.).
WO 97/42129 PCT/EP97/02432 The size composition is preferably prepared by diluting and mixing each of the polyurethane, copolymer and coupling agent separately with water to form a premix prior to being combined with the other components in a main mixing tank. Acetic acid is added to the coupling agent premix or to the combined mixture as needed to reach a final pH of from 4 to 5. After all of the premixed materials are added to the main mix tank, a sufficient amount of water is added to obtain a total solids content in the composition of from about 4 to about 16 weight percent. The size composition may be prepared using suitable equipment and techniques known in the art.
As mentioned previously, the size is preferably applied to the fibers and dried such that the size is present on the fibers in an amount of from about 0.6 to about by weight based on fibers. This is measured by the loss on ignition (LOI) of the rovings. By loss on ignition, it is meant the reduction in weight of the fibers after heating by burning or pyrolyzing to remove the organic size from the fibers.
To achieve the desired solids content on the fibers, the amount of water added to the dilute the size mixture may be varied. For example, to obtain an LOI of 1.2% on the fibers, the following size composition may be used (percents are based on the total weight of the composition): 4.8 by weight (6,675 g) ofImpranil DLS as the first film former; 17.5 by weight (24,483 g) of Vinamul 88127 as the second film former; 1.2 by weight (1,691 g) of Al 100 as the silane coupling agent; 0.6 by weight (829 g) acetic acid; and 75.9 by weight (106,322 g) water. An exemplary composition having an 0.6 LOI value contains: 1.50 by weight (6,675 g) Impranil DLS; 5.50 by weight (24,483 g) Vinamul 88127; 0.38 by weight (1,691 g) Al 100; 0.19 by weight (829 g) acetic acid; and 92.43 by weight (411,322 g) water. To obtain an LOI of a composition may be prepared containing 6.1 by weight (6,675 g) of Impranil
DLS;
22.3 by weight (24,483 g) Vinamul 88127; 1.5% by weight (1,691 g) of Al 100; 0.8% by weight (829 g) acetic acid; and 69.4% by weight (76,322 g) water.
The size composition is preferably applied to fibers having a diameter of from about 9 to about 20 microns, with fibers of from about 14 to about 16 microns in diameter being more preferred.
The preferred roving yield, or tex, for bundles of the sized fibers is from to 500 tex, with 75 tex being especially preferred. Tex is a measure of weight per unit length of the roving expressed in grams per kilometer. Tex measurements are used to WO 97/42129 PCT/EP97/02432 ascertain whether consistent glass loadings have been achieved during the compounding process, and involve splitting the strands as they are wound with the use of a comb. The number of bundles of strands separated by the comb is equal to the number of splits. For example, a strand exiting the bushing at 300 tex being separated into 4 splits produces a strand made of 4 bundles of 75 tex each. A strand of 400 tex can be separated into 6 splits to give bundles of approximately 67 tex per bundle. It should be appreciated that the tex of the strands formed from the bushing is dependent on the bushing type and the fiber diameter.
Values of from 1200 up to 9600 tex are preferred for the assembled strands, with 2400 to 4800 tex being more preferred. Such tex values allow a sufficient repartition of the glass on the SMC line. Higher tex strands are difficult to chop and result in non-homogeneous repartition of the glass. Lower tex strands have better fiber dispersion, but are more expensive to produce and manipulate (they require more cakes per SMC line including creel and feeding pipes). Values of 2400 and 4800 tex are standard values. In some cases, such as BMC preparation, 9600 tex can be used.
The smaller (finer) the bundle tex, the better the glass repartition in the SMC molding. The mechanical properties are also improved with finer bundle tex. The most common tex are in the range of from 37.5 to 75 tex.
While the size composition is described as being applied to glass fibers, it should be appreciated that the size may also be applied to preformed fibers (fibers which were previously formed off-line), synthetic fibers (non-glass fibers) such as Kevlar®, carbon or graphite fibers, silicon carbide (SiC) fibers, polymeric fibers (preformed or continuously formed), and other non-glass fibers.
The size composition may be applied to the fibers by conventional methods known in the art. Generally, the size composition is applied to the fibers as they exit the bushing using an applicator roller as described in U.S. Application Serial No. 08/311,817, filed September 26, 1994, the disclosure of which is hereby incorporated by reference.
In the production of the glass fibers, the fibers may be split into strands at a gathering shoe and then wound onto a collet into forming packages or cakes. The packages are preferably cured in an oven at a temperature of from 100 0 C to 130 0 C for a period of 12 to 18 hours to remove water and cure the size on the surface of the fibers.
