WO1994015884A1 - Encollage de fibres de verre - Google Patents

Encollage de fibres de verre Download PDF

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Publication number
WO1994015884A1
WO1994015884A1 PCT/US1994/000353 US9400353W WO9415884A1 WO 1994015884 A1 WO1994015884 A1 WO 1994015884A1 US 9400353 W US9400353 W US 9400353W WO 9415884 A1 WO9415884 A1 WO 9415884A1
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WO
WIPO (PCT)
Prior art keywords
weight percent
glass fiber
aqueous
basis
vinyl acetate
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.)
Ceased
Application number
PCT/US1994/000353
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English (en)
Inventor
Chester S. Temple
Peter C. Gaa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Publication of WO1994015884A1 publication Critical patent/WO1994015884A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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

Definitions

  • the present invention is directed to chemically treated glass fibers, strands or yarn where the fibers impart improved strength in reinforcing thermoplastics such as polypropylene .
  • Glass fibers may be in various forms such as chopped or unchopped, woven, twisted or as a mat.
  • the fibers are generally treated upon formation with various chemical treatments or sizings to increase their compatibility with different polymers and to make the fibers more easy to process .
  • thermoplastics to be reinforced are preferably chemically coupled polypropylenes .
  • the objects of this invention are achieved with glass fibers which have been treated with a sizing having from 0.5 to 20 weight percent on a non-aqueous basis of a thermoplastic compatible film former mixture or an epoxy functional acrylic polymer and a vinyl acetate copolymer; from 0.5 to 10 weight percent on a non-aqueous basis of a silane coupling agent; from 25 to 75 weight percent on a non-aqueous basis of an emulsified polypropylene composition; from 0.01 to 10 weight percent on a non-aqueous basis of a lubricant; from 10 to 30 weight percent on a non-aqueous basis of an adhesion promoter; and water in an amount to produce an aqueous sizing composition.
  • Other components may optionally be added to the invention and more than one of the above components may be used.
  • any glass fiber suitable for reinforcing may suitably be treated in accordance with the present invention.
  • the production of glass fibers is well known in the art and is described, for example, in The Manufacturing Technology of Continuous Glass Fibers by K. L. Lowenstein, published in 1973 by Elsevier Scientific Publishing Company, Library of Congress Card Number 72-97429.
  • sizing to glass fibers is well known in the art and may be accomplished by conventional methods such as a belt applicator, a "kiss-roll” applicator, by spraying, etc.
  • the amount of sizing deposited on the glass is around 0.01 to 5 weight percent of the treated glass fiber strand. After the strands have been sized, they are usually at least partially dried to remove residual moisture.
  • the glass fiber strands are collected and where intended for use as reinforcement, are generally cut or chopped into lengths from about a sixteenth (1.6 mm) to about 3 (76.2 mm) inches.
  • the fibers may also be collected as continuous strand roving for long fiber applications and may also be made into a mat of either chopped strands or continuous fibers.
  • the sized glass fibers of this invention are advantageously used to reinforce thermoplastics such as polypropylene and other polyolefin ⁇ such as polyethylene, polybutylene, 5-methyl-pentene, etc.
  • the thermoplastic may be a homopolymer or copolymer and may be chemically coupled. Chemically coupled polypropylene is the preferred thermoplastic for use with the sized fibers of this invention.
  • “Chemically coupled” is a term used to identify the product resulting from the grafting of a polar moiety into a non-polar hydrocarbon such as polypropylene, to enhance adhesion to other polar molecules.
  • Suitable polar moieties are anhydrides like maleic anhydride, or acrylic acids.
  • the actual quantity of grafted polar moiety is small as compared to the hydrocarbon matrix, accounting for less than 0.1 weight percent of the solids of the base hydrocarbon. Because the level is low, maleic anhydride grafted polypropylene is often referred to as "chemically coupled propylene homopolymer" .
  • Chemically coupled versions of various polyolefins at varying levels of polar moieties which provide the desired levels of chemical coupling are commercially available.
