WO2006001984A1 - Fatty amide composition for wet use chopped strand glass fibers - Google Patents
Fatty amide composition for wet use chopped strand glass fibers Download PDFInfo
- Publication number
- WO2006001984A1 WO2006001984A1 PCT/US2005/019664 US2005019664W WO2006001984A1 WO 2006001984 A1 WO2006001984 A1 WO 2006001984A1 US 2005019664 W US2005019664 W US 2005019664W WO 2006001984 A1 WO2006001984 A1 WO 2006001984A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- asphalt
- sizing composition
- fatty amide
- glass
- silane coupling
- Prior art date
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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
-
- 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
- C03C25/25—Non-macromolecular compounds
-
- 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
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
- E04D1/12—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface
- E04D1/20—Roofing elements shaped as plain tiles or shingles, i.e. with flat outer surface of plastics; of asphalt; of fibrous materials
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/02—Roof covering by making use of flexible material, e.g. supplied in roll form of materials impregnated with sealing substances, e.g. roofing felt
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
Definitions
- the present invention relates generally to a sizing composition for glass fibers, and more particularly, to a sizing composition for wet use chopped strand glass fibers that contains a fatty amide lubricant synthesized from a (poly)ethylene amine and an unsaturated C 5 - C 2 o fatty acid.
- a composite roofing material formed from a reinforcing fiber material sized with the sizing composition is also provided.
- Glass fibers are useful in a variety of technologies. For example, glass fibers are commonly used as reinforcements in the building composite industry because they do not shrink or stretch in response to changing atmospheric conditions.
- roofing materials such as roofing shingles, roll roofing, and commercial roofing, are typically constructed of a glass fiber mat, an asphalt coating on the fibrous mat, and a surface layer of granules embedded in the asphalt coating.
- glass fibers are first formed by attenuating streams of a molten glass material from a bushing or orifice. The molten glass may be attenuated by a winder which collects gathered filaments into a package or by rollers which pull the fibers before they are collected and chopped.
- aqueous sizing composition is typically applied to the fibers after they are drawn from the bushing to protect the fibers from breakage during subsequent processing, to retard interfilament abrasion, and to improve the compatibility of the fibers with the matrix resins that are to be reinforced.
- the fibers are packaged in their wet condition as wet use chopped strand glass (WUCS).
- WUCS chopped strand glass
- the wet, chopped fibers are then dispersed in a water slurry which may contain surfactants, viscosity modifiers, or other chemical agents and agitated to disperse the fibers.
- the slurry containing the dispersed fibers is then deposited onto a moving screen where a substantial portion of the water is removed to form a web.
- a binder is then applied, and the resulting mat is heated to remove the remaining water and cure the binder.
- asphalt is applied to the mat, such as by spraying the asphalt onto one or both sides of the mat or by passing the mat through a bath of molten asphalt to place a layer of asphalt on both sides of the mat and fill in the interstices between the individual glass fibers.
- the coated mat is then cut to an appropriate shape and size to form the shingle.
- Conventional sizing compositions for wet use chopped strand glass typically contain a film-forming polymeric or resinous component, a coupling agent, and a lubricant dissolved or dispersed in a liquid medium. Unfortunately, such conventional size compositions are not always compatible with the asphalt used to coat the fibrous mats and form the roofing shingles.
- the synthesized fatty amide compound is formed of an amine- based hydrophilic midsection with hydrophobic tails at either end.
- the hydrophobic tails are preferably conjugated and contain a high degree of unsaturation.
- the (poly)ethylene amine is tetraethylenepentamine and the fatty acid is a conjugated fatty acid.
- the fatty amide lubricant may or may not be modified by an elastomer such as a maleinized rubber or a carboxylated rubber during the synthesis of the fatty amide lubricant.
- Secondary lubricants, viscosity modifiers, pH adjusters, biocides, and coalescents such as glycols and glycol ethers may also be included in the sizing composition.
- the reinforcing fiber material may be one or more strands of glass, natural fibers, carbon fibers, or one or more synthetic polymers.
