CA1243559A - Chemically treated glass fibers for reinforcing polymeric matrices - Google Patents
Chemically treated glass fibers for reinforcing polymeric matricesInfo
- Publication number
- CA1243559A CA1243559A CA000505373A CA505373A CA1243559A CA 1243559 A CA1243559 A CA 1243559A CA 000505373 A CA000505373 A CA 000505373A CA 505373 A CA505373 A CA 505373A CA 1243559 A CA1243559 A CA 1243559A
- Authority
- CA
- Canada
- Prior art keywords
- glass fibers
- silane coupling
- coupling agent
- treating composition
- treated glass
- Prior art date
- 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.)
- Expired
Links
Classifications
-
- 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
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/326—Polyureas; Polyurethanes
-
- 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
-
- 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
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- Y10T428/2904—Staple length fiber
- Y10T428/2907—Staple length fiber with coating or impregnation
-
- 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
Abstract of the Disclosure Chemically treated glass fibers in the form of continuous bundles of glass fibers and chopped bundles of glass fibers are provided that have good handleability and thermal aging characteristics in reinforcing thermoplastic polymers. The chemically treated glass fibers have a dried residue of an aqueous chemical treating composition. The aqueous chemical treating composition has two aqueous soluble, dispersible, or emulsifiable film forming polymers which can be either epoxy polymers and polyurethane polymers or epoxy polyurethane copolymers and polyurethane polymers and an amino alkyl functional silane coupling agent and at least a second silane coupling agent which can be a lubricant modified amine organo functional silane coupling agent, a polyamino organo functional silane coupling agent, an epoxy organo functional silane coupling agent or a vinyl organo functional silane coupling agent and a reaction product process aid. The reaction product process aid is obtained by reacting alkoxylated nitrogen-containing compound such as an alkoxylated fatty amine and an alkoxylated fatty amide with a polycarboxylic acid to produce a product which is reacted with an epoxide compound. The amount of water in the aqueous chemical treating composition is that to give an effective solids content for treating the glass fibers. The chemically treated glass fibers as chopped bundles of glass fibers are suitable for reinforcing such thermoplastic polymers as polybutylene terephthalate, polyphenylene sulfide, polyphenylene oxide and polyacetals.
Description
S~;9 CHEMICALLY TREATED GLASS FIBERS FOR REINFORCING POLYMERIC MATRICES
The present invention relates to chemically treated glass fibers for reinforcing polymers to produce fiber reinforced polymers.
More particularly, the treated glass fibers in the form of chopped bundles of glass fibers provide good reinforcement for thermoplastic polymer matrices like polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide and polyacetals.
Glass fibers have proved useful in reinforcing thermosetting polymers and thermoplastic polymers. Thermoplastic polymer reinforcement with glass fibers provides a challenge, since there is an absence or a reduced occurrence of any crosslinking reactions between the matrix polymer and the surface chemical treatment on the glass fibers. Chopped strands of glass fibers used to reinforce thermoplastic polymers in various molding operations should have various characteristics to be successful. For the facile production of the chopped glass fiber strands or bundles, the glass fibers should have good choppability whether in a wet or dry chop operation. For molding the thermoplastlc polymer with chopped strand, the chopped strand should have good resistance to filamentation and good handleability. also, the glass fiber reinforced thermoplastic article should have good thermal aging properties, where the chemical treatment on the glass fibers does not detrimentally affect the matrix polymer to reduce the thermal aging properties.
~2~L3559 It is an object of the present invention to provide chemically treated glass fibers which have good integrity, good flow and a good bulk density for reinforcing thermoplastlc polymers.
It is a further object of the present invention to provide chopped bundles of the chemically treated glass fibers for reinforcing thermoplastic polymers to provide reinforced thermoplastic articles having good thermal aging properties.
SUMMARY OF THE INVENTION
The aforementioned objects and other objects deduced from the following disclosure are accomplished by the chemically treated glass fibers of the present invention. The glass fibers have a dried residue of an aqueous chemical treating composition. The aqueous chemical treating composition has two film forming polymers, which can be an epoxy polymer and polyurethane polymer or an epoxy polyurerhane copolymer and a polyurethane polymer, an amino alkyl silane coupling agent, a second organo silane coupling agent which is a lubrlcant modified amlno functional organo silane coupling agent and/or a polyamino functional organo silane coupling agent or an epoxy functional organo silane coupling agent or a vinyl functional organo silane coupling agent, and a process aid and water. The process aid acts as a binder stabilizer and is a reaction product obtained by reacting alkoxylated nitrogen-containing compound like an alkoxylated fatty amine or an alkoxylated fatty amide with a polycarboxylic acid and reacting the resulting product with an epoxide compound. The film forming polymers are dispersible, soluble or emulsifiable in the aqueous medium as is the reaction product processing aid. The amount of water in the aqueous ~L243S~9 chemical treating composition is that amount which gives an effective solids content so that the aqueous chemical treating composition can be applied to glass fibers.
Any known glass fibers can be treated with the aqueous chemical treating composition by any conventional method for producing chopped or continuous glass fibers. The aqueous chemical treating composition can be applied to the glass fibers in a wet chop operation, where the fibers are gathered into bundles of fibers and chopped directly in the forming process or the chemically treated glass fibers can be gathered into bundles or strands of glass fibers and wound into a forming package on a winder and subsequently chopped. The chopped bundles of the chemically treated glass fibers are dried if they were not dried before chopping and can be used to reinforce thermoplastic polymers such as polybutylene terephthalate, polypropylene oxide, polyphenylene sulfide and polyacetals in conventional molding operations.
DETAILED DESCRIPTION OF THE INVENTION
The two film forming polymers present in the aqueous chemical treating composition provide for an epoxy and polyurethane or isocyanate functionality. The two film forming polymers which are soluble3 dispersible or emulsifiable in aqueous medium can be a combination of one epoxy polymer and one polyurethane polymer or a combination of an epoxy polyurethane copolymer and a polyurethane polymer. The ratio of epoxy functionality to isocyanate or polyurethane repeating unit functionality is in the range of 99:1 to 1:99. These film forming materials provide a cure and/or evaporative film on the glass fibers and/or strands to assist in holding the filaments together in a bundle of filaments commonly ~Z435S~
called a strand. In addition, the film forming polymers have the Eunctional groups that assist in bonding the filaments to the organo functional end of the silane coupling agent or Jo the thermoplastlc polymer. The latter would be through hydrogen bondlng or Van der Walls forces.
A suitable epoxy compound for use in the aqueous sizing of the present invention is one that contains more than one group whlch has an oxygen atom attached to adjacent carbon atoms9 known as an o~irane ring and depicted by the formula / O\
G C
It is well known that epoxy resins may be prepared as a reaction product of a halohydrin and a phenol. One group of polyepoxy compounds which may be used is obtained by the reaction of a stochiometric excess of an epihalohydrin, such as an eplchlorohydrin, with a polyhydric phenol such as bis-(4-hydroxy phenyl)-2,2-propane, bis(hyroxy phenyl) methane (obtained by the acid condensation of two moles of phenol with one mold of formaldehyde), hydroquinone9 resorcinol, etc., or with a polyhydroxy alcohol such as glycol, polyethylene glycol, sorbitol, glycerol, etc.
The epoxy resin has an epoxy equivalent weight of about 170 to about 900. By varying the proportions of the epihalohydrin and the phenolic polyhydroxic compounds and/or by varying the reaction conditions, compounds of varying epoxide equivalents within this range can be produced which range from liquid to solid, but are preferably liquid.
Typically, the molecular weight range can be between about 300 to about 900, and more preferably between about 300 and 600. The epoxy resin or resins can be used in an amount of about 0.1 to about 10 weight percent of the aqueous sizing composition and preferably about 0.2 to about 3.5 percent by weight based on the total weight of the aqueous sizing composition. A particularly suitable epoxy resin for use in the sizing composition of the present invention is designated "Epi-rez CMD 35201"
commercially available from Celanese Polymer Specialties Co. This epoxy resin is an epoxy resin dispersion which has 60~ nonvolatiles with the only volatile being water and a weight per epoxide of approximately 530, a pH of 8.3 and an average particle size between l and 4 microns. Th;s epoxy resin may be cured using any conventional epoxy curing agents with allowance being made for the water environment. Another suitable epoxy resin that can be used is deslgnated "Genepoxy 370-H55" which is commercially available from General Mills Chemical Division. Another example of a suitable epoxy polymer is the epoxy novolak materials; and nonexclusive examples oE these include Celanese 5003 material from Celanese Chemical Company and the Polymene 510 material available from Quaker Chemical Companyr The polyurethane polymer can be any aqueous dispersible, emulsifiable or solubilizable polymeric reaction product of a polyol, including glycols, and polyisocyanates including diisocyanates with limited formation of allophanate and biuret groups. Nonexclusive examples of suitable polyisocyanates, which are employed to produce the polyurethane polymer used with the aqueous sizing composition of the present invention include those having an average NC0 functionality of at least about 2, such as, for example, polymethylene polvphenyl isocyanates, suitable organic diisocyanates, for example,
The present invention relates to chemically treated glass fibers for reinforcing polymers to produce fiber reinforced polymers.
More particularly, the treated glass fibers in the form of chopped bundles of glass fibers provide good reinforcement for thermoplastic polymer matrices like polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide and polyacetals.
Glass fibers have proved useful in reinforcing thermosetting polymers and thermoplastic polymers. Thermoplastic polymer reinforcement with glass fibers provides a challenge, since there is an absence or a reduced occurrence of any crosslinking reactions between the matrix polymer and the surface chemical treatment on the glass fibers. Chopped strands of glass fibers used to reinforce thermoplastic polymers in various molding operations should have various characteristics to be successful. For the facile production of the chopped glass fiber strands or bundles, the glass fibers should have good choppability whether in a wet or dry chop operation. For molding the thermoplastlc polymer with chopped strand, the chopped strand should have good resistance to filamentation and good handleability. also, the glass fiber reinforced thermoplastic article should have good thermal aging properties, where the chemical treatment on the glass fibers does not detrimentally affect the matrix polymer to reduce the thermal aging properties.
~2~L3559 It is an object of the present invention to provide chemically treated glass fibers which have good integrity, good flow and a good bulk density for reinforcing thermoplastlc polymers.