  • the components of the sizing of this invention are from 0.5 to 20 weight percent on a non-aqueous basis of a thermoplastic compatible mixture of certain film formers; from 0.5 to 10 weight percent on a non-aqueous basis of a silane coupling agent; from 5 to 20 weight percent on a non-aqueous basis of an emulsified polypropylene composition; from 0.01 to 20 weight percent on a non-aqueous basis of a lubricant; from 1 to 10 weight percent on a non-aqueous basis of an adhesion promoter; and water in an amount to produce an aqueous sizing composition.
  • a specific thermoplastic compatible film former mixture particularly useful in this invention comprises an epoxy functional acrylic polymer and a vinyl acetate polymer.
  • the epoxy-functional acrylic polymer is a polymer having a backbone derived by polymerizing one or more acrylic monomers and having pendant epoxy groups.
  • the pendant epoxy groups are normally obtained from a monomer such as glycidyl acrylate or methacrylate.
  • Homopolymers of epoxy functional acrylic monomers may be used, but also useful are interpolymers of such monomers with other copolymerizable acrylic monomers such as acrylic acid, methacrylic acid and alkyl esters of acrylic and methacrylic acid.
  • Such comonomer ⁇ may include, at least in small proportion, monomers having other functional groups, such as urethane or urethane- producing moieties, carbonyl, amido groups, etc., and non-acrylic ethylenic monomers such as styrene.
  • the epoxy equivalent of the epoxy-functional polymer is preferrably between about 125 to about 165, however, polymers with epoxy equivalents outside of this preferred range would also function, since epoxy-funtionality of any amount would have some effect.
  • the preferred epoxy-functional acrylic polymer is a glycidyl methacrylate polymer, i.e. , a homopolymer of glycidyl methacrylate or a copolymer of glycidyl methacrylate with minor amounts of one or more other monomers, such as acrylic or methacrylic acids or esters.
  • a glycidyl methacrylate polymer is commercially available as Fulatex® PN-3620J emulsion from the H.B. Fuller Company and has an epoxy equivalent of about 142, a solids percentage of 44 to 46 percent (Ohaus Moisture Balance) , a viscosity of 10 to 150 cps (Brookfield Viscometer Model RVF, at 20 RPM at 25°C) , a density of about 8.8 pounds per gallon, an opaque white color and a glass transition temperature (Tg) of 56 ⁇ 2°C.
  • the vinyl acetate polymer may be poly(vinyl acetate) or may be a vinyl acetate copolymer which contains at least 80% vinyl acetate copolymerized with other monomers, which may contain various functional groups.
  • Other monomers which may be used include, for example, alkylacrylates and methacrylates, acrylamide, methylacrylamide, N-ethylacrylamide, acrylic acid, styrene and similar copolymerizable ethylenic monomers.
  • the preferred vinyl acetate polymer is that available as a stiff self-reactive emulsion of a copolymer of vinyl acetate and acrylamide which has 52% solids, a viscosity of 5800 cps (RVF Brookfield viscosity, #3 spindle, 20 RPM at 70°F) , a density of 9.2 pounds per gallon at 72°F, and a particle size of about 1 micron.
  • a material is commercially available as Resyn 2828 from National Starch & Chemical .
  • the epoxy-functional acrylic polymer may be present in an amount of 0.5 to 10 weight percent on a non-aqueous basis of the components (i.e., the components other than water) and the vinyl acetate polymer in an amount of 0.5 to 10 weight percent on a non-aqueous basis. It is preferred that the weight ratio of the epoxy functional acrylic polymer to vinyl acetate polymer be about 1:1 based on the solids or non-volatiles .
  • the silane coupling agent may be an organofuctional silane or one or more of its hydrolysis products.
  • Any suitable organofunctional silanes known to those skilled in the art may be used.
  • Particularly suitable silanes are the amino- and mercapto- functional silanes. Examples of different types of these silane coupling agents and their amounts are disclosed in U.S. Patents Nos . 4,271,229 and 4,457,970.
  • the preferred silanes for this invention is gamma- aminoalkyltrialkoxy silanes, an example of which is gamma-aminopropyltriethoxy silane available under the tradename A-1100 from Union Carbide Corporation.
  • the emulsified polypropylene composition used in this invention is an emulsion of polypropylene polymer, the polypropylene having been modified to provide dispersibility in water by grafting small amounts of acid or anhydride groups which are then neutralized.
  • emulsions may be prepared, for example, by reacting an acid or anhydride, such as maleic anhydride, with polypropylene and then neutralizing the anhydride grafted polypropylene resin with an organic amine or an alkali metal hydroxide like potassium hydroxide and dispersing the neutralized anhydride grafted polypropylene through the use of a non-ionic emulsifier.