- glass fibers are sized with the sizing composition and packaged as wet use chopped strand glass that is subsequently used to form reinforced building or roofing composites such as shingles.
- a sizing composition that includes one or more firm forming agents, at least one coupling agent, and a fatty amide lubricant synthesized from a (poly)ethylene amine and a C 5 - C 20 unsaturated fatty acid as described above.
- Gd valent bonding between the glass and the asphalt may be established through a vulcanizing mechanism in which the unsaturated - ⁇ hydrophobic tails on the synthesized fatty, amide react with the asphalt in the presence of ; sulfur at an elevated temperature and crosslink the glass and the asphalt.
- This interfacial bonding results in increased mechanical performance and improved tear strength in the composite article formed from fibers sized with the inventive sizing composition.
- a further advantage of the synthesized fatty amide lubricant is that the high hydrophobicity and low surface energy of the hydrophobic tails on the fatty amide lubricant enhances the compatibility between the glass and the asphalt during the formation of asphalt roofing products and improves glass/asphalt interactions through the reduced interfacial tensions.
- the sizing composition includes one or more film forming agents, at least one coupling agent, and a fatty amide lubricant synthesized from a (poly)ethylene amine and a C 5 - C 2 o unsaturated fatty acid.
- the fatty amide lubricant may or may not be modified by an elastomer.
- Conventional lubricants, viscosity modifiers, pH adjusters, biocides, and coalescents such as glycols and glycol ethers may also be included in the . sizing composition.
- the film forming polymer component of the.sizing composition may be any suitable polymer that can be dispersed or dissolved into an aqueous medium and which will coalesce to form a film when the sizing composition has been dried, hi addition, the film former is desirably chosen to have compatibility with the. matrix resin in which the sized glass fibers will be used.
- film forming agents for use in the size composition include polyester polymers, polyurethahes, acrylic polymers, vinyl polymers, mixtures of such polymers, copolymers of the corresponding monomers, carboxylic acid or anhydride modified polyolefins, cellulose, polyvinyl alcohols (PVA), and mixtures thereof.
- the film forming polymer is a polyvinyl alcohol, and in an even more preferred embodiment, the film forming polymer is a partially hydrolyzed polyvinyl alcohol having approximately 87 - 89% hydrolysis and a low to intermediate molecular weight.
- suitable polyvinyl alcohols for use in the size include Celvol 203, 205, and 325 from Celanese Chemicals.
- the film forming agent or agents may be present in the size composition in an amount of approximately 30 - 80% by weight of dry solids.
- the sizing composition contains one or more coupling agents.
- at least one of the coupling agents is a silane coupling agent.
- Silane coupling agents function to enhance the adhesion of the film forming polymer to the glass fibers and to reduce the level of fuzz, or broken fiber filaments, during subsequent processing.
- Examples of silane coupling agents which may be used in the size composition may be characterized by the functional groups amino, epoxy, vinyl, methacryloxy, ureido, isocyanato, and azamido.
- Suitable silane coupling agents for use in the size include, but are not limited to, ⁇ - 5 aminopropyltriethoxysilane (A- 1100), n-trimethoxy-silyl-propyl-ethylene-diamine (A- 1120), ⁇ -glycidoxypropyltrimethoxysilane (A-187), ⁇ -methacryloxypropyltrimethoxysilane (A- 174), n- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane (A-1120), methyl-trichlorosilane (A- 154), methyl-trimethoxysilane (A- 163), ⁇ -mercaptopropyl-trimethoxy-silane (A- 189), ⁇ -chloropropyl-trimethoxy-silane (A-143), vinyl-triethoxy-silane (A-151), vinyl-tris-(2- 10 methoxyethoxy
- the size composition v >; ⁇ ⁇ . : contains both an aminosilane coupling agent and a vinyl silane coupling agent.
- the • ;i. 15 ⁇ coupling agent or agents may be present in the sizing composition in an amount of from 5 : i : • :-, - 30%, and preferably, in an amount of from 10 - 20% by weight of the dry solids. ?..,, - ' ⁇ ...
- the sizing composition also contains a fatty amide lubricant synthesized from a (poly)ethylene amine and an unsaturated C 5 - C 20 fatty acid such as linoleic acid or oleic acid.