WO 97/42129 PCT/EP97/02432 The packages are then put into :acreel and the strands are wound together into a continuous roving.
Preferably, an antistatic agent is applied to the roving during the winding step. Suitable antistatic agents include a mix ofEmerstat T 6660. a quaternary ammonium antistat available from Henkel, and FC-430, which is a product containing fluoroaliphatic polymeric esters available from 3M. The antistatic agent is preferably applied to the roving at about 0.001 to about 0.3 by weight.
Optionally, the wound roving may be subjected to a suitable postovening treatment to improve properties without substantially affecting solubility. For example, to improve run-out, the wound, antistat-treated roving may be positioned unpacked on a shelf (to allow hot air to circulate easily around it), and then placed in a ventilated oven and heated at a temperature of about 130 0 C for a period of from about 2 to about 8 hours, with the precise conditions being suitably selected for the particular roving bobbin size and tex. Such treatment is preferably conducted to improve run-out at the end of the bobbin.
The rovings are then allowed to cool.
The rovings may then be appropriately packaged and shipped to a customer for the desired SMC, BMC or other processing into a composite part. A non-pigmented SMC formulation or paste which may be used for processing with the sized glass fibers of the present invention may include an unsaturated polyester resin as the matrix, a thermoplastic low-profile additive such as polyethylene which reduces the resin contraction during polymerization, a filler such as calcium carbonate, and a thickener such as magnesium oxide. The paste may also include an organic peroxide such as tertbutylperbenzoate which initiates crosslinking polymerization of the matrix resin, and a demolding agent such as zinc stearate.
The paste is deposited onto a moving carrier film and sized glass fiber rovings are fed into a chopper and chopped to a length which may vary from about 6 mm to about 50 mm. The chopped fibers are dropped onto the resin paste, then a second carrier film is coated with resin paste and laid (resin side down) on top of the chopped fibers, and the glass fibers are wet out with the resin paste. The glass fibers are compounded with the paste in a proportion of about 30 by weight glass and about 70 by weight paste. The SMC sheet is then taken 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 cit WO 97/42129 PCT/EP97/02432 pieces are then assembled into a charge pattern of a shape and volume which will fill the mold cavity. The charge is then placed in the mold, which generally comprises a matched set of steel dies, and compressed. The SMC is then cured, and the mold is opened and the resulting part removed.
The SMC molded parts which utilize the sized fibers of the present invention as reinforcements include molded electrical cabinets which house electrical networks, bathtubs, and structural parts for automobiles. Rovings of sized fibers are useful in a wide variety of SMC applications, such as valve covers, semi-structural and structural applications, and electrical housing and business equipment, and are especially advantageous in light-pigmentable SMC formulations, such as sanitary and appliance equipment.
A bulk molding compound (BMC) formulation which may be used with the sized fibers of the present invention includes a polyester resin, a low profile thermoplastic resin, a pigment, a crosslinking agent, a catalyst, a thickening agent, a mold lubricant, and powdered mineral fillers. In a BMC process, the compounds may be prepared by mixing the BMC resin matrix with the sized chopped fibers using a sigma blade mixer.
Alternatively, the roving may be pulled through a dip tank of BMC resin and then chopped. The resulting material is then ready for molding. Typical bulk molding compounds are processed by compression, transfer or injection molding. In BMC molding, an important characteristic is the flow of the BMC material into the mold. As mentioned previously, the size composition of the present invention improves the flow of the matrix resin or paste such that less pressure may be used to fill the mold.
BMC molded parts which utilize the sized fibers of the present invention as reinforcements include headlamp reflectors, iron casings, toasters, electrical boxes, and switch bases.
It should be appreciated that while the invention is preferably directed to a size for SMC and BMC applications, the size may also be used in other applications such as Zanella molding compounds (ZMC), dough molding compounds (DMC), knead molding compounds (KMC), thick molding compounds (TMC), continuously impregnated compounds (CIC), granular molding compounds (GMC), nodular molding compounds (NMC), and pellet molding compounds (PMC). Due to its slow dissolution and good wetthrough, the size composition may also be used for reaction injection molding (RIM). The WO 97/42129 PCT/EP97/02432 size may also be used in resin transfer molding applications, particularly the Owens Coming process described in “Industrial RTM–New Developments in Molding and Preforming Technologies” (Advanced Composite Materials: New Developments and Applications Conference Proceedings, Detroit, Michigan Sept. 30 Oct. 3, 1991), the disclosure of which is hereby incorporated by reference.