It is a further object of the present invention to provide chopped bundles of the chemically treated glass fibers for reinforcing thermoplastic polymers to provide reinforced thermoplastic articles having good thermal aging properties.
SUMMARY OF THE INVENTION
The aforementioned objects and other objects deduced from the following disclosure are accomplished by the chemically treated glass fibers of the present invention. The glass fibers have a dried residue of an aqueous chemical treating composition. The aqueous chemical treating composition has two film forming polymers, which can be an epoxy polymer and polyurethane polymer or an epoxy polyurerhane copolymer and a polyurethane polymer, an amino alkyl silane coupling agent, a second organo silane coupling agent which is a lubrlcant modified amlno functional organo silane coupling agent and/or a polyamino functional organo silane coupling agent or an epoxy functional organo silane coupling agent or a vinyl functional organo silane coupling agent, and a process aid and water. The process aid acts as a binder stabilizer and is a reaction product obtained by reacting alkoxylated nitrogen-containing compound like an alkoxylated fatty amine or an alkoxylated fatty amide with a polycarboxylic acid and reacting the resulting product with an epoxide compound. The film forming polymers are dispersible, soluble or emulsifiable in the aqueous medium as is the reaction product processing aid. The amount of water in the aqueous ~L243S~9 chemical treating composition is that amount which gives an effective solids content so that the aqueous chemical treating composition can be applied to glass fibers.
Any known glass fibers can be treated with the aqueous chemical treating composition by any conventional method for producing chopped or continuous glass fibers. The aqueous chemical treating composition can be applied to the glass fibers in a wet chop operation, where the fibers are gathered into bundles of fibers and chopped directly in the forming process or the chemically treated glass fibers can be gathered into bundles or strands of glass fibers and wound into a forming package on a winder and subsequently chopped. The chopped bundles of the chemically treated glass fibers are dried if they were not dried before chopping and can be used to reinforce thermoplastic polymers such as polybutylene terephthalate, polypropylene oxide, polyphenylene sulfide and polyacetals in conventional molding operations.
DETAILED DESCRIPTION OF THE INVENTION
The two film forming polymers present in the aqueous chemical treating composition provide for an epoxy and polyurethane or isocyanate functionality. The two film forming polymers which are soluble3 dispersible or emulsifiable in aqueous medium can be a combination of one epoxy polymer and one polyurethane polymer or a combination of an epoxy polyurethane copolymer and a polyurethane polymer. The ratio of epoxy functionality to isocyanate or polyurethane repeating unit functionality is in the range of 99:1 to 1:99. These film forming materials provide a cure and/or evaporative film on the glass fibers and/or strands to assist in holding the filaments together in a bundle of filaments commonly ~Z435S~
called a strand. In addition, the film forming polymers have the Eunctional groups that assist in bonding the filaments to the organo functional end of the silane coupling agent or Jo the thermoplastlc polymer. The latter would be through hydrogen bondlng or Van der Walls forces.
A suitable epoxy compound for use in the aqueous sizing of the present invention is one that contains more than one group whlch has an oxygen atom attached to adjacent carbon atoms9 known as an o~irane ring and depicted by the formula / O\
G C
It is well known that epoxy resins may be prepared as a reaction product of a halohydrin and a phenol. One group of polyepoxy compounds which may be used is obtained by the reaction of a stochiometric excess of an epihalohydrin, such as an eplchlorohydrin, with a polyhydric phenol such as bis-(4-hydroxy phenyl)-2,2-propane, bis(hyroxy phenyl) methane (obtained by the acid condensation of two moles of phenol with one mold of formaldehyde), hydroquinone9 resorcinol, etc., or with a polyhydroxy alcohol such as glycol, polyethylene glycol, sorbitol, glycerol, etc.
The epoxy resin has an epoxy equivalent weight of about 170 to about 900. By varying the proportions of the epihalohydrin and the phenolic polyhydroxic compounds and/or by varying the reaction conditions, compounds of varying epoxide equivalents within this range can be produced which range from liquid to solid, but are preferably liquid.
Typically, the molecular weight range can be between about 300 to about 900, and more preferably between about 300 and 600. The epoxy resin or resins can be used in an amount of about 0.1 to about 10 weight percent of the aqueous sizing composition and preferably about 0.2 to about 3.5 percent by weight based on the total weight of the aqueous sizing composition. A particularly suitable epoxy resin for use in the sizing composition of the present invention is designated "Epi-rez CMD 35201"
commercially available from Celanese Polymer Specialties Co. This epoxy resin is an epoxy resin dispersion which has 60~ nonvolatiles with the only volatile being water and a weight per epoxide of approximately 530, a pH of 8.3 and an average particle size between l and 4 microns. Th;s epoxy resin may be cured using any conventional epoxy curing agents with allowance being made for the water environment. Another suitable epoxy resin that can be used is deslgnated "Genepoxy 370-H55" which is commercially available from General Mills Chemical Division. Another example of a suitable epoxy polymer is the epoxy novolak materials; and nonexclusive examples oE these include Celanese 5003 material from Celanese Chemical Company and the Polymene 510 material available from Quaker Chemical Companyr The polyurethane polymer can be any aqueous dispersible, emulsifiable or solubilizable polymeric reaction product of a polyol, including glycols, and polyisocyanates including diisocyanates with limited formation of allophanate and biuret groups. Nonexclusive examples of suitable polyisocyanates, which are employed to produce the polyurethane polymer used with the aqueous sizing composition of the present invention include those having an average NC0 functionality of at least about 2, such as, for example, polymethylene polvphenyl isocyanates, suitable organic diisocyanates, for example,
2,3-toluene-diisocyanate, 2,6-toluene-diisocyanate, hexamethylenediisocyanate, p~p'-diphenylemthanediisocyanate, ~2~3559 p-phenylenediisocyanate, hydrogenated methylene diphenyldiisocyanate, polyisocyanate naphthalene diisocyanate, dianisidine diisocyanate, mixtures of one or more polyisocyanates and the like. Also NCO-containing prepolymers can be used and these include the reaction products of an excess of an organic diisocyanate with polyhydroxyl-containing compounds having from 2 to about 8 OH groups per molecule such as, for example, ethylene glycol, glycerine, trimethylolpropane, pentaerylthritol, sorbitol, sucrose9 mixtures thereof and/or with dihydroxyl-containing compound such that the average hydroxyl functionality in the mixture is at least about 2Ø It is preferred that these polyurethanes are liquid, however, in the event that they are solids or semisolids or of a relatively high viscosity such that blending with the other components would be difficult or inconvenient, they may be prepared in a suitable solvent or by melting and then emulsified into an oil-in-water emulsion with suitable surfactants. Nonexclusive examples of suitable polyol or dihydroxyl-containing compounds which may be used in forming the polyurethane include, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol9 diethyleneglycol, dipropylene glycol, bisphenol A, resorcinol, catechol, hydroquinone, mixtures thereof, adducts of a dihydroxyl-containing compound and a vlscinal epoxy compound such as, for example, ethyleneoxide, 1,2-propylene oxide, 1,2-butyleneoxide, epichlorohydrin9 epibromohydrin, mixtures thereof and the like. When the dihydroxyl-containing compound is a solid, it is suitably employed by either dissolving it in a suitable solvent or melting it and then converting it into an oil-in-water emulsion by use of suitable surfac~ants and water ~:435~9 Of this class of polyurethanes, curable, blocked, polyurethane polymers can be used which are aromatic, aliphatic or alicyclic in nature. The emulsions or dispersions are formed by dissolving the polyurethane prepolymer in a nonreactive organic solvent for the polyurethane in a sufficient amount, for example 20-50 percent bv weight based upon the weight of the solution, adding sufficient surfactants with the proper HLB range and then gradually mixing the solution with sufficient water to form a stable emu]sion of droplets of the solution in the water. These blocked polyurethane resins are formed by the reaction of a polylsocyanate, such as toluene diisocyanate adducts of hydroxyl terminated polyether or polyester resins with an end blocking compound containing active hydrogen atoms such as an amide or polyamide according to conventional techniques for the production of polyurethane resins.
The polyisocyanate can be referred to as a prepolymer i.e., an adduct of a simple diisocyanate with a suitable polyfunctional resin. Particularly suitable polyurethare polymers are those that are substantially aliphatic or alicyclic in nature where the majority of the polyurethane polymeric chain is constituted of aliphatic or hydrogenated aromatic, or alicyclic moieties. Particularly suitable aqueous emulsions of polyurethane polymers are designated "Rucothane " latices designated as 2010L, 2n20L, 2030L, 2040L, 2050L, and 2060L. These materials are available from the Ruco Chemical Corporation, New York. These materials include thermoplastic urethane latice having varied particle sizes and characterized as high molecular weight aliphatic isocyanate based thermoplastic elastomers in aqueous dispersions using anionic or nonionic surfactants. The most preferred polyurethane used is one that is a carboxylated polyurethane to assist in water dispersibility. The ~:9L3559 Rucothane la~ices are based on aliphatic components and have a polymer solids content in stable emulsions ranging from 55-62% by weight. The Rucothane latices have a Brookfield viscosity P~VF4 in centipoise at 2 RPM
ranging from 7,000 for about 2060L and 2030L latices up to 25,000 for the 2020L latex.
An additional example of a polyurethane resin that can be used are the polyurethane resins available from Witco Chemical Company under the trade ~s~g~&~e~ Witcobond, like the material Witcobond W290H. This material has a solids content of between 51 and 63 percent, a viscosity, Brookfield (Spindle 3, 60 RPM, LVF) between 200 centipoise and 600 centipoise, a pH between 7 and 9 and a particle size of 5 microns. The particle charge for the W290H is anionic. Also, the Mobay XW urethane latices can be used and these are available from Mobay Chemical r Corporation, the Organics Division under the trade dog s ~-110, XW-111 and XW-114 materials.
The amount of the polyurethane polymer used in the aqueous sizing composition is in the range of about 0.1 to about 10 weight percent of the aqueous sizing composition, preferably 1 to 3 weight percent or about 20 to about 60 weight percent of the solids of the aqueous sizing composition.