- a fatty amide lubricant synthesized from a (poly)ethylene amine and an unsaturated C 5 - C 20 fatty acid such as linoleic acid or oleic acid.
- vegetable-based unsaturated fatty acids such as, but not limited to, Agri- 20 Pure 130 (Cargill, Inc.) and Agri-Pure 150 (Cargill, Inc.) maybe used to synthesize the fatty amide lubricant.
- the unsaturated fatty acid is a fatty acid containing conjugated double bonds such as linoleic acid, Edenor UKD 5010 (Cognis Corp.), Edenor UKD 5020 (Cognis Corp.), and Edenor UKD 6010 (Cognis Corp.).
- Non-exclusive examples of (poly)ethylene amines that may be used to form the fatty amide lubricant 25 include tetraethylenepentamine (TEPA), diethylenetriamine (DETA), tetraethylenetriamine (TETA), ethylene diamine, diethylene triamine, triethylene tetramine, and pentaethylene hexamine.
- the (polyethylene amine is tetraethylenepentamine.
- the synthesized fatty amide compound is formed of an amine-based hydrophilic midsection with hydrophobic tails at either end.
- the hydrophobic tails are preferably 30 conjugated and contain a high degree of unsaturation.
- the fatty amide lubricant may be present in the size in an amount of from 5 - 30% by weight of the dry solids, and more preferably in an amount of from 10 - 20% by weight of the dry solids.
- the fatty amide lubricant may be modified with an elastomer by incorporating a maleinized rubber or a carboxylated rubber during the synthesis of the fatty amide lubricant.
- incorporación of hydrophobic rubbers or elastomers in the synthesized fatty amide aids in reducing the surface energy of the glass fibers and in enhancing interactions between glass and asphalt.
- the elastomers may serve as an energy buffer or barrier to dissipate the energy passed between the high modulus rigid glass and low modulus soft asphalt when asphalt roofing products are subjected to an impact force.
- suitable maleinized rubbers include adducts of maleic anhydride and polybutadiene and adducts of maleic anhydric and polybutadiene styrene copolymers.
- the maleinized rubber or carboxylated rubber may be present in an amount of 5 - 40% by weight of the fatty amide lubricant, and even more preferably in an amount of from 10 - 30% by weight of the fatty amide lubricant.
- the size composition may also contain a secondary lubricant to facilitate manufacturing.
- the secondary lubricant may be:.
- any conventional lubricant such as, but are not limited to, water-soluble ethyleneglycol , stearates (e.g., polyethyleneglycol monostearate, butoxyethyl stearate, and- polyethylene - ⁇ .: i glycol monooleate), ethyleneglycol oleates, ethoxylated fatty amines, glycerine, emulsified-, mineral oils, organopolysiloxane emulsions, stearic ethanolamide (sold under the trade designation Lubesize K- 12 (Alpha/Owens Corning)), Stantex G-8145 (Cognis Corp.), SF- 8275 (Cognis Corp.), and Emery 6760 (Cognis Corp).
- stearates e.g., polyethyleneglycol monostearate, butoxyethyl stearate, and- polyethylene - ⁇ .: i glycol monooleate
- the secondary lubricant may be present in the size in an amount of from 0 - 10% by weight of the dry solids.
- the sizing composition may contain a viscosity modifier such as a polyacrylamide, a hydroxyethyl cellulose, or a polyamine viscosity modifier.
- a viscosity modifier such as a polyacrylamide, a hydroxyethyl cellulose, or a polyamine viscosity modifier.
- specific examples of viscosity modifiers include Nalco 7530 (ONDEO Nalco), 01PF067 (ONDEO Nalco), Superfloc C-507 (Cytec Industries, Inc.), Superfloc MX 40 (Cytec Industries, Inc.), Superfloc MX 80 (Cytec Industries, Inc.), and Superfloc SD-2065 (Cytec Industries, Inc.).
- the viscosity modifier acts as a secondary dispersant in the size composition.
- the viscosity modifier may be present in the sizing composition in an amount of from 0 - 5% by weight of the dry solids.