In order that the invention may be more readily understood, reference is made to the following examples, which are intended to be illustrative of the invention, but are not intended to be limiting in scope.
Example 1 A size composition in accordance with the present invention was prepared by diluting 6.675 kg Impranil DLS (Bayer) in 42 liters ofdemineralized water. The solution was mixed for 10 minutes, transferred to a main mix tank and flushed with 2.8 liters of water. Then 24.483 kg of Vinamul 88127 (Vinamul was diluted in 42 liters of demineralized water, mixed for 10 minutes and transferred to the main tank and flushed with 2.8 liters of water. Next, 1691 grams of A- 100 (OSI Specialties) was diluted in 28 liters of demineralized water and stirred for 15 minutes. Glacial acetic acid was then progressively added to the coupling agent solution in 28-gram increments, with 10 minutes of agitation between additions, until the mixture reached a pH of 4 to 5. When such a pH was reached, the mixture was transferred to the main mix tank and flushed with 2.8 liters of water.
The prepared size composition was applied to several samples of 16-p diameter fibers as they exited a bushing using a conventional in-line graphite applicator roller. A resulting 400-tex fiber strand was then split into six strands which were wound onto a collet to form a single forming cake. The forming cake was then cured in a conventional ventilated oven for 17 hours at 130 0 C. Six such forming cakes were then placed on a creel and the strands were wound together into a 2 4 00-tex continuous roving.
An antistatic agent in a water solution was applied to the roving at a level of 0.09% solids on the strand. The antistatic agent was prepared according to the following composition: Material Active Solids by Weight kg/100 liters Emerstat 6660 100 40.82 40.746 FC-340 100 0.42 0.419 Demineralized Water 0 58.76 58.662 WO 97/42129 PCT/EP97/02432 The rovings were then tested for tex, loss on ignition (LOI), and solubility.
The results are shown below in Table I.
Table I Solubility In/ Sample 1 2 3 Example 2 (a/ltm\ T FT 0/\ L, j CLif 2496 2493 2483 1.22 1.32 1.32 77.95 75.36 76.66 A size composition was prepared as in Example 1. The prepared size was then conventionally applied to 14-4 diameter fibers as they exited, unsplit, from a bushing.
In this example, a 300-tex strand was not split to enhance the size of the bundle (and, consequently, its effect on the visual appearance of the molded panel) and to allow easier colorimetry testing. Eight forming cakes were assembled into a 2400-tex roving. The 2400-tex rovings were then fed via polyethylene pipes, spaced at 50 mm, to a commercially available Finn Fram, Inc., chopper of a conventional SMC impregnation machine. The chopping length was set to 25 mm. The glass was compounded with nonpigmented general purpose SMC paste of the following composition: Ingredient Technical Description Parts Weight (g) SYN.0020-N-2 unsaturated polyester resin 100 32.18 13,000 (Synolite 0020-N-2, available from DSM)
TBPB
(available from Laporte) Coathylene (H-grade, available from Plast-Labor SA (Hoechst)) Zn stearate (available from Oleofina) tert-butylperbenzoate 2 0.64 260 polyethylene 10 3.22 1,300 zinc stearate 4 1.29 WO 97/42129 PCT/EP97/02432 BLP/2 99.75% calcium carbonate 100 32.18 13,000 (available from (5 a avg. diameter) OMYA S.A.) Maglide D MgO, thickener 1.5 0.48 195 (available from Merck) The chopper speed and carrier speed were adjusted to compound the glass with the paste in a proportion of 30% by weight glass and 70% by weight paste. The resulting prepreg, which had a surface weight of 5 kg/m 2 was maturated for 3 days at 0
C.
Panels were then molded by superimposing three layers of prepreg material in a 500T Battenfeld press so that 70% of the projection of the mold surface was covered.
The part, a rectangular box measuring 40 cm by 60 cm by 9 cm with a part thickness of mm, was molded at a pressure of 80 to 90 kg/cm 2 for a cycle time of 3 minutes. The bottom of the box was cut out and used for mechanical testing and surface quality measurements as described below.
Each panel was measured for color homogeneity using a spectrophotometer using color parameters L, a, b (coordinates based on CIE-L*a*b* system; ASTM method E 308). For each molded specimen, 20 measurements were recorded randomly on the surface of the specimens. The ranges of variation of the 3 color parameters L, a, b were then calculated statistically. The ranges of variation were small when the panel had a homogeneous surface appearance and were high when the panel did not have a homogeneous surface appearance. The ranges of variation of the color parameters were then consolidated into one value with the addition of the 3 color parameter range of variation, represented by the sum R L variation range a variation range b variation range. The color homogeneity is dependent on the quantity of size on the strand (LOI) and the degree of solubility (determined by Soxhiet extraction). A higher solubility corresponds to a more homogeneous surface for the resulting molded part.