In addition to the epoxy polymer and polyurethane polymer or just with the polyurethane polymer, a copolymer of an epoxy polymer and polyurethane polymer can be used These materials can be formed by use of polyepoxide prepolymer having one or more oxirane rings and also having open oxirane rings, which are used as hydroxyl groups for the dihydroxyl-containing compounds for reaction with diisocyanates or polyisocyanates. The isocyanate moiety opens the oxirane ring and the of' Go 35ii~3 reaction continues as an isocyanate reaction with a primary or secondary hydroxyl group. There should be sufficient epoxide functionality on the polyepoxide resin to enable the production of an epoxy polyurethane copolymer still having effective oxirane rings. Linear polymers are produced through reactions of diepoxides and diisocyanates. The di- or polyisocyanates can be aromatic or aliphatlc although the aliphatic di-or polyisocyanates are preferred for better thermal stability and non-yellowing of the chemically treated glass fibers. The aqueous dispersion or emulsion of an epoxy polyurethane copolymer can be prepared by reacting the copolymer with a primary or secondary amine to form an epoxide-amine adduct. With the secondary amine, the reaction occurs through the amine opening the epoxide ring forming a eertiary amine and a secondary hydroxyl group. The epoxide amine adduct is solublized and obtalns a cationic character by further reaction with an acid to form a tertiary amine acid salt. Optionally a solvent such as a water-miscible solvent, nonexclusive examples of which are esters, ethers or ke~ones can be employed. A suitable class of polyepoxide resins having isocyanate or polyisocyana~e functionality is a polymeric material containing two or more epoxy groups per molecule. The polyepoxides are of a relatively high molecular weight having molecular weights of at least 350, and preferably within the range of 350 to 2,000. These polyepoxides are combined with the blocked, crosslinkable isocyanate derivaeives. The blocked isocyanate derivatives act as crosslinking or curing agents for the polyepoxide to produce epoxy polyurethane copolymers. Types of polyepoxide polymers which can form the epoxide amine adducts are given in U.S. Patent 4,148,772 (Marchetti et al.).
a ~3~
Also the polyepoxide amlne adducts which are chain extended with organic polyols with or without the use of a catalyst can be employed as taught in U.S.
Patent 4,148977 A suitable epoxy polyurethane copolymer for the present invention is that available from Celanese Chemical Company Specialty Resins, under the trade mark CMDW 60-5520 epoxy resin dispersion.
This material is an aqueous dispersion of a urethane modified epoxy resin with an epoxide equivalent weight of 540 having a solids content of 60 percent. There are no organic solvents present and the dispersion is thixotropic. The epoxy polyurethane polymer can be cured through both epoxy functionality and hydroxyl functionality. Curing agents most conveniently employed are those which are water soluble or dispersible and which are stable in aqueous medium. For instance, dicyandiamide, substituted amidizoles, aliphatic and aromatic amines 9 melamine resins and urea formaldehyde resins. Although it is preferred that curing agents are not used in the aqueous chemical treating composition for the film forming polymers. The amount of the epoxy polyurethane copolymer in the aqueous treating composition can be in the range of about 0.1 to about 10 weight percent and preferably about 3 to about 7 weight percent of the aqueous treating composition.
The amounts of the film forming polymers in the aqueous chemical treating composition can vary somewhat depending upon the polymeric matrix to be reinforced. when the polymeric matrix is an epoxy, higher amounts of the epoxy polymer or more epoxy functionality in the epoxy polyurethane polymer can be present in the aqueous chemical ~3559 treating composition. When the epoxy polyurethane copolymer is used with the polyurethane polymer 9 it is preferred that the epoxy polyurethane copolymer is present in a predominant amount of the solids of the film forming materials present in the aqueous chemical treating composition.
The amount of the film forming materials present in the aqueous chemical treating composition can range in an amount between about 1 and about 20 weight percent of the aqueous chemical treating compositlon.
The aqueous chemical treating composition also has present at least two organo functional silane coupling agents. One of the organo functional silane coupling agents is always an amino alkyl functional silane coupling agent like gamma aminopropyltriethoxy silane. Thls material i5 available from Union Carbide Corporation under she trade s ~s~g~*~0~ A-1100. The second organo silane coupling agent present in the aqueous chemical treating composition can be a lubricant modified, amine functional organo silane coupling agent, a polyamino functional organo silane coupling agent, mixtures of these and an epoxy functional organo silane coupling agent and a vinyl functional organo silane coupling agent. The lubricant modified amine functional organo silane coupling agent is available from Union Carbide under the trade deo~na~iv~ A-1108 coupling agent. The polyamino functional organo silane coupling agent is available from Union Carbide under the trade d~it~u~h~ A-1120. It is preferred to have an amount of the total organo functional silane coupling agents present in the aqueous chemical treating composition in an amount of about 0.01 to about 2 weight percent of the aqueous chemical treating composition. Preferably, the organo functional silane coupling agents are a combination of the amino alkyl functional silane coupling agent9 the lubricant modified amino functional ~2~L35S~
silane coupling agent and the polyarnino functional organo silane coupling agent. Most preferably, the comblnation is a 1:1:1 mixture, although the solids content of the lubricant modified amino silane coupling agent will make this material the predominant amount of the solids of the three silane coup].ing agents present in the aqueous chemical ereating composition.
The aqueous chemical treating composition also has a reaction product process aid which is believed to function as a stabilizer for the treating composition and as a process aid in reducing stickiness of the dried treated glass fibers. The reaction product process aid is obtained by reacting an alkoxylated nitrogen containing compound such as an alkoxylated fatty amine or amide with a polycarboxylic acid and then reacting the resulting product with an epoxide compound. This compound and the method of producing it are taught in U.S. Patent 3,459,585.
The reaction product is preferably produced by reacting one mole of the alkoxylated nitrogen containing compound with two moles of the polycarboxylic acid. The resutting reaction product is then reacted with two moles of an epoxide compound, preferably a polyepoxide compound. The reaction product process aid is present in the aqueous chemical treating composition in an amount of about 0.01 to about 0.1 weight percent of the aqueous chemical treating composition or in an amount of about 0.1 to about 1 weight percent of the solids of the aqueous chemical treating compGsition. This amount is effective to serve as a lubricant and processability agent as well as to impart the stabilizirg function.
The aqueous chemical treating composition has a sufficient amount of water to give a total solids tnon-aqueous content) of the ~2~3559 aqueous chemical treating composition in the range of about 1 to about 25 weight percent, preferably 3 to about 11 weight percent and most preferably about 4 to about 7 weight percent. In all events, the amounts of the various components should not exceed that amount which will cause the viscoslty of the solution to be greater than 100 centipoise at 20C.
Solutions having viscosities greater than 100 centipoise are difficult to apply to glass fibers during their formation with standard type applicator equipment without breaking the continuity of the fibers. It is preferred that the viscosity of the aqueous chemical treating composition be between about 1 and 20 centipoise at 20C for best results.
The aqueous chemical treating composition is essentially free of film formers like polyvinyl acetate homopolymer and polyester homopolymers. The presence of these materials would tend to degrade the thermal aging properties of the glass fiber reinforce polymer.
The aqueous chemical treating composition can be prepared by adding any of the components simultaneously or sequentially to each other to form the aqueous chemical treating composition. It is preferred to predilute all of the components before they are added together and combined with water. For example, the silane coupling agents are added to water and hydrolyzed and the film forming polymers are individually diluted and added to the mix and the reaction product processing aid is added to the mixture and the entire mixture is diluted with water to the desired volume.
Glass fibers treated with the aqu20us chemical treating composition can be any known glass fibers such as "E-glass", "621-glass", and low boron or low fluorine derivatives thereof and the like. The 35~i9 aqueous chemical treating composition is applied to the glass fibers preferably in the forming operation in a wet chop operation. Although the aqueous chemical treating composition can be applied to the glass fibers in a continuous strand winding operation in forming or can be applied to the glass fibers after forming. The amount of the aqueous chemical treating composition on the glass fibers can range in an amount of about 0.1 to about 1.5 percent LOI, preferably 0.45 to about 0.75 LOI. The glass fiber strands can be chopped into any choppable length such as less than 1/16 of an inch to greater than 2 inches but preferably is in the range of about 1/8 of an inch to around 3/16 of an inch. The chopped glass fiber strands are dried to remove residual moisture and to adequately cure the chemically treated glass fibers. Under curing can result in poorer integrity of the strand.
The dried chopped glass fiber strands can be used to reinforce thermoplastic polymers such as polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide, and polyacetals by any conventional injection molding operation. The chopped glass fiber strands can be made into pellets with the matrix polymer and injected molded. Also, the strands of the treated glass fibers can be used as continuous strands and roving and in producing chopped, continuous or needled mats.
PREFERRED EMBODIMENT OF THE INVENTION
The glass fibers to be treated with the aqueous chemical treating composition are preferably "E-glass" or "621-glass" fibers. The glass fibers can be formed into any conventional filament diameters but are preferably of a diameter in the range of about 11 to about 16 microns. The aqueous chemical treating composition for treating the _ 14 -~L2~355~3 glass fibers preferably has the two film forming polymers comprising an aqueous emulsifiable epoxy polyurethane copolymer and an aqueous emulsifiable polyurethane polymer in a ratio of around 2:1 to around
The polyisocyanate can be referred to as a prepolymer i.e., an adduct of a simple diisocyanate with a suitable polyfunctional resin. Particularly suitable polyurethare polymers are those that are substantially aliphatic or alicyclic in nature where the majority of the polyurethane polymeric chain is constituted of aliphatic or hydrogenated aromatic, or alicyclic moieties. Particularly suitable aqueous emulsions of polyurethane polymers are designated "Rucothane " latices designated as 2010L, 2n20L, 2030L, 2040L, 2050L, and 2060L. These materials are available from the Ruco Chemical Corporation, New York. These materials include thermoplastic urethane latice having varied particle sizes and characterized as high molecular weight aliphatic isocyanate based thermoplastic elastomers in aqueous dispersions using anionic or nonionic surfactants. The most preferred polyurethane used is one that is a carboxylated polyurethane to assist in water dispersibility. The ~:9L3559 Rucothane la~ices are based on aliphatic components and have a polymer solids content in stable emulsions ranging from 55-62% by weight. The Rucothane latices have a Brookfield viscosity P~VF4 in centipoise at 2 RPM
ranging from 7,000 for about 2060L and 2030L latices up to 25,000 for the 2020L latex.