  • the preferred product is a maleic anhydride grafted polypropylene neutralized with an organic amine such as diethylethanolamine
  • the material may be emulsified in water using a surfactant such as an alkoxylated phenol or others known in the art .
  • the preferred emulsified polypropylene composition is a maleonated polypropylene which has a percent solids of 32%, is a tan to grey color, has a specific gravity of 0.98 and is available as Protolube RL-5440 from National Starch and Chemical Corporation, Proctor Chemicals of Salisbury, NC.
  • Another useful emulsified polypropylene composition is maleonated polypropylene available as Protolube RL-3974, also from National Starch and Chemical Corporation.
  • polyether polyols such as polyalkylene or polyoxyalkylene polyol.
  • the polyether polyol may be either solid or liquid so long as it is dispersible or emulsifiable or soluble in water.
  • the most effective molecular weight of the polyol is that which forms a non-homogeneous lubricious phase with non-rigid film forming polymers. Examples of the suitable average molecular weight range of these polyether polyols is generally about 300 to about 12,000 and preferably about 700 to around 10, 000.
  • One suitable polyether polyol is an ethylene glycol-propylene glycol copolymer sold as Pluracol ® V-10 polyol by BASF-Wyandotte Corporation and having the properties shown below.
  • Suitable class of lubricant are the water soluble, nonionic poly (ethylene oxide) homopolymers ranging in molecular weight from 100,000 to 5,000,000.
  • the general formula of such polyether resins is - (0-CH2CH2)n- . where n may range from about 2000 to about 100,000.
  • These resins are available from the Union Carbide Corporation under the designation Polyox ® water soluble resins.
  • Preferred is Polyox ® WSR-301 resin which has an approximate molecular weight of 4,000,000.
  • adheresion promoter is meant a substance which increases the adhesion, through crosslinking or otherwise, between the thermoplastic and the glass fiber. A number of such adhesion promoters are known in the art and used in sizing compositions and can be used in this invention.
  • adhesion promoters are blocked organic polyisocyanates, preferably those comprising an aliphatic diisocyanate such as trimethylene, tetramethylene, hexamethylene, 1, 4-cyclohexane diisocyanates and the like.
  • the blocking agent may be a ketoxime, caprolactam, phenol, alcohol or other typical blocking agent known to those skilled in the art.
  • the preferred blocking agents are ketoximes .
  • the preferred adhesion promoter is 1,6 hexamethylene diisocyanate commercially available as a light brown to yellow liquid with a specific gravity of 1.1 at 25°C, and a bulk density of 9.2 pounds per gallon, sold by Mobay Corp., Pittsburgh, PA under the product name Baybond XW-116 Crosslinker.
  • the sizing is mixed with water to have an amount of solids less than 40% and preferably about 7%, as is known to those skilled in the art.
  • EXAMPLE Add 85.1 pounds (38,600 grams) of maleonated polypropylene emulsion (Protolube RL-5440) to 20 gallons (75.7 liters) of deionized water at room temperature in a large tank with gentle stirring. It is important to avoid air entrainment and foam generation in the mixture. In a separate tank, add 10.6 pounds (4808 grams) of gamma-aminopropyltriethoxy silane to 20 gallons of deionized water at room temperature. After gentle stirring for about 10 minutes, add to the prior mixture with moderate stirring.
  • Glass fibers were sized with the sizing prepared as described above, with a roller applicator, and were then chopped in the wet state and subsequently dried. The fibers were then compound extruded with a commercially available chemically coupled polypropylene at a 30 weight percent glass content. This chemically coupled polypropylene was one which contained about 0.05 to 0.07 weight percent maleic anhydride and is available as PC072 from Himont Chemical Co. The pellets of extruded glass and polypropylene were molded in a 200 ton injection molding unit and then tested for strength.
  • the tensile and Izod strength tests were carried out in accordance with test procedures ASTM-D638 and ASTM-D256 respectively.
  • the unnotched impact test was carried out by the same procedure as the Izod test except that the notch was deleted.
  • the fibers sized as taught herein clearly enhanced the strength of the molded polypropylene to a greater degree than did the competitive fibers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