WO 97/42129 PTE9/23 PCT/EP97/02432 Example 3 A size composition was produced as in Example 1, which was coated on glass fibers having an average diameter of 16 The properties of the fibers were measured and compared with the properties of other fibers coated with commercially available size compositions. The comparative results are shown below in Table II.
Table II Commercial Commercial Commercial Property Trial product I product 2 Ex. 1 product 3 TEX (g/km) 1 2416 2501 2466 2391 2 2320 2471 2486 2432 3 2294 2504 2384 2440 0’0+ MOISTURE 1 0.0484 0.0816 0.0458 0.0589 0.0517 0.0737 0.041 0.0592 3 0.0488 0.0611 0.0289 0.0512 2 1.12 0.94 1.41 0.97 3 1.08 0.91 1.40 0.95 -5 T C 2 64.17 67.47 82.85 74.72 3 62.06 66.93 79.30 76.21 7 RUTN-OUT 2 0.0145 0.0208 0.0287 0.0171 g/kg) 3 0.0159 0.0295 0.0225 0.0105 W SEVERITY 2 0.0371 0.0414 0.03 14 0.08 (g/kg) 3 0.03 12 0.0589 0.0309 0.0582 BMC flow (bar) 52.8 54.91 50.64 (P3 -PI) WO 97/42129 PCTIEP97/02432 By fuzz run-out is meant the weight of the fuzz collected when the bobbin is run out. This is done to simulate the fuzz a customer would have in its creel before the strand enters the guiding pipes. By fuzz severity is meant the fuzz generated when the strand is passed through a series of tensioning bars in a closed box. This is done to simulate the fuzz generated on the customer line at the chopping step. As can be seen, the size of the present invention achieves the lowest levels of fuzz. This is achieved without the aid of lubricants or other processing aids which are normally applied to fibers during manufacturing and compounding to reduce fuzz.
Example 4 Another embodiment of a size composition in accordance with the present invention was prepared by diluting 4.918 kg Impranil DLS in 30 liters of demineralized water. The solution was mixed for 10 minutes, transferred to a main mix tank and flushed with 3 liters of water. Then 18.907 kg of Vinamul 88127 was diluted in 30 liters of demineralized water, mixed for 10 minutes and transferred to the main tank and flushed with 3 liters of water. Next, 1246 grams of A-1100 was diluted in 20 liters of demineralized water and stirred for 15 minutes. Then 551 grams ofmaleic anhydride was added to the coupling agent solution and stirred for 15 minutes. Glacial acetic acid was then progressively added to the coupling agent solution in 28-gram increments, with minutes of agitation between additions, until the mixture reached a pH of 4 to 5. When such a pH was reached, the premix was transferred to the main mix tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the total volume of the mix to 140 liters.
In the manner described in Example 1, the prepared size composition was applied to 16-micron fibers, and the resulting 400-tex fiber strand was split into six strands, which were formed into a 2 4 0 0-tex roving. Three samples of rovings were thus prepared and tested, producing the following results (values are averages for the three samples): LOI 1.22 solubility 86 Example An additional embodiment of a size composition in accordance with the present invention was prepared by diluting 4.918 kg Impranil DLS in 20 liters of demineralized water. The solution was mixed for 10 minutes, transferred to a main mix WO 97/42129 PCT/EP97/02432 tank and flushed with 3 liters ofwater. Then 18.040 kg ofVinamul 88127 was diluted in liters of demineralized water, mixed for 10 minutes and transferred to the main tank and flushed with 3 liters of water. Next, 415 grams of A-1100 was diluted in 20 liters of demineralized water and stirred for 15 minutes. Then 203 grams of glacial acetic acid was added to the coupling agent solution and stirred for 15 minutes. Additional glacial acetic acid was then progressively added to the coupling agent solution in 28-gram increments, with 10 minutes of agitation between additions, until the mixture reached a pH of 4 to When such a pH was reached, the mixture was transferred to the main mix tank and flushed with 3 liters of water. Next, 332 grams of glacial acetic acid was diluted in liters ofdemineralized water. Then, 830 grams of A174 (gammamethacryloxypropyltrimethoxysilane, available from OSI Specialties) was added and stirred for 30 minutes. Once the solution was 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 mix to a total of 140 liters.
In the manner described in Example 1, the prepared size composition was applied to 16-micron fibers, and the resulting 400-tex fiber strand was split into six strands, which were formed into a 2400-tex roving. Three samples of rovings were thus prepared and tested, producing the following results (values are averages for the three samples): LOI 1.28 solubility 80 Example 6 A further embodiment of a size composition in accordance with the present invention was prepared by diluting 4.918 kg Impranil DLS in 30 liters of demineralized water. The solution was mixed for 10 minutes, transferred to a main mix tank and flushed with 3 liters of water. Then 6.013 kg of Vinamul 88127 and 12.367 kg ofFulatex PD- 8000 (Fuller) were diluted successively together in 30 liters of demineralized water, mixed for 10 minutes, transferred to the main tank and flushed with 3 liters of water. Next, 1246 grams of A-1100 was diluted in 20 liters of demineralized water and stirred for 15 minutes.