An additional example of a polyurethane resin that can be used are the polyurethane resins available from Witco Chemical Company under the trade ~s~g~&~e~ Witcobond, like the material Witcobond W290H. This material has a solids content of between 51 and 63 percent, a viscosity, Brookfield (Spindle 3, 60 RPM, LVF) between 200 centipoise and 600 centipoise, a pH between 7 and 9 and a particle size of 5 microns. The particle charge for the W290H is anionic. Also, the Mobay XW urethane latices can be used and these are available from Mobay Chemical r Corporation, the Organics Division under the trade dog s ~-110, XW-111 and XW-114 materials.
The amount of the polyurethane polymer used in the aqueous sizing composition is in the range of about 0.1 to about 10 weight percent of the aqueous sizing composition, preferably 1 to 3 weight percent or about 20 to about 60 weight percent of the solids of the aqueous sizing composition.
In addition to the epoxy polymer and polyurethane polymer or just with the polyurethane polymer, a copolymer of an epoxy polymer and polyurethane polymer can be used These materials can be formed by use of polyepoxide prepolymer having one or more oxirane rings and also having open oxirane rings, which are used as hydroxyl groups for the dihydroxyl-containing compounds for reaction with diisocyanates or polyisocyanates. The isocyanate moiety opens the oxirane ring and the of' Go 35ii~3 reaction continues as an isocyanate reaction with a primary or secondary hydroxyl group. There should be sufficient epoxide functionality on the polyepoxide resin to enable the production of an epoxy polyurethane copolymer still having effective oxirane rings. Linear polymers are produced through reactions of diepoxides and diisocyanates. The di- or polyisocyanates can be aromatic or aliphatlc although the aliphatic di-or polyisocyanates are preferred for better thermal stability and non-yellowing of the chemically treated glass fibers. The aqueous dispersion or emulsion of an epoxy polyurethane copolymer can be prepared by reacting the copolymer with a primary or secondary amine to form an epoxide-amine adduct. With the secondary amine, the reaction occurs through the amine opening the epoxide ring forming a eertiary amine and a secondary hydroxyl group. The epoxide amine adduct is solublized and obtalns a cationic character by further reaction with an acid to form a tertiary amine acid salt. Optionally a solvent such as a water-miscible solvent, nonexclusive examples of which are esters, ethers or ke~ones can be employed. A suitable class of polyepoxide resins having isocyanate or polyisocyana~e functionality is a polymeric material containing two or more epoxy groups per molecule. The polyepoxides are of a relatively high molecular weight having molecular weights of at least 350, and preferably within the range of 350 to 2,000. These polyepoxides are combined with the blocked, crosslinkable isocyanate derivaeives. The blocked isocyanate derivatives act as crosslinking or curing agents for the polyepoxide to produce epoxy polyurethane copolymers. Types of polyepoxide polymers which can form the epoxide amine adducts are given in U.S. Patent 4,148,772 (Marchetti et al.).
a ~3~
Also the polyepoxide amlne adducts which are chain extended with organic polyols with or without the use of a catalyst can be employed as taught in U.S.
Patent 4,148977 A suitable epoxy polyurethane copolymer for the present invention is that available from Celanese Chemical Company Specialty Resins, under the trade mark CMDW 60-5520 epoxy resin dispersion.
This material is an aqueous dispersion of a urethane modified epoxy resin with an epoxide equivalent weight of 540 having a solids content of 60 percent. There are no organic solvents present and the dispersion is thixotropic. The epoxy polyurethane polymer can be cured through both epoxy functionality and hydroxyl functionality. Curing agents most conveniently employed are those which are water soluble or dispersible and which are stable in aqueous medium. For instance, dicyandiamide, substituted amidizoles, aliphatic and aromatic amines 9 melamine resins and urea formaldehyde resins. Although it is preferred that curing agents are not used in the aqueous chemical treating composition for the film forming polymers. The amount of the epoxy polyurethane copolymer in the aqueous treating composition can be in the range of about 0.1 to about 10 weight percent and preferably about 3 to about 7 weight percent of the aqueous treating composition.
The amounts of the film forming polymers in the aqueous chemical treating composition can vary somewhat depending upon the polymeric matrix to be reinforced. when the polymeric matrix is an epoxy, higher amounts of the epoxy polymer or more epoxy functionality in the epoxy polyurethane polymer can be present in the aqueous chemical ~3559 treating composition. When the epoxy polyurethane copolymer is used with the polyurethane polymer 9 it is preferred that the epoxy polyurethane copolymer is present in a predominant amount of the solids of the film forming materials present in the aqueous chemical treating composition.
The amount of the film forming materials present in the aqueous chemical treating composition can range in an amount between about 1 and about 20 weight percent of the aqueous chemical treating compositlon.
The aqueous chemical treating composition also has present at least two organo functional silane coupling agents. One of the organo functional silane coupling agents is always an amino alkyl functional silane coupling agent like gamma aminopropyltriethoxy silane. Thls material i5 available from Union Carbide Corporation under she trade s ~s~g~*~0~ A-1100. The second organo silane coupling agent present in the aqueous chemical treating composition can be a lubricant modified, amine functional organo silane coupling agent, a polyamino functional organo silane coupling agent, mixtures of these and an epoxy functional organo silane coupling agent and a vinyl functional organo silane coupling agent. The lubricant modified amine functional organo silane coupling agent is available from Union Carbide under the trade deo~na~iv~ A-1108 coupling agent. The polyamino functional organo silane coupling agent is available from Union Carbide under the trade d~it~u~h~ A-1120. It is preferred to have an amount of the total organo functional silane coupling agents present in the aqueous chemical treating composition in an amount of about 0.01 to about 2 weight percent of the aqueous chemical treating composition. Preferably, the organo functional silane coupling agents are a combination of the amino alkyl functional silane coupling agent9 the lubricant modified amino functional ~2~L35S~
silane coupling agent and the polyarnino functional organo silane coupling agent. Most preferably, the comblnation is a 1:1:1 mixture, although the solids content of the lubricant modified amino silane coupling agent will make this material the predominant amount of the solids of the three silane coup].ing agents present in the aqueous chemical ereating composition.
The aqueous chemical treating composition also has a reaction product process aid which is believed to function as a stabilizer for the treating composition and as a process aid in reducing stickiness of the dried treated glass fibers. The reaction product process aid is obtained by reacting an alkoxylated nitrogen containing compound such as an alkoxylated fatty amine or amide with a polycarboxylic acid and then reacting the resulting product with an epoxide compound. This compound and the method of producing it are taught in U.S. Patent 3,459,585.
The reaction product is preferably produced by reacting one mole of the alkoxylated nitrogen containing compound with two moles of the polycarboxylic acid. The resutting reaction product is then reacted with two moles of an epoxide compound, preferably a polyepoxide compound. The reaction product process aid is present in the aqueous chemical treating composition in an amount of about 0.01 to about 0.1 weight percent of the aqueous chemical treating composition or in an amount of about 0.1 to about 1 weight percent of the solids of the aqueous chemical treating compGsition. This amount is effective to serve as a lubricant and processability agent as well as to impart the stabilizirg function.
The aqueous chemical treating composition has a sufficient amount of water to give a total solids tnon-aqueous content) of the ~2~3559 aqueous chemical treating composition in the range of about 1 to about 25 weight percent, preferably 3 to about 11 weight percent and most preferably about 4 to about 7 weight percent. In all events, the amounts of the various components should not exceed that amount which will cause the viscoslty of the solution to be greater than 100 centipoise at 20C.
Solutions having viscosities greater than 100 centipoise are difficult to apply to glass fibers during their formation with standard type applicator equipment without breaking the continuity of the fibers. It is preferred that the viscosity of the aqueous chemical treating composition be between about 1 and 20 centipoise at 20C for best results.
The aqueous chemical treating composition is essentially free of film formers like polyvinyl acetate homopolymer and polyester homopolymers. The presence of these materials would tend to degrade the thermal aging properties of the glass fiber reinforce polymer.
The aqueous chemical treating composition can be prepared by adding any of the components simultaneously or sequentially to each other to form the aqueous chemical treating composition. It is preferred to predilute all of the components before they are added together and combined with water. For example, the silane coupling agents are added to water and hydrolyzed and the film forming polymers are individually diluted and added to the mix and the reaction product processing aid is added to the mixture and the entire mixture is diluted with water to the desired volume.
Glass fibers treated with the aqu20us chemical treating composition can be any known glass fibers such as "E-glass", "621-glass", and low boron or low fluorine derivatives thereof and the like. The 35~i9 aqueous chemical treating composition is applied to the glass fibers preferably in the forming operation in a wet chop operation. Although the aqueous chemical treating composition can be applied to the glass fibers in a continuous strand winding operation in forming or can be applied to the glass fibers after forming. The amount of the aqueous chemical treating composition on the glass fibers can range in an amount of about 0.1 to about 1.5 percent LOI, preferably 0.45 to about 0.75 LOI. The glass fiber strands can be chopped into any choppable length such as less than 1/16 of an inch to greater than 2 inches but preferably is in the range of about 1/8 of an inch to around 3/16 of an inch. The chopped glass fiber strands are dried to remove residual moisture and to adequately cure the chemically treated glass fibers. Under curing can result in poorer integrity of the strand.
The dried chopped glass fiber strands can be used to reinforce thermoplastic polymers such as polybutylene terephthalate, polyphenylene oxide, polyphenylene sulfide, and polyacetals by any conventional injection molding operation. The chopped glass fiber strands can be made into pellets with the matrix polymer and injected molded. Also, the strands of the treated glass fibers can be used as continuous strands and roving and in producing chopped, continuous or needled mats.