- the size composition may optionally include a pH adjusting agent such as acetic acid, citric acid, sulfuric acid, or phosphoric acid in an amount sufficient to adjust the pH to a desired level.
- the pH may be adjusted depending on the intended application, or to facilitate the compatibility of the ingredients of the size composition.
- the sizing composition has a pH of from 3 - 6, and more preferably a pH of from 4 - 5.
- the size may optionally contain conventional additives such as dyes, oils, fillers, thermal stabilizers, anti-foaming agents, anti-oxidants, dust suppression agents, wetting agents, and/or other conventional adjuvants, hi addition, the size may include coalescents such as glycols and glycol ethers to aid in fiber storage stability and/or biocides such as Amerstad 250 (Ashland Chemicals) and Nalco 9380 (ONDEO Nalco).
- the balance of the size composition is composed of water, hi particular, water may be added to dilute the aqueous sizing composition to a viscosity that is suitable for its application to glass fibers and to achieve the desired solids content.
- the sizing composition may contain up to approximately 99.5% water.
- the size composition maybe applied to strands of glass formed by conventional techniques such as by drawing molten glass through a heated bushing to form substantially " ⁇ continuous glass fibers.
- Any type of glass such as A-type glass, C-type glass, E-type glass, S-type glass, or modifications thereof, is suitable for use as the fiber material.
- the boron oxide is replaced by magnesium oxide.
- the sizing composition may be applied to strands of one or more synthetic polymers such as polyester, polyamide, aramid, and mixtures thereof.
- the polymer strands may be used alone as the reinforcing fiber material, or they can be used in combination with glass strands such as those described above.
- natural fibers may be used as the reinforcing fiber material.
- the size composition is preferably applied to the fibers such that the size is present on the fibers in an amount of from about 0.02 to about 0.50 percent by weight based on the total weight of the fibers, and even more preferably in an amount of from about 0.05 to about 0.30 percent by weight. This can be determined by the loss on ignition (LOI) of the WUCS fibers, which is the reduction in weight experienced by the fibers after heating them to a temperature sufficient to burn or pyrolyze the organic size from the fibers.
- the size composition may be applied to fibers having a diameter of from about 6 - 23 microns, with fibers of from about 11 - 20 microns in diameter being more preferred.
- the sizing composition may be applied to the fibers in any conventional manner using any conventional applications such as by spraying or drawing the fibers to be sized across a rotating or stationary roll wet with the sizing composition.
- the size composition is preferably applied to the fibers in an amount sufficient to provide the fibers with a moisture content of from about 10% by weight to about 15% by weight of the WUCS fibers.
- glass fibers are sized with the sizing composition and packaged as wet use chopped strand glass that is subsequently used to form reinforced building or roofing composites such as shingles.
- the sized glass fibers are chopped while wet and dispersed into a water slurry which may contain surfactants, viscosity modifiers, or other chemical agents.
- the slurry containing the dispersed fibers is then deposited onto a moving screen where a substantial portion of the water is removed.
- a binder e.g., a: urea formaldehyde binder or a polycarboxylic acid based binder
- the formed non- woven mat is an assembly of randomly oriented, dispersed, individual glass filaments.
- the mat may be dried by in any conventional manner, such as by passing the mat through an oven.
- Asphalt is then applied to the dried/cured mat in any known manner, such as by passing the mat through a bath containing an asphalt mix that may include molten asphalt, fillers, and optionally sulfur to place a layer of asphalt on at least one side of the mat and fill in the interstices between the individual glass fibers.
- the asphalt-coated mat is then cut to the appropriate shape and size to form a shingle.
- the hot asphalt-coated mat may then be passed beneath one or more granule applicators which apply protective surface granules to portions of the asphalt-coated mat prior to cutting into the desired shape.
- the synthesized fatty amide is designed not only to function as a lubricant and a dispersant, but also to interact with the asphalt in the asphalt mix.
- one advantage provided by the fatty amide is its built-in reactivity with other components.