Then 611 grams of glacial acetic acid was added to the coupling agent solution and stirred for 15 minutes. Additional glacial acetic acid was then progressively added to the coupling agent solution in 28-gram increments, with 10 minutes of agitation between additions, until the mixture reached a pH of 4 to 5. When such a pH was reached, the mixture was WO 97/42129 PCT/EP97/02432 transferred to the main mix tank and flushed with 3 liters of water. Finally, water was added to the main tank to complete the mix to 140 liters.
Example 7 Another embodiment of a size composition in accordance with the present invention was prepared by diluting 4.918 kg Impranil DLS in 30 liters of demineralized water. The solution was mixed for 10 minutes, transferred to a main mix tank and flushed with 3 liters of water. Then 6.013 kg of Vinamul 88127 and 12.367 kg of Fulatex PD-366 (Fuller) were diluted successively together in 30 liters of demineralized water, mixed for minutes, transferred to the main tank and flushed with 3 liters of water. Next, 1246 grams of A-1100 was diluted in 20 liters of demineralized water and stirred for 15 minutes.
Then 611 grams of glacial acetic acid was added to the coupling agent solution and stirred for 15 minutes. Glacial acetic acid was then progressively added to the coupling agent solution in 28-gram increments, with 10 minutes of agitation between additions, until the mixture reached a pH of 4 to 5. When such a pH was reached, the mixture was transferred to the main mix tank and flushed with 3 liters of water. Finally, water was added to the main tank to complete the mix to 140 liters total.
Example 8 An additional embodiment of a size composition in accordance with the present invention was prepared by diluting 6.148 kg Baybond MWH 0949 (Bayer) in liters of demineralized water. The solution was mixed for 10 minutes, transferred to a main mix tank and flushed with 3 liters of water. Then 18.040 kg of Vinamul 88127 was diluted in 30 liters of demineralized water, mixed for 10 minutes and transferred to the main tank and flushed with 3 liters of water. Next, 1246 grams of A-1100 was diluted in liters of demineralized water and stirred for 15 minutes. Glacial acetic acid was then progressively added to the premix of A-1100 in 28-gram increments, with 10 minutes of agitation between additions, until the mixture reached a pH of 4 to 5. When such a pH was reached, the premix was transferred to the main mix tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the total volume of the mix to 140 liters.
In the manner described in Example 1, the prepared size composition was applied to 16-micron fibers, and the resulting 400-tex fiber strand was split into six strands, which were formed into a 2400-tex roving. Three samples of rovings were thus WO 97/42129 PCT/EP97/02432 prepared and tested, producing the following results (values are averages for the three samples): LOI 1.17 solubility 82 Example 9 A further embodiment of a size composition in accordance with the present invention was prepared by diluting 6.305 kg Baybond MWH 0948 (Bayer) in 30 liters of demineralized water. The solution was mixed for 10 minutes, transferred to a main mix tank and flushed with 3 liters of water. Then 18.040 kg of Vinamul 88127 was diluted in liters of demineralized water, mixed for 10 minutes and transferred to the main tank and flushed with 3 liters of water. Next, 1246 grams of A-1100 was diluted in 20 liters of demineralized water and stirred for 15 minutes. Glacial acetic acid was then progressively added to the premix of A-1100 in 28-gram increments, with 10 minutes of agitation between additions, until the mixture reached a pH of 4 to 5. When such a pH was reached, the premix was transferred to the main mix tank and flushed with 3 liters of water. Finally, water was added to the main tank to bring the total volume of the mix to 140 liters.
In the manner described in Example 1, the prepared size composition was applied to 16-micron fibers, and the resulting 400-tex fiber strand was split into six strands, which were formed into a 2400-tex roving. Three samples of rovings were thus prepared and tested, producing the following results (values are averages for the three samples): LOI 1.19 solubility 79 The above description of the invention has been made to illustrate preferred features and embodiments of the invention. Other embodiments and modifications will be apparent to skilled artisans through routine practice of the invention. Thus, the invention is intended not to be limited to the features and embodiments described above, but to be defined by the appended claims and equivalents thereof