PREFERRED EMBODIMENT OF THE INVENTION
The glass fibers to be treated with the aqueous chemical treating composition are preferably "E-glass" or "621-glass" fibers. The glass fibers can be formed into any conventional filament diameters but are preferably of a diameter in the range of about 11 to about 16 microns. The aqueous chemical treating composition for treating the _ 14 -~L2~355~3 glass fibers preferably has the two film forming polymers comprising an aqueous emulsifiable epoxy polyurethane copolymer and an aqueous emulsifiable polyurethane polymer in a ratio of around 2:1 to around
3:1. Also the amine alkyl organo functional sllane is a gamma aminopropyltriethoxy silane. This silane is present along with a lubricant modified amine functional organo functional silane coupling agent and a polyamino organo functional sllane coupling agent. The silanes are present in approximately equal ratios to each other, but the lubricant modified amine functional silane may be present in a greater amount because of a higher solids content. The reaction product processing aid is preferably prepared from alkoxylated nitrogen containing compounds selected from the group consisting of (CH2CH20)XH
Pi \
(CH2C~120)yH
¦~ / (CH2CH2)x RC-N
(CH2CH20)yH
where R is a fatty alkyl group containing from 12 to 18 carbon atoms and x and y are 1 to 100. One mole of the alkoxylated nitrogen containing compound is reacted with two moles of a polycarboxylic acid to ob$ain a reaction product having a molecular weight of approximately 300 to 11,000 and an acid number of 20 to 300 and the unesterified carboxyl groups of the intermediate product are esterified with two moles of polyepoxide compound such as Epon 826 available from Shell Chemical Company. The 355~i preferred aqueous chemical treating composition has a solids content of around 5 to 6 and most preferahly 5.3 to 5.7 and a pH of around 9.5 to 10.5.
The most preferred aqueous chemical treating composition for treating glass fibers is shown in Table 1.
Table 1 Gms As Is % Solids of % Solids Materials for S Gal. % As Is Gms Solids Total Sol ds of Binder Gamma aminopropyltriethoxy 125 0.661 75.863 6.89 0.38 silane (A-1100) Lubricant modified amino-functional 125 0.661 111.575 10.13 0.56organo silane (A-1108) Polyamino functional organo 125 0.661 99.675 9.05 0.50 silane (~1120) Aqueous emulsion of epoxy 962 5.083 577.200 52.39 2.88 polyurethane copolymer (CMD W60-5520) Aqueous emulsion of polyurethane 350 1.849 227.500 20.64 1.13 polymer (Witco W19OH) Reaction product process aid 50 0.264 10.000 0.90 0.05 Water (Deionized) H20 for silanes 6000 H20 for epoxy po burethane emulsions 1000 H20 for polyurethane emulsion 1000 H20 for reaction product process aid 500 The method of preparing the aqueous chemical treating composition involves placing deionized water for the silanes into a main vessel and adding the gamma aminopropyltriethoxy silane and the lubricant ~L2~35~9 modified amino functional organo si3ane coupling agent and adding the polyamino organo functional silane coupling agent with a five minute stirring lnterval between each addition. The aqueous emulsion of the epoxy polyurethane copolymer having a solids content of around 60 percent is diluted with water in about a 1:1 ratio and added to the main mix tank. The aqueous dispersion of the polyurethane polymer is diluted with water from its solids content of 65 weight percent in a ratio of less than 1:1 of the emulsion to water. This dilution is then added to the main mix tank. The reaction product processing aid is dlluted with water in a ratio of 1:10 process aid to water and added to the main mix tank.
The total mixture is then diluted with water to the desired volume. The viscosity of the aqueous chemical treatlng composition is preferably around 1.25 to 1.55 centipoise at 72F (22C).
Preferably, the aqueous chemical treating composition is applied to the glass fibers in a wet chop operation rnd the glass fibers can be chopped into lengths in the range of about 1/8 of an inch to 1/4 of an inch. The percent LOI on the bundles of the treated glass fibeTs is in the range of about 0.045 to 0.75. Preferably, the moisture is around 9 to 14 percent for the K diameter filaments. The chopped glass fiber strands are dried so that the dry chop glass fiber strands have a bulk density in the range of about 38 to 44 pounds per cubic feet, a funnel flow of 2 to 5 seconds per 1,000 grams.
Preferably, the chopped glass fiber strands are used to reinforce the thermopiastic polymer polybutylene terephthalate in injection molding operations.
35S~t EXAMPLES
Eour aqueous chemical treating compositions were prepared in a manner similar to that of the preferred embodiment and the components and their amounts are listed in Table 2.
Table 2 AQUEOUS CHEMICAL TREATING COMPOSITIONS
Example 1Example 2 Example 3 Example 4 (gms) (gms)_ (gms) (gms) Materials Gamma aminopropyltriethoxy 125 125 125 125 silane (A-1100) Lubricant modified amine- 125 125 125 125 organo functional silane (A~1108) Polyamine organo functional 125 125 125 125 silane (A-1120) Water 6000 6000 - 6000 6000 Reaction product process aid 50 50 50 50 Water 1000 500 500 500 Aqueous emulsion of epoxy 962 962 962 962 polyurethane copolymer C~-W-60-5520 Water -- 1000 1000 1000 Aqueous emulsion of polyurethane Uitco W290H 350 350 -- 350 Ruco 201lL -- -- 370 --Waxer 1000 100 1000 1000 pH 10.1 10.0 9.7 10.5 Solids 5.6 5.5 5.6 5.8 ~L2~355~
The aqueous chemical treating compositions of Table 2 were used to treat glass fibers prepared into strand constructions of K 6.6.
Chopped strand LOIs (loss on ignition) and handling properties are given in Table 3.
Table 3 Chopped Bundles of Treated Glass Fibers Example 1 Example 2 Example 3 Example 4 Chopped Length (inch) 3/16" 1/8" 1/8" 1/8"
LOI 0.46-0.49 0.64 0.63 0.70 Bulk density, lb/ft3 40.9 41.4 40.5 41.9 Funnel flow 2.5 2.0 2.0 2.0 : secs/1000gm ~L3~i~9 In the preferred embodiment and in the following examplesJ the bulk denslty test measures a slip flow chl~racteristic in relation to compaction of chopped glass fiber strands. Compaction comes into play in moldlng reinforced thermoplastic materials. Bulk density is measured by fllling a test tube with a known volume of chopped glass fiber strands.
The test tube is placed on a shaker and the volume occupied by the strands after shaking is recorded. Higher volumes indicate better bulk density.
The funnel flow tests was conducted by placlng a given quant$ty of chopp d glass fiber strands either dry chopped or dried wet chopped in a funnel equipped for vibration. The time it took the total weight of chopped glass fiber strands to pass through the funnel was recorded. The lower time on this jest indicates better flow is the better result.
The chopped glass fiber strands having the dried residue of the aqueous chemical treating composition of Example 4 were used in molding of fiber reinforced thermoplastic polymers. Also used were commercially available chopped glass fiber strands for purposes of comparison.
Table 4 compares the thermal aging properties of 1/8 inch chopped glass fiber strands of Example 4 as compared against the 1/8 inch commercial standard A, 3/16 inch commercial standard B, and 1/4 inch commercial standard C. All test data were gathered with specimens that were direct dry blend molded on the same day using the same molding parameters at a 30 percent chopp d strand level with a polybutylene terephthalate resin available from Celanese Chemical Company under the trade designation Celanex 2002-2PBT resln.
Table 4 shows the equivalent or superior performance of the Example 4 chopped glass fiber strand to the competitive chopped strands.
:~2435~;i9 l o o o o _, o o o oo CO
ol o o o o o o o C
o ) 00 ool o g o o ox Ul $
o a o cry En O O O O
O o o o o o Jo _ o _ Q
O g g g I, ¢
En ~J
æ
¢
O
I; O O O O
us o K --o o o o o o o o O ô
O
.
o g g o O
o o o O
¢
,~
Q~ U U U
ql l h Us X O
~;~43~59 Table 5 shows the good handling properties of the chopped glass fiber strand of Example 4.
Table 5 DIRECT CHOP FOR PBT
HANDLING PROPERTIES
BULK DENSITYFUNNEL FLOW
CHOPPED STRAND LOI PC~ SEC/1 KG
1/8" Example 4 .60 44.0 3.0 3/16" Commercial B .85 39.2 3.4 Table 6 shows the mechanical properties of chopped strands treated with the aqueous chemical treating composition of Examples 1 and 2 and commercial sample B dry blend injection molded at 25 percent chopped glass fiber content in Celcon acetal copolymer resin.
The tensile flexural and izod impact tests reported in Table 6 were conducted in accordance with the test methods of the American Society of Testing and Materials (ASTM). These tests included respectively D-638, D-790, and D-256.
~3559 f o æ a _, Us .
!~3 æ
a r-cn E-t ~4 I O O
JO oo ~0 En Xl ' O
Us ' 00 Ox Ox 00 O
, ~0 Pi CO l l En I;
En Pi cr, z O I; 00
Pi \
(CH2C~120)yH
¦~ / (CH2CH2)x RC-N
(CH2CH20)yH
where R is a fatty alkyl group containing from 12 to 18 carbon atoms and x and y are 1 to 100. One mole of the alkoxylated nitrogen containing compound is reacted with two moles of a polycarboxylic acid to ob$ain a reaction product having a molecular weight of approximately 300 to 11,000 and an acid number of 20 to 300 and the unesterified carboxyl groups of the intermediate product are esterified with two moles of polyepoxide compound such as Epon 826 available from Shell Chemical Company. The 355~i preferred aqueous chemical treating composition has a solids content of around 5 to 6 and most preferahly 5.3 to 5.7 and a pH of around 9.5 to 10.5.
The most preferred aqueous chemical treating composition for treating glass fibers is shown in Table 1.
Table 1 Gms As Is % Solids of % Solids Materials for S Gal. % As Is Gms Solids Total Sol ds of Binder Gamma aminopropyltriethoxy 125 0.661 75.863 6.89 0.38 silane (A-1100) Lubricant modified amino-functional 125 0.661 111.575 10.13 0.56organo silane (A-1108) Polyamino functional organo 125 0.661 99.675 9.05 0.50 silane (~1120) Aqueous emulsion of epoxy 962 5.083 577.200 52.39 2.88 polyurethane copolymer (CMD W60-5520) Aqueous emulsion of polyurethane 350 1.849 227.500 20.64 1.13 polymer (Witco W19OH) Reaction product process aid 50 0.264 10.000 0.90 0.05 Water (Deionized) H20 for silanes 6000 H20 for epoxy po burethane emulsions 1000 H20 for polyurethane emulsion 1000 H20 for reaction product process aid 500 The method of preparing the aqueous chemical treating composition involves placing deionized water for the silanes into a main vessel and adding the gamma aminopropyltriethoxy silane and the lubricant ~L2~35~9 modified amino functional organo si3ane coupling agent and adding the polyamino organo functional silane coupling agent with a five minute stirring lnterval between each addition. The aqueous emulsion of the epoxy polyurethane copolymer having a solids content of around 60 percent is diluted with water in about a 1:1 ratio and added to the main mix tank. The aqueous dispersion of the polyurethane polymer is diluted with water from its solids content of 65 weight percent in a ratio of less than 1:1 of the emulsion to water. This dilution is then added to the main mix tank. The reaction product processing aid is dlluted with water in a ratio of 1:10 process aid to water and added to the main mix tank.