Fibre de verre utilisée pour renforcer des matières thermoplastiques, et comprenant, outre de l'eau, un mélange d'un polymère acrylique à fonctionnalité époxy et d'un polymère d'acétate vinylique, un agent de couplage à base de silane, une composition de polypropylène émulsifiée, un lubrifiant, et un promoteur d'adhérence. La résistance de matières thermoplastiques moulées renforcées par des fibres de verre encollées selon cette invention est supérieure à celle des autres matières thermoplastiques.
PCT/US1994/000353 1993-01-12 1994-01-11 Encollage de fibres de verre Ceased WO1994015884A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US320493A 1993-01-05 1993-01-05
US08/003,204 1993-01-12

Publications (1)

Publication Number Publication Date
WO1994015884A1 true WO1994015884A1 (fr) 1994-07-21

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ID=21704705

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/000353 Ceased WO1994015884A1 (fr) 1993-01-12 1994-01-11 Encollage de fibres de verre

Country Status (1)

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WO (1) WO1994015884A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0729829A3 (fr) * 1995-02-28 1997-04-02 Azdel Inc Composites d'une polyoléfine fonctionnalisée renforcée par des fibres
US5827612A (en) * 1992-06-17 1998-10-27 Ppg Industries, Inc. Aqueous coating compositions for glass fibers, fiber strands coated with such compositions and optical fiber cable assemblies including such fiber strands
US6051315A (en) * 1992-06-17 2000-04-18 Ppg Industries Ohio, Inc. Optical fiber cable assembly and method of reducing water wicking in the same
US6379794B1 (en) 1992-06-17 2002-04-30 Ppg Industries Ohio, Inc. Acrylic impregnant for fibers
WO2008036224A3 (fr) * 2006-09-18 2008-05-22 Ocv Intellectual Capital Llc Composition d'encollage à deux constituants pour fibres de renforcement
USRE44893E1 (en) 2004-03-26 2014-05-13 Hanwha Azdel, Inc. Fiber reinforced thermoplastic sheets with surface coverings

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3803069A (en) * 1968-05-03 1974-04-09 Ppg Industries Inc Glass fiber size of curable,blocked polyurethane emulsion with amino silane
US3814715A (en) * 1969-05-21 1974-06-04 Ppg Industries Inc Glass fiber size containing polyolefin emulsion
US4271229A (en) * 1979-09-04 1981-06-02 Ppg Industries, Inc. Sizing composition to yield sized glass fibers with improved UV stability
US4457970A (en) * 1982-06-21 1984-07-03 Ppg Industries, Inc. Glass fiber reinforced thermoplastics
US4608304A (en) * 1982-09-30 1986-08-26 Mobay Corporation Glass fibers coated with aqueously dispersed coating compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3803069A (en) * 1968-05-03 1974-04-09 Ppg Industries Inc Glass fiber size of curable,blocked polyurethane emulsion with amino silane
US3814715A (en) * 1969-05-21 1974-06-04 Ppg Industries Inc Glass fiber size containing polyolefin emulsion
US4271229A (en) * 1979-09-04 1981-06-02 Ppg Industries, Inc. Sizing composition to yield sized glass fibers with improved UV stability
US4457970A (en) * 1982-06-21 1984-07-03 Ppg Industries, Inc. Glass fiber reinforced thermoplastics
US4608304A (en) * 1982-09-30 1986-08-26 Mobay Corporation Glass fibers coated with aqueously dispersed coating compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5827612A (en) * 1992-06-17 1998-10-27 Ppg Industries, Inc. Aqueous coating compositions for glass fibers, fiber strands coated with such compositions and optical fiber cable assemblies including such fiber strands
US5925462A (en) * 1992-06-17 1999-07-20 Ppg Industries Ohio, Inc. Aqueous coating compositions for glass fibers, fiber strands coated with such compositions and optical fiber cable assemblies including such fiber strands
US6051315A (en) * 1992-06-17 2000-04-18 Ppg Industries Ohio, Inc. Optical fiber cable assembly and method of reducing water wicking in the same
US6379794B1 (en) 1992-06-17 2002-04-30 Ppg Industries Ohio, Inc. Acrylic impregnant for fibers
EP0729829A3 (fr) * 1995-02-28 1997-04-02 Azdel Inc Composites d'une polyoléfine fonctionnalisée renforcée par des fibres
USRE44893E1 (en) 2004-03-26 2014-05-13 Hanwha Azdel, Inc. Fiber reinforced thermoplastic sheets with surface coverings
WO2008036224A3 (fr) * 2006-09-18 2008-05-22 Ocv Intellectual Capital Llc Composition d'encollage à deux constituants pour fibres de renforcement

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