Claims (22)

1. A size composition for treating glass fibers useful to reinforce polymeric materials comprising: a first film former comprising a polyester-based thermoplastic polyurethane formed from a saturated polyester which does not crosslink; a second film former comprising a vinyl acetate glycidyl methacrylate copolymer or (ii) a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer; a silane coupling agent; and water.

2. The size composition of claim 1 having a solubility in styrene, toluene or acetone of at least about 70

3. The size composition of claim 1 in which said polyurethane comprises a reaction product of said polyester and a diisocyanate.

4. The size composition of claim 1 in which said vinyl acetate glycidyl methacrylate copolymer has a weight average molecular weight of from about 50,000 to about 150,000.

5. The size composition of claim 1 in which said polyurethane is in the form of an anionic dispersion.

6. The size composition of claim 1 in which said silane coupling agent is selected from the group consisting of aminosilanes, the reaction products of aminosilanes and maleic anhydrides, vinylsilanes, ureidosilanes, and blends thereof.

7. The size composition of claim 1 further comprising acetic acid.

8. The size composition of claim 1 having a pH of from about 4 to about 6.

9. The size composition of claim 1 wherein the first film former is present in amount, based on total solids, of from about 10 to about 30 by weight, the second film former is present in an amount, based on total solids, of from about 60 to about 85 by weight, and the silane coupling agent is present in an amount, based on WO 97/42129 PCT/EP97/02432 total solids, of from about 1 to about 10 by weight; and the total amount of solids in the composition is from about 4 to about 16 by weight.

A fiber product comprising at least one glass fiber coated with a dried size composition as defined in claim 1.

11. A molded product comprising a polymeric material reinforced with a plurality of glass fibers coated with a dried size composition as defined in claim 1.

12. An aqueous size composition for treating glass fibers useful to reinforce polymeric materials comprising: from about 10 to about 30 by weight based on total solids of a first film former comprising a polyester-based thermoplastic polyurethane; from about 60 to about 85 by weight based on total solids of a second film former comprising a vinyl acetate glycidyl methacrylate copolymer or (ii) a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer; and from about 1 to about 10 by weight based on total solids of a silane coupling agent; wherein the size composition has a solubility in styrene, toluene or acetone of at least

13. The size composition of claim 12 further comprising an amount of an organic acid such that said composition has a pH of from about 4 to about 6.

14. The size composition of claim 12 wherein said polyester-based thermoplastic polyurethane has been formed from a saturated polyester.

The size composition of claim 12 further comprising a lubricant.

16. A fiber product comprising a glass fiber coated with a dried size composition as defined in claim 12.

17. A molded product comprising a polymeric material reinforced with a plurality of glass fibers coated with a dried size composition as defined in claim 12.

18. A method of preparing sized glass fibers for reinforcing polymeric materials, comprising the steps of: applying a size composition to a plurality of glass fibers to form coated fibers, said size composition comprising a first film former comprising a polyester-based thermoplastic polyurethane formed from a saturated polyester WO 97/42129 PCT/EP97/02432 which does not crosslink, a second film former comprising a vinyl acetate glycidyl methacrylate copolymer or (ii) a mixture of a vinyl acetate glycidyl methacrylate copolymer and a vinyl acetate homopolymer, a silane coupling agent, and water; and drying said size on said fibers to form size-coated fibers.

19. The method of claim 18 in which said size composition is present on said coated fibers in an amount of from about 0.6 to about 2.0 by weight as measured by loss on ignition.

The method of claim 18 further comprising the step of: applying an antistatic coating to said size-coated fibers.

21. The method of claim 20 wherein said antistatic coating is applied to said fibers in an amount of about 0.001 to about 0.3 by weight.

22. The method of claim 18 further comprising the steps of: winding said size-coated fibers into a roving; applying an antistatic agent to said roving during said winding step; and heating the wound roving in an oven.