The total mixture is then diluted with water to the desired volume. The viscosity of the aqueous chemical treatlng composition is preferably around 1.25 to 1.55 centipoise at 72F (22C).
Preferably, the aqueous chemical treating composition is applied to the glass fibers in a wet chop operation rnd the glass fibers can be chopped into lengths in the range of about 1/8 of an inch to 1/4 of an inch. The percent LOI on the bundles of the treated glass fibeTs is in the range of about 0.045 to 0.75. Preferably, the moisture is around 9 to 14 percent for the K diameter filaments. The chopped glass fiber strands are dried so that the dry chop glass fiber strands have a bulk density in the range of about 38 to 44 pounds per cubic feet, a funnel flow of 2 to 5 seconds per 1,000 grams.
Preferably, the chopped glass fiber strands are used to reinforce the thermopiastic polymer polybutylene terephthalate in injection molding operations.
35S~t EXAMPLES
Eour aqueous chemical treating compositions were prepared in a manner similar to that of the preferred embodiment and the components and their amounts are listed in Table 2.
Table 2 AQUEOUS CHEMICAL TREATING COMPOSITIONS
Example 1Example 2 Example 3 Example 4 (gms) (gms)_ (gms) (gms) Materials Gamma aminopropyltriethoxy 125 125 125 125 silane (A-1100) Lubricant modified amine- 125 125 125 125 organo functional silane (A~1108) Polyamine organo functional 125 125 125 125 silane (A-1120) Water 6000 6000 - 6000 6000 Reaction product process aid 50 50 50 50 Water 1000 500 500 500 Aqueous emulsion of epoxy 962 962 962 962 polyurethane copolymer C~-W-60-5520 Water -- 1000 1000 1000 Aqueous emulsion of polyurethane Uitco W290H 350 350 -- 350 Ruco 201lL -- -- 370 --Waxer 1000 100 1000 1000 pH 10.1 10.0 9.7 10.5 Solids 5.6 5.5 5.6 5.8 ~L2~355~
The aqueous chemical treating compositions of Table 2 were used to treat glass fibers prepared into strand constructions of K 6.6.
Chopped strand LOIs (loss on ignition) and handling properties are given in Table 3.
Table 3 Chopped Bundles of Treated Glass Fibers Example 1 Example 2 Example 3 Example 4 Chopped Length (inch) 3/16" 1/8" 1/8" 1/8"
LOI 0.46-0.49 0.64 0.63 0.70 Bulk density, lb/ft3 40.9 41.4 40.5 41.9 Funnel flow 2.5 2.0 2.0 2.0 : secs/1000gm ~L3~i~9 In the preferred embodiment and in the following examplesJ the bulk denslty test measures a slip flow chl~racteristic in relation to compaction of chopped glass fiber strands. Compaction comes into play in moldlng reinforced thermoplastic materials. Bulk density is measured by fllling a test tube with a known volume of chopped glass fiber strands.
The test tube is placed on a shaker and the volume occupied by the strands after shaking is recorded. Higher volumes indicate better bulk density.
The funnel flow tests was conducted by placlng a given quant$ty of chopp d glass fiber strands either dry chopped or dried wet chopped in a funnel equipped for vibration. The time it took the total weight of chopped glass fiber strands to pass through the funnel was recorded. The lower time on this jest indicates better flow is the better result.
The chopped glass fiber strands having the dried residue of the aqueous chemical treating composition of Example 4 were used in molding of fiber reinforced thermoplastic polymers. Also used were commercially available chopped glass fiber strands for purposes of comparison.
Table 4 compares the thermal aging properties of 1/8 inch chopped glass fiber strands of Example 4 as compared against the 1/8 inch commercial standard A, 3/16 inch commercial standard B, and 1/4 inch commercial standard C. All test data were gathered with specimens that were direct dry blend molded on the same day using the same molding parameters at a 30 percent chopp d strand level with a polybutylene terephthalate resin available from Celanese Chemical Company under the trade designation Celanex 2002-2PBT resln.
Table 4 shows the equivalent or superior performance of the Example 4 chopped glass fiber strand to the competitive chopped strands.
:~2435~;i9 l o o o o _, o o o oo CO
ol o o o o o o o C
o ) 00 ool o g o o ox Ul $
o a o cry En O O O O
O o o o o o Jo _ o _ Q
O g g g I, ¢
En ~J
æ
¢
O
I; O O O O
us o K --o o o o o o o o O ô
O
.
o g g o O
o o o O
¢
,~
Q~ U U U
ql l h Us X O
~;~43~59 Table 5 shows the good handling properties of the chopped glass fiber strand of Example 4.
Table 5 DIRECT CHOP FOR PBT
HANDLING PROPERTIES
BULK DENSITYFUNNEL FLOW
CHOPPED STRAND LOI PC~ SEC/1 KG
1/8" Example 4 .60 44.0 3.0 3/16" Commercial B .85 39.2 3.4 Table 6 shows the mechanical properties of chopped strands treated with the aqueous chemical treating composition of Examples 1 and 2 and commercial sample B dry blend injection molded at 25 percent chopped glass fiber content in Celcon acetal copolymer resin.
The tensile flexural and izod impact tests reported in Table 6 were conducted in accordance with the test methods of the American Society of Testing and Materials (ASTM). These tests included respectively D-638, D-790, and D-256.
~3559 f o æ a _, Us .
!~3 æ
a r-cn E-t ~4 I O O
JO oo ~0 En Xl ' O
Us ' 00 Ox Ox 00 O
, ~0 Pi CO l l En I;
En Pi cr, z O I; 00
Claims (22)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Glass fibers having a dried residue of an aqueous chemical treating composition, comprising:
a) two aqueous soluble, dispersible or emulsifiable film forming polymers selected from the group consisting of epoxy polymers and polyurethane polymers, and epoxy polyurethane copolymers and polyurethane polymers, b) an amino alkyl silane coupling agent, c) a second organo silane coupling agent selected from the group consisting of lubricant-modified amine organo functional silane coupling agent, polyamino organo functional silane coupling agent, epoxy organo functional silane coupling agent and vinyl functional organo silane coupling agent, d) reaction product obtained by reacting alkoxylated nitrogen-containing compound selected from the group consisting of an alkoxylated fatty amine and an alkoxylated fatty amide with a polycarboxylic acid and the resulting product reacted with an epoxide-containing compound, e) water in an amount to give an effective solids content for treating glass fibers.
a) two aqueous soluble, dispersible or emulsifiable film forming polymers selected from the group consisting of epoxy polymers and polyurethane polymers, and epoxy polyurethane copolymers and polyurethane polymers, b) an amino alkyl silane coupling agent, c) a second organo silane coupling agent selected from the group consisting of lubricant-modified amine organo functional silane coupling agent, polyamino organo functional silane coupling agent, epoxy organo functional silane coupling agent and vinyl functional organo silane coupling agent, d) reaction product obtained by reacting alkoxylated nitrogen-containing compound selected from the group consisting of an alkoxylated fatty amine and an alkoxylated fatty amide with a polycarboxylic acid and the resulting product reacted with an epoxide-containing compound, e) water in an amount to give an effective solids content for treating glass fibers.
2. Treated glass fibers of Claim 1 having the epoxy polyurethane copolymer and polyurethane polymer present in a ratio of around 2:1 to 3:1.
3. Treated glass fibers of Claim 1, wherein the amount of the epoxy polyurethane copolymer in the aqueous chemical treating composition is in the range of about 0.1 to 10 weight percent.
4. Chemically treated glass fibers of Claim 1, wherein the amount of the polyurethane polymer present in the aqueous chemical treating composition is in the range of about 0.1 to about 10.
5. Treated glass fibers of Claim 1, wherein the amount of the amine alkyl functional silane coupling agent is in the amount of about 0.1 to about 2 weight percent of the aqueous chemical treating composition.
6. Treated glass fibers of Claim 1, wherein the amount of the second silane coupling agent present in the aqueous chemical treating composition is in the range of about 0.1 to about 2 weight percent.
7. Treated glass fibers of Claim 1, wherein in addition to the amine alkyl functional silane coupling agent there are present a lubricant modified amine organo functional silane coupling agent and a polyamine organo functional silane coupling agent where the total amount of the silane coupling agent present in the aqueous chemical treating composition is in the range of about 0.3 to about 3 weight percent.
8. Treated glass fibers of Claim 7, wherein the three silane coupling agents are present in an amount in a ratio of 1:1:1.
9. Aqueous chemical treating composition of Claim 1, wherein the reaction product is present as a process aid in an amount of about 0.01 to about 1 weight percent of the aqueous chemical treating composition.
10. Treated glass fibers of Claim 1, wherein the reaction product process aid has an alkoxylated nitrogen containing compound selected from the group consisting of:
wherein R is an alkyl group containing from 12 to 18 carbon atoms and x and y are 1 to 100 and wherein the reaction of the alkoxylated nitrogen containing compound with the polycarboxylic acid is in a mole ratio of 1 to 2 moles to produce an intermediate compound having a molecular weight of approximately 300 to 11,000 and an acid number of 20 to 300 and further reacting the intermediate compound to esterify the unesterified carboxyl groups with two moles of a polyepoxide compound.
wherein R is an alkyl group containing from 12 to 18 carbon atoms and x and y are 1 to 100 and wherein the reaction of the alkoxylated nitrogen containing compound with the polycarboxylic acid is in a mole ratio of 1 to 2 moles to produce an intermediate compound having a molecular weight of approximately 300 to 11,000 and an acid number of 20 to 300 and further reacting the intermediate compound to esterify the unesterified carboxyl groups with two moles of a polyepoxide compound.
Claim 11. Chemically treated glass fibers of Claim 1 that are chopped.