- covalent bonding e.g., interfacial bonding
- the unsaturated hydrophobic tails on the synthesized fatty amide react with the asphalt in the presence of sulfur at an elevated temperature and crosslink the glass and the asphalt, hi this reaction, the sulfur acts as a catalyst.
- the interfacial bonding between the glass and the asphalt increases the mechanical strength of the resulting composite article.
- the nitrogens present in the hydrophilic amine-based mid section of the synthesized fatty amide, once neutralized with an acid become cationic nitrogens.
- fatty amide modifies the surface energy of the glass to make the glass more compatible with the asphalt.
- the high hydrophobicity and low surface energy of the hydrophobic tails on the fatty amide lubricant enhances the compatibility between the glass and the asphalt and improves glass/asphalt interactions through the reduced interfacial tensions.
- the new fatty amide also acts as an adhesion promoter.
- Table 2 illustrates a 1 kg charge based on the ingredients set forth in Table 1.
- the stearic acid was charged and melted at 200 0 F under a light nitrogen blanket. Once all of the stearic acid was melted, it was agitated under a nitrogen blanket. When the temperature was controlled at 200 °F, the heat was removed. Tetraethylenepentamine (TEPA) was then slowly added from a dropping funnel. After an exotherm peak, the heating was resumed. Once all of the TEPA was added, the temperature was raised as fast as the foaming permitted. At approximately 380 °F, it was determined that approximately 50% of the distillate had been removed. At this time, the nitrogen blanket was removed and a low nitrogen sparge was applied. After the low nitrogen sparge was applied, heat was again applied towards a maximum temperature of 480 °F until the distillate stopped.
- TEPA Tetraethylenepentamine
- the reaction mixture was cooled to a temperature of approximately 160 - 170 °F by ambient air.
- the total distillate removed from the stearic acid and TEPA was determined to be approximately 12% of the total charge.
- Acetic acid was then added over a period of approximately 15 minutes. A slight exotherm of approximately 10 °F was noted as the acetic acid was added.
- the mixture was agitated for approximately 10 minutes and then poured onto release paper where it was permitted to cool and solidify.
- the final product at 1% in water had a pH in the range of 4.5 - 5.0.
- the final product prior to acid neutralization had a residual acid value of 0.4% and a non- detectable iodine value.
- the solidified product was determined to be Lubesize K-12.
- Example 2 Synthesis of an Unsaturated Fatty Amide Lubricant Containing Conjugated Diene Structure ⁇ : The experiment set forth in Example 1 was repeated except that stearic acid was replaced with linoleic acid on an equivalent basis.
- the linoleic acid used was Emersol 315 linoleic acid from Cognis Corp.
- the finished product prior to acid neutralization had a residual acid value of 0.29% and an iodine value of 24.8.
- the iodine value of Emersol 315 linoleic acid was 27.4. It was determined that approximately 90.5% of the unsaturation in the fatty acid was maintained in the synthesized product.
- Example 3 Synthesis of an Unsaturated Fatty Amide Lubricant Containing No Conjugated Diene Structure
- the experiment set forth in Example 1 was repeated except that stearic acid was replaced with oleic acid on an equivalent basis.
- the oleic acid used was Emersol 213 oleic acid from Cognis Corp.
- the synthesized product prior to acid adjustment had a residual acid value of 0.18% and an iodine value of 21.8.
- the iodine value of Emerson 213 oleic acid was 24.3. It was determined that approximately 90% of the unsaturation in the fatty acid was maintained in the synthesized product.
- Example 4 Synthesis of a Rubber Modified Unsaturated Fatty Amide The experiment set forth in Example 1 was repeated except that the stearic acid was replaced with 90% of Emersol 315 linoleic acid (Cognis Corp.) and 10% Ricon 130MA13 maleinized polybutadiene (Sartomer) on a weight basis.
- the synthesized product prior to acid neutralization had a residual acid value of 0.21% and an iodine value of 27.7.
- the iodine value of the raw mixture of linoleic acid and maleinized polybutadiene prior to the condensation reaction was 36.3. It was determined that 76.3% of the unsaturation in the fatty acid was retained in the synthesized product.