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Families Citing this family (17)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US6025073A
(en)

*

1997-06-04
2000-02-15
N.V. Owens-Corning S.A.
High solubility size composition for fibers

US5877240A
(en)

*

1997-09-26
1999-03-02
Owens Corning Fiberglas Technology, Inc.
Sizing composition for glass fibers for reinforcement of engineered thermoplastic materials

JPH11286873A
(en)

*

1998-03-31
1999-10-19
Nitto Boseki Co Ltd
Sizing agent for glass fiber

DE19929301A1
(en)

*

1999-06-25
2000-12-28
Basf Ag
Welded composite material, e.g. for moulded or laminated housings and other parts in cars, has at least one moulded part consisting of polyester material reinforced with aminosilane- and epoxy resin-treated fibres

AU2768701A
(en)

*

2000-01-05
2001-07-16
Owens Corning
Catalytically polymerized fiber-reinforced composites

US6787226B2
(en)

*

2001-10-23
2004-09-07
Asahi Fiber Glass Company Limited
Chopped strands and molded product of unsaturated polyester resin BMC employing them

AU2003252128A1
(en)

*

2002-07-23
2004-02-09
Ppg Industries Ohio, Inc.
Glass fiber sizing compositions, sized glass fibers, and polyolefin composites

US7078451B2
(en)

*

2002-12-19
2006-07-18
Owens Corning Fiberglas Technology, Inc.
Formulation and process for compression molded component parts

CN1325594C
(en)

*

2004-06-22
2007-07-11
姜堰鼎盛特种化工有限公司
Polyurethane binder

CN100351289C
(en)

*

2005-07-13
2007-11-28
安徽大学
Radiation polymerization method for aqueous polyurethane-siliceous acrylic resin fabric coating

US20070082199A1
(en)

*

2005-10-11
2007-04-12
Schweizer Robert A
Fiber size, sized reinforcements, and articles reinforced with such reinforcements

DE102007055692A1
(en)

*

2007-12-03
2009-06-04
Wacker Chemie Ag

Radically crosslinkable polymer compositions containing epoxy-functional copolymers

DE102007055694A1
(en)

2007-12-03
2009-06-04
Wacker Chemie Ag

Crosslinkable vinyl ester copolymers and their use as low-profile additives

WO2009112515A1
(en)

*

2008-03-11
2009-09-17
Dsm Ip Assets B.V.
Fibre coated with a sizing composition

DE102008054482A1
(en)

2008-12-10
2010-06-17
Wacker Chemie Ag

Graft copolymers and their use as low-profile additives

EP2620419A1
(en)

2012-01-27
2013-07-31
3B Fibreglass
Polyamide based sizing composition for glass fibres

EP2828313B1
(en)

2012-03-20
2016-05-18
3B-Fibreglass SPRL
Two part sizing composition for coating glass fibres and composite reinforced with such glass fibres

Citations (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US4457970A
(en)

*

1982-06-21
1984-07-03

Ppg Industries, Inc.

Glass fiber reinforced thermoplastics

US4694034A
(en)

*

1986-05-29
1987-09-15

Owens-Corning Fiberglas Corporation

Size composition

US4745028A
(en)

*

1985-03-29
1988-05-17

Ppg Industries, Inc.

Sized glass fibers and reinforced polymers containing same

Family Cites Families (18)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

FR2398702A1
(en)

*

1977-07-28
1979-02-23
Saint Gobain

PREPARATION OF GLASS FIBERS FOR SMC PREIMREGNES

US4370439A
(en)

*

1979-03-22
1983-01-25
Ppg Industries, Inc.
Method of preparing a sizing composition for treating glass fibers

GB2076730B
(en)

*

1980-06-02
1984-06-06
Pont A Mousson
Device for the injection of plastics materials elastomers or other similar materials

FR2483318A1
(en)

*

1980-06-02
1981-12-04
Pont A Mousson
Injection moulding device – in which injection section is moved bodily to the mould and includes facility for avoiding breaking reinforcing fibres

US4338234A
(en)

*

1980-06-04
1982-07-06
Ppg Industries, Inc.
Sizing composition and sized glass fibers and strands produced therewith

US4341877A
(en)

*

1980-06-04
1982-07-27
Ppg Industries, Inc.
Sizing composition and sized glass fibers and process

US4370157A
(en)

*

1981-03-09
1983-01-25
Ppg Industries, Inc.
Stable sizing compositions used during forming of glass fibers and resulting fiber

US4477496A
(en)