Claim 12. Glass fibers having a dried residue of an aqueous chemical treating composition, comprising:
a) two film forming polymers, wherein the first film forming polymer is an aqueous soluble, dispersible or emulsifiable epoxy polyurethane copolymer and wherein the second film forming polymer is an aqueous soluble, dispersible or emulsifiable polyurethane polymer, wherein the epoxy polyurethane copolymer is present in a predominant amount to the polyurethane polymer, b) three organo silane coupling agents wherein the first organo silane coupling agent is an amino alkyl silane coupling agent, the second coupling agent is a lubricant modified amine-functional organo silane coupling agent, and the third coupling agent is a polyamino organo functional silane coupling agent wherein the total amount of the silane coupling agents is in the range of about 0.3 to about 3 weight percent of the aqueous chemical treating composition, c) reaction product obtained by reacting alkoxylated nitrogen-containing compound selected from the group consisting of an alkoxylated fatty amine and an alkoxylated fatty amide with a polycarboxylic acid and the resulting product being reacted with an epoxide-containing compound, d) water in an amount to give an effective solids content for treating glass fibers.
a) two film forming polymers, wherein the first film forming polymer is an aqueous soluble, dispersible or emulsifiable epoxy polyurethane copolymer and wherein the second film forming polymer is an aqueous soluble, dispersible or emulsifiable polyurethane polymer, wherein the epoxy polyurethane copolymer is present in a predominant amount to the polyurethane polymer, b) three organo silane coupling agents wherein the first organo silane coupling agent is an amino alkyl silane coupling agent, the second coupling agent is a lubricant modified amine-functional organo silane coupling agent, and the third coupling agent is a polyamino organo functional silane coupling agent wherein the total amount of the silane coupling agents is in the range of about 0.3 to about 3 weight percent of the aqueous chemical treating composition, c) reaction product obtained by reacting alkoxylated nitrogen-containing compound selected from the group consisting of an alkoxylated fatty amine and an alkoxylated fatty amide with a polycarboxylic acid and the resulting product being reacted with an epoxide-containing compound, d) water in an amount to give an effective solids content for treating glass fibers.
13. Treated glass fibers of Claim 11, wherein the three silane coupling agents are present in a ratio of 1:1:1.
14. Treated glass fibers of Claim 11, wherein the epoxy polyurethane copolymer has an epoxide equivalent weight of 540 and is present as an aqueous emulsion having 60 percent total solids diluted around 1:1 to 1:5 with water.
15. Treated glass fibers of Claim 12, wherein the epoxy polyurethane copolymer is present in an amount of about 0.1 to about 10 weight percent of the aqueous chemical treating composition.
16. Chemically treated glass fibers of Claim 12, wherein a 62 weight percent solids aqueous polyurethane emulsion diluted for use in an aqueous chemical treating composition is present in the aqueous chemical treating composition in an amount of about 0.1 to 10 weight percent.
17. Treated glass fibers of Claim 11, wherein the reaction product process aid has an alkoxylated nitrogen containing compound selected from the group consisting of:
wherein R is an alkyl group containing from 12 to 18 carbon atoms and x and y are 1 to 100 and wherein the reaction of the alkoxylated nitrogen containing compound with the polycarboxylic acid is in a mole ratio of 1 to 2 moles to produce an intermediate compound having a molecular weight of approximately 300 to 11,000 and an acid number of 20 to 300 and further reacting the intermediate compound to esterify the unesterified carboxyl groups with two moles of a polyepoxide compound.
wherein R is an alkyl group containing from 12 to 18 carbon atoms and x and y are 1 to 100 and wherein the reaction of the alkoxylated nitrogen containing compound with the polycarboxylic acid is in a mole ratio of 1 to 2 moles to produce an intermediate compound having a molecular weight of approximately 300 to 11,000 and an acid number of 20 to 300 and further reacting the intermediate compound to esterify the unesterified carboxyl groups with two moles of a polyepoxide compound.
18. Treated glass fibers of Claim 11, wherein the process aid is present in an amount of about 0.01 to about 1 weight percent of the aqueous chemical treating composition.
19. Treated glass fibers of Claim 12 having a total solids content in the range of about 3 to about 11 weight percent.
20. Chemically treated glass fibers of Claim 12 having an LOI
of around 0.1 to about 1.5 percent.
of around 0.1 to about 1.5 percent.
21. Chemically treated glass fibers of Claim 12 having the dried residue resulting from drying imparts to the chopped glass fiber strands a bulk density in pounds per cubic feet ranging from about 37 to at least 39 and a funnel flow in seconds per one kilogram at least as low as 4 to 6 seconds.
22. Process for producing fiber reinforced thermoplastic polymers, comprising combining glass fibers of Claim l with thermoplastic polymers selected from the group consisting of polybutylene terephthalate, polyphenylene sulfide, polyphenylene oxide and polyacetals.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/717,760 US4615946A (en) | 1985-03-29 | 1985-03-29 | Chemically treated glass fibers for reinforcing polymeric matrices |
US717,760 | 1985-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1243559A true CA1243559A (en) | 1988-10-25 |
Family
ID=24883365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000505373A Expired CA1243559A (en) | 1985-03-29 | 1986-03-27 | Chemically treated glass fibers for reinforcing polymeric matrices |
Country Status (5)
Country | Link |
---|---|
US (1) | US4615946A (en) |
EP (1) | EP0201691B1 (en) |
JP (1) | JPS61256947A (en) |
CA (1) | CA1243559A (en) |
DE (1) | DE3676553D1 (en) |
Families Citing this family (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4745028A (en) * | 1985-03-29 | 1988-05-17 | Ppg Industries, Inc. | Sized glass fibers and reinforced polymers containing same |
US5030668A (en) * | 1987-03-06 | 1991-07-09 | E. I. Du Pont De Nemours And Company | Stabilized glass reinforced polyacetal compositions |
US5258227A (en) * | 1987-12-03 | 1993-11-02 | Ppg Industries, Inc. | Chemically treated glass fibers with improved reinforcement properties |
JPH0649599B2 (en) * | 1988-12-12 | 1994-06-29 | ピーピージー・インダストリーズ・インコーポレーテッド | Heat-stable chemically treated glass fiber |
US5229202A (en) * | 1990-05-22 | 1993-07-20 | Mitsubishi Kasei Corporation | Carbon fiber and carbon fiber-reinforced resin composition using it |
US5213964A (en) * | 1990-07-16 | 1993-05-25 | Cholestech Corporation | High-density lipoprotein solid-base precipitation assay method |
ATE175702T1 (en) * | 1991-03-22 | 1999-01-15 | Phillips Petroleum Co | GLASS REINFORCED GRAFTED-BRANCHED HIGHER ALPHA-OLEFINS |
FR2686828A1 (en) * | 1992-01-30 | 1993-08-06 | Vetrotex France Sa | PROCESS FOR OBTAINING A COMPOSITE PRODUCT BY MOLDING. |
WO1994016129A1 (en) * | 1993-01-13 | 1994-07-21 | Ppg Industries, Inc. | Chemically treated inorganic oxide fibers with thermal stability suitable for high temperature polymers |
DE4305728C2 (en) * | 1993-02-25 | 1995-06-22 | Bayer Ag | Molding compounds and their use |
ES2103609T3 (en) * | 1993-09-27 | 1997-09-16 | Ppg Industries Inc | COMPOSITION OF AN AGENT FOR THE PREPARATION OF GLASS FIBERS; FIBERS OF GLASS ASI TIGHTENED AND ITS USE. |
US5437928A (en) * | 1993-10-29 | 1995-08-01 | Ppg Industries, Inc. | Glass fiber size and mat |
US5605757A (en) * | 1994-01-27 | 1997-02-25 | Ppg Industries, Inc. | Glass fiber sizing compositions, sized glass fibers and methods of reinforcing polymeric materials using the same |
FR2729654A1 (en) * | 1995-01-19 | 1996-07-26 | Vetrotex France Sa | ENSIMES GLASS YARNS FOR STRENGTHENING ORGANIC MATERIALS |
US5670255A (en) * | 1995-01-23 | 1997-09-23 | Ppg Industries, Inc. | Antioxidant compositions for coating substrates, substrates coated with the same and methods for inhibiting the oxidation of such compositions applied to a substrate |
DE19523512A1 (en) * | 1995-06-28 | 1997-01-02 | Bayer Ag | Sizing composition, sized glass fibers and their use |
FR2743362B1 (en) * | 1996-01-05 | 1998-02-06 | Vetrotex France Sa | SIZING COMPOSITION FOR GLASS WIRES, PROCESS USING THIS COMPOSITION AND RESULTING PRODUCTS |
US5840370A (en) | 1996-05-02 | 1998-11-24 | Owens Corning Fiberglas Technology, Inc. | In-line processing of continous glass fibers with thermoset solution epoxy |
US5824413A (en) * | 1996-07-15 | 1998-10-20 | Ppg Industries, Inc. | Secondary coating for fiber strands, coated strand reinforcements, reinforced polymeric composites and a method of reinforcing a polymeric material |
US5804313A (en) * | 1996-07-15 | 1998-09-08 | Ppg Industries, Inc. | Polyamide and acrylic polymer coated glass fiber reinforcements, reinforced polymeric composites and a method of reinforcing a polymeric material |
US5877240A (en) * | 1997-09-26 | 1999-03-02 | Owens Corning Fiberglas Technology, Inc. | Sizing composition for glass fibers for reinforcement of engineered thermoplastic materials |
DE10039750C1 (en) * | 2000-08-16 | 2002-05-08 | Bayer Ag | Sizing composition for glass fibers and their use |
DE60207196T2 (en) | 2002-04-09 | 2006-07-20 | Cholestech Corp., Hayward | Method and apparatus for quantification of high density lipoprotein cholesterol |