- Example 5 Synthesis of a Polybutadiene Styrene Copolymer Rubber Modified Unsaturated Fatty Amide
- the experiment set forth in Example 1 was repeated except that the stearic acid was replaced with 90% of Emersol 315 linoleic acid (Cognis Corp.) and 10% Ricon 184MA6 maleinized polybutadiene styrene rubber (Sartomer) on a weight basis.
- the iodine content of the starting raw mixture of linoleic acid and polybutadiene styrene rubber prior to the condensation reaction was 32.2.
- the synthesized product prior to acid neutralization had a residual acid value of 0.25% and an iodine value of 30.7. It was determined that approximately 95.3% of the unsaturation of the fatty acid was maintained in the synthesized product.
- Example 6 Comparison of Lubesize K- 12 and Unsaturated Fatty Amide Lubricant Containing Conjugated Diene Structure Fiber samples were coated with sizing compositions containing the fatty amides prepared in Examples 1 and 2 above. The sized fiber samples were formed into roofing mats on a sheet former. The mat samples were then converted to lab shingle samples by coating the mats with an asphalt mix containing 0%, 0.2%, or 0.8% post-added elemental sulfur. The results are summarized in Table 3. TABLE 3
- CD cross direction Tear strengths were measured on an Elmendorf Tear Strength Tester following the procedure set forth in ASTM D-3462 Units for tear strength are in grams
- the performance improvement data in this Example shows that a lab shingle formed from fibers sized with a sizing composition containing a fatty amide synthesized from TEPA and a conjugated fatty acid had improved tear strength with or without external sulfur in the asphalt coating formulation.
- a lab shingle formed from fibers sized with a sizing composition containing a fatty amide synthesized from TEPA and a conjugated fatty acid had improved tear strength with or without external sulfur in the asphalt coating formulation.
- Example 7 Comparison of Lubesize K- 12 and Unsaturated Fatty Amide Lubricant Containing No Conjugated Diene Structure Fiber samples were coated with sizing compositions containing the fatty amides prepared in Examples 1 and 3 above. The sized fiber samples were formed into roofing mats on a sheet former. The mat samples were then converted to lab shingle samples by coating the mats with an asphalt mix containing 0% and 0.2% post-added elemental sulfur. The results are summarized in Table 4. TABLE 4
- CD cross direction Tear strengths were measured on an Elmendorf Tear Strength Tester following the procedure set forth in ASTM D-3462 Units for tear strength are in grams
- the performance improvement data in this Example shows that a lab shingle formed from fibers sized with a sizing composition containing a fatty amide synthesized from TEPA and a non-conjugated unsaturated fatty acid had improved tear strength with or without external sulfur in the asphalt coating formulation.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20050758435 EP1765741A1 (en) | 2004-06-15 | 2005-06-03 | Fatty amide composition for wet use chopped strand glass fibers |
JP2007516532A JP2008502573A (en) | 2004-06-15 | 2005-06-03 | Aliphatic amide composition for chopped strand glass fiber for wet use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/868,231 US20050276960A1 (en) | 2004-06-15 | 2004-06-15 | Fatty amide composition for wet use chopped strand glass fibers |
US10/868,231 | 2004-06-15 |
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WO2006001984A1 true WO2006001984A1 (en) | 2006-01-05 |
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PCT/US2005/019664 WO2006001984A1 (en) | 2004-06-15 | 2005-06-03 | Fatty amide composition for wet use chopped strand glass fibers |