*

1981-06-15
1984-10-16
Ppg Industries, Inc.
Process for preparing sized glass fiber roving

US4338233A
(en)

*

1981-06-15
1982-07-06
Ppg Industries, Inc.
Aqueous sizing composition and sized glass fibers and method

US4410645A
(en)

*

1981-06-15
1983-10-18
Ppg Industries, Inc.
Aqueous sizing composition and sized glass fibers and method

US4435474A
(en)

*

1981-06-15
1984-03-06
Ppg Industries, Inc.
Aqueous sizing composition and sized glass fibers and method

US4394418A
(en)

*

1981-12-24
1983-07-19
Ppg Industries, Inc.
Aqueous sizing composition and glass fibers made therewith for reinforcing thermosetting polymers

FR2589473B1
(en)

*

1985-10-30
1988-09-16
Saint Gobain Vetrotex

POLYMERIZABLE RESIN COMPOSITION REINFORCED BY CUT WIRES

US4755557A
(en)

*

1986-06-19
1988-07-05
Union Carbide Corporation
Fiber reinforced molding compositions providing improved surface characteristics

JPS63265839A
(en)

*

1987-04-22
1988-11-02
Nippon Glass Fiber Co Ltd
Sizing agent for glass fiber

US5185117A
(en)

*

1989-09-05
1993-02-09
Composite Products, Inc.
Process for compounding thermoplastic resin and fibers

DE69402882T2
(en)

*

1993-09-27
1997-09-11
Ppg Industries Inc

FIBERGLASS FINISHING COMPOSITIONS, COATED GLASS FIBERS AND METHOD FOR USE THEREOF

US5491182A
(en)

*

1994-07-27
1996-02-13
National Starch And Chemical Investment Holding Corporation
Glass fiber sizing compositions and methods of using same

1996

1996-05-08
US
US08/646,606
patent/US5712036A/en
not_active
Expired – Fee Related

1997

1997-05-05
IN
IN808CA1997
patent/IN191977B/en
unknown

1997-05-06
AU
AU29537/97A
patent/AU714552B2/en
not_active
Ceased

1997-05-06
EP
EP97923878A
patent/EP0897376B1/en
not_active
Expired – Lifetime

1997-05-06
DK
DK97923878T
patent/DK0897376T3/en
active

1997-05-06
WO
PCT/EP1997/002432
patent/WO1997042129A1/en
active
IP Right Grant

1997-05-06
CA
CA002252602A
patent/CA2252602A1/en
not_active
Abandoned

1997-05-06
DE
DE69709633T
patent/DE69709633T2/en
not_active
Expired – Lifetime

1997-05-06
ES
ES97923878T
patent/ES2171940T3/en
not_active
Expired – Lifetime

1997-05-06
AT
AT97923878T
patent/ATE212007T1/en
not_active
IP Right Cessation

1997-05-06
JP
JP9539557A
patent/JP2000509698A/en
not_active
Ceased

1997-05-06
CN
CN97194461.XA
patent/CN1218445A/en
active
Pending

Patent Citations (3)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US4457970A
(en)

*

1982-06-21
1984-07-03
Ppg Industries, Inc.
Glass fiber reinforced thermoplastics

US4745028A
(en)

*

1985-03-29
1988-05-17
Ppg Industries, Inc.
Sized glass fibers and reinforced polymers containing same

US4694034A
(en)

*

1986-05-29
1987-09-15
Owens-Corning Fiberglas Corporation
Size composition

Also Published As

Publication number
Publication date

IN191977B
(en)

2004-01-31

AU2953797A
(en)

1997-11-26

EP0897376B1
(en)

2002-01-16

DE69709633T2
(en)

2002-10-17

CA2252602A1
(en)

1997-11-13

WO1997042129A1
(en)

1997-11-13

DK0897376T3
(en)

2002-04-22

EP0897376A1
(en)

1999-02-24

US5712036A
(en)

1998-01-27

JP2000509698A
(en)

2000-08-02

CN1218445A
(en)

1999-06-02

ATE212007T1
(en)

2002-02-15

ES2171940T3
(en)

2002-09-16

DE69709633D1
(en)

2002-02-21

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Legal Events

Date
Code
Title
Description

2000-05-04
FGA
Letters patent sealed or granted (standard patent)

2000-10-12
HB
Alteration of name in register

Owner name:
OWENS CORNING COMPOSITES S.P.R.L.

Free format text:
FORMER NAME WAS: N.V. OWENS-CORNING S.A.

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