US7264669B1 (en) * | 2005-02-03 | 2007-09-04 | Tribofilm Research, Inc. | Scratch resistant gradient coating and coated articles |
US7375167B2 (en) | 2005-05-09 | 2008-05-20 | Basf Se | Hydrolysis-resistance composition |
US20070057404A1 (en) * | 2005-09-12 | 2007-03-15 | Hager William G | Compression and injection molding applications utilizing glass fiber bundles |
US20070059506A1 (en) * | 2005-09-12 | 2007-03-15 | Hager William G | Glass fiber bundles for mat applications and methods of making the same |
US20070148429A1 (en) * | 2005-12-19 | 2007-06-28 | Mcgrath Ralph D | Tri-excluded WUCS glass fiber reinforced plastic composite articles and methods for making such articles |
US20120100784A1 (en) * | 2006-09-15 | 2012-04-26 | Saint-Gobain Abrasifs | Microfiber Reinforcement for Abrasive Tools |
US8808412B2 (en) | 2006-09-15 | 2014-08-19 | Saint-Gobain Abrasives, Inc. | Microfiber reinforcement for abrasive tools |
CA2671889C (en) * | 2006-12-15 | 2012-01-31 | Ppg Industries Ohio, Inc. | Sizing compositions and glass fiber reinforced thermoplastic composites |
US20080160281A1 (en) * | 2006-12-29 | 2008-07-03 | Vickery Eric L | Sizing composition for glass fibers |
WO2008086019A1 (en) | 2007-01-09 | 2008-07-17 | Cholestech Corporation | Device and method for measuring ldl-associated cholesterol |
US20110027592A1 (en) * | 2007-10-26 | 2011-02-03 | Attila Molnar | Aqueous binder or sizing composition |
DE202008015660U1 (en) | 2008-11-26 | 2009-03-12 | S.D.R. Biotec Verfahrenstechnik Gmbh | Aqueous textile sizing for the treatment of R, E, ECR and S glass fibers |
DE102008064662B4 (en) | 2008-11-26 | 2013-08-22 | S.D.R. Biotec Verwaltungs GmbH | Fibers of R, E, ECR or S glass and use of the fibers |
TW201024034A (en) * | 2008-12-30 | 2010-07-01 | Saint Gobain Abrasives Inc | Bonded abrasive tool and method of forming |
CN101955668A (en) * | 2010-09-30 | 2011-01-26 | 广东美的电器股份有限公司 | Composite material for manufacturing silencer of air-condition compressor |
KR20140065465A (en) * | 2011-09-23 | 2014-05-29 | 오씨브이 인텔렉츄얼 캐피탈 엘엘씨 | Reinforcing fibers and their use for concrete reinforcement |
US10131782B2 (en) | 2014-09-05 | 2018-11-20 | Sabic Global Technologies B.V. | Polyoxymethylene compositions, method of manufacture, and articles made therefrom |
CN109517383B (en) * | 2017-09-19 | 2020-12-25 | 比亚迪股份有限公司 | Resin composite material and preparation method thereof |
CN109592912B (en) * | 2019-01-24 | 2022-02-01 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
CN112830688B (en) * | 2021-04-16 | 2022-08-09 | 巨石集团有限公司 | Impregnating compound for glass fiber and preparation and application thereof |
CN113912985B (en) * | 2021-11-18 | 2023-02-28 | 北京化工大学 | High-strength high-modulus epoxy molding compound and preparation method thereof |
CN116040967A (en) * | 2022-12-13 | 2023-05-02 | 巨石集团有限公司 | Impregnating compound for glass fiber direct yarns, preparation method, product and application of impregnating compound |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3044898A (en) * | 1960-10-21 | 1962-07-17 | Deering Milliken Res Corp | Textile sizing composition, applicating method and resulting product |
US3475149A (en) * | 1966-05-19 | 1969-10-28 | Nalco Chemical Co | Glass fiber lubricant in sizing process |
US3459585A (en) * | 1966-12-05 | 1969-08-05 | Ppg Industries Inc | Novel reaction product and use thereof as a glass fiber size |
FR2007727B1 (en) * | 1968-05-03 | 1973-03-16 | Ppg Industries Inc | |
GB1431693A (en) * | 1973-04-16 | 1976-04-14 | De Beers Ind Diamond | Metal coating of diamond |
US4039716A (en) * | 1974-09-20 | 1977-08-02 | Owens-Corning Fiberglas Corporation | Resin coated glass fibers and method of producing same through use of an aqueous silane-containing sizing composition whereby hydrolysis and polymerization of the silane is inhibited |
GB1522148A (en) * | 1974-10-03 | 1978-08-23 | Owens Corning Fiberglass Corp | Glass fibres coated with a size which provides forming and bonding properties |
US4029623A (en) * | 1974-10-07 | 1977-06-14 | Ppg Industries, Inc. | Glass fiber sizing compositions for the reinforcement of resin matrices |
CA1111598A (en) * | 1976-01-14 | 1981-10-27 | Joseph R. Marchetti | Amine acide salt-containing polymers for cationic electrodeposition |
US4413085A (en) * | 1978-08-21 | 1983-11-01 | Ppg Industries, Inc. | Storage stable polyolefin compatible non-crosslinking size for fiber glass strands |
US4283322A (en) * | 1979-02-12 | 1981-08-11 | Ppg Industries, Inc. | Emulsion composition and method for use in treating glass fibers |
US4271229A (en) * | 1979-09-04 | 1981-06-02 | Ppg Industries, Inc. | Sizing composition to yield sized glass fibers with improved UV stability |
US4382991A (en) * | 1979-09-04 | 1983-05-10 | Ppg Industries, Inc. | Sizing composition and sized strand useful as reinforcement |
US4301052A (en) * | 1979-09-04 | 1981-11-17 | Ppg Industries, Inc. | Sizing composition and sized strand useful as reinforcement for reinforced molded composites having improved physical properties |
US4341877A (en) * | 1980-06-04 | 1982-07-27 | Ppg Industries, Inc. | Sizing composition and sized glass fibers and process |
FR2495129B1 (en) * | 1980-12-03 | 1986-05-02 | Ppg Industries Inc | SIZING COMPOSITION PROVIDING GLASS FIBERS WITH IMPROVED ULTRAVIOLET RADIATION STABILITY |
US4455343A (en) * | 1980-12-29 | 1984-06-19 | Ppg Industries, Inc. | Aqueous treating composition for glass fiber strands used to produce mats for thermoplastics |
US4432850A (en) * | 1981-07-20 | 1984-02-21 | Ppg Industries, Inc. | Ungelled polyepoxide-polyoxyalkylenepolyamine resins, aqueous dispersions thereof, and their use in cationic electrodeposition |
US4358502A (en) * | 1981-12-14 | 1982-11-09 | Owens-Corning Fiberglas Corporation | Glass fiber mat for reinforcing polyamides |
US4374177A (en) * | 1981-12-24 | 1983-02-15 | Ppg Industries, Inc. | Aqueous sizing composition for glass fibers and sized glass fibers for thermoplastic reinforcement |
US4457970A (en) * | 1982-06-21 | 1984-07-03 | Ppg Industries, Inc. | Glass fiber reinforced thermoplastics |
US4542065A (en) * | 1984-05-21 | 1985-09-17 | Ppg Industries, Inc. | Chemically treated glass fibers and strands and dispersed products thereof |
CA1290994C (en) * | 1984-07-30 | 1991-10-22 | Mikhail Milad Girgis | Flexible, chemically treated bundles of fibers, woven and nonwoven fabrics and coated fabrics thereof |
-
1985
- 1985-03-29 US US06/717,760 patent/US4615946A/en not_active Expired - Lifetime
-
1986
- 1986-03-17 DE DE8686103554T patent/DE3676553D1/en not_active Expired - Lifetime
- 1986-03-17 EP EP86103554A patent/EP0201691B1/en not_active Expired - Lifetime
- 1986-03-27 CA CA000505373A patent/CA1243559A/en not_active Expired
- 1986-03-28 JP JP61070633A patent/JPS61256947A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH057336B2 (en) | 1993-01-28 |
EP0201691A3 (en) | 1987-12-23 |
US4615946A (en) | 1986-10-07 |
EP0201691A2 (en) | 1986-11-20 |
EP0201691B1 (en) | 1990-12-27 |
DE3676553D1 (en) | 1991-02-07 |
JPS61256947A (en) | 1986-11-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1243559A (en) | Chemically treated glass fibers for reinforcing polymeric matrices | |
US4374177A (en) | Aqueous sizing composition for glass fibers and sized glass fibers for thermoplastic reinforcement | |
US4745028A (en) | Sized glass fibers and reinforced polymers containing same | |
US5130198A (en) | Polymeric-containing compositions with improved oxidative stability | |
US4637956A (en) | Sized glass fibers and reinforced polymers containing same | |
US4330444A (en) | Sizing composition and sized fibers with increased hardness | |
US4681802A (en) | Treated glass fibers and aqueous dispersion and nonwoven mat of the glass fibers | |
EP1290082B1 (en) | Binder for mineral wool products | |
US4487797A (en) | Glass fibers to reinforce polymeric materials | |
EP0593647B1 (en) | Chemical treating composition for glass fibers having emulsified epoxy with good stability and the treated glass fibers | |
EP0725729B1 (en) | Glass fiber size and mat | |
US5247004A (en) | Polymeric-containing compositions with improved oxidative stability | |
US7267782B2 (en) | Two-part combination of compositions for forming substantially colorless thermoplastic reinforcements | |
EP0741676A1 (en) | Glass fiber sizing compositions, sized glass fibers and methods of reinforcing polymeric materials using the same | |
US4592956A (en) | Treated glass fibers and aqueous dispersion and nonwoven mat of the glass fibers | |
US4536447A (en) | Treated glass fibers and aqueous dispersion and nonwoven mat of glass fibers | |
US4626289A (en) | Treated glass fibers and aqueous dispersion and nonwoven mat of glass fibers | |
US4927869A (en) | Chemically treated glass fibers for reinforcing polymers | |
KR930006327B1 (en) | Chemically treated inorganic oxide fibers with thermal stability suitable for high temperature polymers | |
EP0104555B1 (en) | Treated glass fibers for use in an aqueous dispersion to manufacture nonwoven mat | |
US7241499B2 (en) | Sizing composition for glass yarns, the glass yarns thus obtained and composite materials comprising said yarns | |
US20060099417A1 (en) | Polyurethane-based anhydrous sizing compositions for glass fibres, glass fibres obtained and composite materials comprising said fibres | |
US3409577A (en) | Method of detackifying tacky resins | |
WO1994016129A1 (en) | Chemically treated inorganic oxide fibers with thermal stability suitable for high temperature polymers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEX | Expiry |