Country Status (6)
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US (1) | US20050276960A1 (en) |
EP (1) | EP1765741A1 (en) |
JP (1) | JP2008502573A (en) |
KR (1) | KR20070015226A (en) |
CN (1) | CN1968906A (en) |
WO (1) | WO2006001984A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2842516B1 (en) * | 2002-07-18 | 2004-10-15 | Saint Gobain Vetrotex | SIZING COMPOSITION FOR VERRANNE, METHOD USING THE SAME AND RESULTING PRODUCTS |
FR2888255B1 (en) * | 2005-07-06 | 2007-11-16 | Saint Gobain Vetrotex | REINFORCING YARNS AND COMPOSITES HAVING IMPROVED FIRE PROTECTION |
US20070006775A1 (en) * | 2005-07-07 | 2007-01-11 | Helwig Gregory S | Method for producing a wet-laid fiber mat |
CN1923740B (en) * | 2006-09-13 | 2010-05-12 | 中材科技股份有限公司 | Enhancement soakage agent for thin glass fiber bulked yarn |
US8080171B2 (en) * | 2007-06-01 | 2011-12-20 | Ocv Intellectual Capital, Llc | Wet-laid chopped strand fiber mat for roofing mat |
US7927459B2 (en) * | 2007-09-17 | 2011-04-19 | Ocv Intellectual Capital, Llc | Methods for improving the tear strength of mats |
US20100055439A1 (en) * | 2008-08-29 | 2010-03-04 | Lee Jerry H C | WUCS Fibers Having Improved Flowing And Dispersing Properties |
US9290584B2 (en) | 2011-07-05 | 2016-03-22 | Exxonmobil Research And Engineering Company | Polyalkylene carboxylic acid polyamine additives for fouling mitigation in hydrocarbon refining processes |
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JP6458843B1 (en) * | 2017-10-13 | 2019-01-30 | 日東紡績株式会社 | Surface treated glass fiber woven fabric and glass fiber reinforced silicone resin film material using the same |
US11332881B2 (en) * | 2018-01-05 | 2022-05-17 | Certainteed Llc | Fiber mat, method of making the fiber mat, and bituminous roofing product |
CN110342836A (en) * | 2019-07-29 | 2019-10-18 | 泰山玻璃纤维邹城有限公司 | Enhance rubber glass fiber infiltration agent and preparation method thereof |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1522148A (en) * | 1974-10-03 | 1978-08-23 | Owens Corning Fiberglass Corp | Glass fibres coated with a size which provides forming and bonding properties |
US4468430A (en) * | 1982-12-23 | 1984-08-28 | Owens-Corning Fiberglas Corporation | Asphalt shingle with glass fiber mat |
EP0450638A1 (en) * | 1990-04-05 | 1991-10-09 | Ppg Industries, Inc. | Chemical composition to produce water soluble curable films on fibrous surfaces and so treated glass fibers |
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 |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2345632A (en) * | 1939-05-20 | 1944-04-04 | Nat Oil Prod Co | Polyamides |
US2425392A (en) * | 1939-05-20 | 1947-08-12 | Nopco Chem Co | Diamide textile lubricants |
US2991196A (en) * | 1950-12-12 | 1961-07-04 | Owens Corning Fiberglass Corp | Sized glass fiber products |
US2671744A (en) * | 1951-02-09 | 1954-03-09 | Owens Corning Fiberglass Corp | Sized strands and method of making same |
US2758026A (en) * | 1952-05-31 | 1956-08-07 | American Cyanamid Co | Sized waterlaid glass fiber products and process of preparing the same |
US3097963A (en) * | 1959-03-30 | 1963-07-16 | Owens Corning Fiberglass Corp | Sized glass fibers and composition |
NL268570A (en) * | 1960-08-24 | |||
NL302868A (en) * | 1963-03-21 | |||
US3827230A (en) * | 1970-04-13 | 1974-08-06 | Owens Corning Fiberglass Corp | Glass fiber size |
US3933711A (en) * | 1972-10-31 | 1976-01-20 | Ppg Industries, Inc. | Forming size of aqueous polyvinylacetate |
US3850869A (en) * | 1973-01-02 | 1974-11-26 | Johns Manville | Glass fiber sizing composition and resultant product with high resistance to abrasion |
US3864155A (en) * | 1973-04-27 | 1975-02-04 | Ppg Industries Inc | Glass fiber size and resulting product |
US3865768A (en) * | 1973-06-25 | 1975-02-11 | Johns Manville | Aqueous fiber glass sizing composition |
US4318960A (en) * | 1977-11-07 | 1982-03-09 | Owens-Corning Fiberglas Corporation | Glass fiber size composition comprising maleic anhydride graft copolymer |
US4179537A (en) * | 1978-01-04 | 1979-12-18 | Rykowski John J | Silane coupling agents |
US4351752A (en) * | 1979-06-18 | 1982-09-28 | Ppg Industries, Inc. | Detackified aqueous sizing composition comprising liquid polymer and free radical generator |
US4361465A (en) * | 1980-03-19 | 1982-11-30 | Ppg Industries, Inc. | Glass fibers with improved dispersibility in aqueous solutions and sizing composition and process for making same |
US4461804A (en) * | 1981-05-29 | 1984-07-24 | Ppg Industries, Inc. | Aqueous sizing composition for glass fibers for use in producing a mat |
US4536446A (en) * | 1982-09-24 | 1985-08-20 | Ppg Industries, Inc. | Treated glass fibers and nonwoven sheet-like mat and method |
US4536447A (en) * | 1982-09-24 | 1985-08-20 | Ppg Industries, Inc. | Treated glass fibers and aqueous dispersion and nonwoven mat of glass fibers |
US4681658A (en) * | 1982-09-24 | 1987-07-21 | Ppg Industries, Inc. | Treated glass fibers and nonwoven sheet-like mat and method |
US4457785A (en) * | 1982-09-24 | 1984-07-03 | Ppg Industries, Inc. | Treated glass fibers and nonwoven sheet-like mat and method |
US4626289A (en) * | 1982-09-24 | 1986-12-02 | Ppg Industries, Inc. | Treated glass fibers and aqueous dispersion and nonwoven mat of glass fibers |
DE3676262D1 (en) * | 1985-03-06 | 1991-01-31 | Pilgrim Eng Dev | IMPROVEMENTS ON MULTI-SCREW TENSIONERS. |
US5354829A (en) * | 1992-06-30 | 1994-10-11 | Ppg Industries, Inc. | Silylated polyamine polymers and a method of treating fibers |
WO1994004731A1 (en) * | 1992-08-21 | 1994-03-03 | Ppg Industries, Inc. | Vinyl polymer compatible treated glass-type substrates |
US5773146A (en) * | 1995-06-05 | 1998-06-30 | Ppg Industries, Inc. | Forming size compositions, glass fibers coated with the same and fabrics woven from such coated fibers |
DE19611850A1 (en) * | 1996-03-26 | 1997-10-02 | Bayer Ag | Aqueous polyurethane-urea dispersions with low film-forming temperature |
US6551707B1 (en) * | 1998-10-30 | 2003-04-22 | Owens Corning Fiberglas Technology, Inc. | Mixed lubricant sizing |
US7172678B2 (en) * | 2003-06-17 | 2007-02-06 | Gaf Materials Corporation | Process of making composite sheet material |
-
2004
- 2004-06-15 US US10/868,231 patent/US20050276960A1/en not_active Abandoned
-
2005
- 2005-06-03 EP EP20050758435 patent/EP1765741A1/en not_active Withdrawn
- 2005-06-03 JP JP2007516532A patent/JP2008502573A/en active Pending
- 2005-06-03 WO PCT/US2005/019664 patent/WO2006001984A1/en not_active Application Discontinuation
- 2005-06-03 CN CNA200580019756XA patent/CN1968906A/en active Pending
- 2005-06-03 KR KR1020067026518A patent/KR20070015226A/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1522148A (en) * | 1974-10-03 | 1978-08-23 | Owens Corning Fiberglass Corp | Glass fibres coated with a size which provides forming and bonding properties |
US4468430A (en) * | 1982-12-23 | 1984-08-28 | Owens-Corning Fiberglas Corporation | Asphalt shingle with glass fiber mat |
EP0450638A1 (en) * | 1990-04-05 | 1991-10-09 | Ppg Industries, Inc. | Chemical composition to produce water soluble curable films on fibrous surfaces and so treated glass fibers |
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 |
Also Published As
Publication number | Publication date |
---|---|
JP2008502573A (en) | 2008-01-31 |
US20050276960A1 (en) | 2005-12-15 |
EP1765741A1 (en) | 2007-03-28 |
CN1968906A (en) | 2007-05-23 |
KR20070015226A (en) | 2007-02-01 |
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