CN1968906A - Fatty amide composition for wet use chopped strand glass fibers - Google Patents
Fatty amide composition for wet use chopped strand glass fibers Download PDFInfo
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- CN1968906A CN1968906A CNA200580019756XA CN200580019756A CN1968906A CN 1968906 A CN1968906 A CN 1968906A CN A200580019756X A CNA200580019756X A CN A200580019756XA CN 200580019756 A CN200580019756 A CN 200580019756A CN 1968906 A CN1968906 A CN 1968906A
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- fatty amide
- size compositions
- glass
- amide lubricant
- lubricant
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- 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
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- 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
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- 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
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- 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
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- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
A size composition containing 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<SUB>5</SUB>-C<SUB>20</SUB> unsaturated fatty acid is provided. The fatty acid is preferably a conjugated fatty acid and the (poly)ethylene amine is preferably tetraethylenepentamine. The fatty amide lubricant may be modified by maleinized rubber or carboxylated rubber. The size is advantageously applied to glass fibers such as wet use chopped strand glass and used to form roofing composites, such as shingles. The fatty amide lubricant facilitates interfacial bonding between the glass and asphalt through a vulcanizing mechanism. The unsaturation of the fatty amide modifies the surface energy of the glass fibers to make the glass more compatible with the asphalt, enhances the compatibility between the glass and the asphalt, and improves glass/asphalt interactions through the reduced interfacial tensions.
Description
Technical field of the present invention and industrial applicibility
The present invention relates generally to a kind of size compositions that is used for glass fibre, relates more particularly to a kind of size compositions of glass fiber bundle of the chopping that is used for wetting use, and said composition contains by (many) ethyleneamines and unsaturated C
5-C
20Lipid acid synthetic fatty amide lubricant.A kind of composite roof material that is formed by the reinforcing fiber materials with this size compositions gluing also is provided.
Background of invention
Glass fibre can be used for various technology.For example, glass fibre generally is used as reinforce in composite building material industry, because they can not shrink or stretch in response to the atmospheric condition that change.Roof cladding for example roof boarding, prepared roofing and commercial roofing is made of the particle surface layer of bituminous coating on glass fiber mats, the fiber mat and embedding bituminous coating usually.
In order to form roof boarding, by flowing attenuate from the fused glass material of sleeve or nozzle and at first forming glass fibre.Fused glass the accumulative silk thread can be collected in the packing up-coiler or by before with fiber collecting and chopping with the roller attenuate of tensile fiber.Usually aqueous size compositions is coated on the fiber after fiber is pulled out from sleeve, with avoid at protection fiber during the processing subsequently rupturing, to stop the wearing and tearing between silk thread and to improve the consistency of fiber and the matrix resin that will be enhanced.After fiber is handled with size compositions, under their wetting conditions with the chopped strand glass (WUCS) of their packings as wetting use.
To wet then, the chopping fiber dispersion in the water slurry that can contain tensio-active agent, viscosity modifier or other chemical reagent and stirring so that fiber dispersion.It is online that the slurries that will contain the dispersive fiber then are deposited on diaphragm, there most water removed to form net.Application of adhesive then, and with the mat heating of gained to remove remainder water and tackiness agent solidified.Next with bitumen coated on mat, for example by on the one or both sides that pitch are injected in mat or by means of make mat by fused pitch body lotion with on the both sides that brea bed placed mat and fill space between the individual glass fibers.Then the mat that applies is cut into suitable shape and size to form roof boarding.
The conventionally glue composition that is used for the chopped strand glass of wetting use comprises film-forming polymer or resin Composition, coupling agent usually and is dissolved in or is scattered in the lubricant of liquid medium.Unfortunately, the size compositions of this class routine usually can not be compatible with the pitch that is used for coated fiber pad and formation roof boarding.This uncompatibility may cause processing difficulties, and may obtain having the roof boarding of for example poor tear strength of poor physicals.In addition, the quantity of the tackiness agent that is used in combination with glue composition conventionally may increase the cost of roof boarding significantly.
Therefore, the improved size compositions that needs a kind of like this glass fiber bundle of the chopping that is used for wetting use in the art: said composition strengthened glass fiber mats to the consistency of the bituminous coating on the pitch composite product, reduced production cost and improved the physicals of matrix material.
Summary of the invention
An object of the present invention is to provide a kind of size compositions of fibrous bundle of the chopping that is used for wetting use, said composition comprises one or more membrane-forming agents, at least a coupling agent and by (many) ethyleneamines and C
5-C
20Unsaturated fatty acids synthetic fatty amide lubricant.This synthetic fatty amide compound is formed with the hydrophobic nature on arbitrary tail end is terminal by the wetting ability middle portion of amine-class.This hydrophobic nature end is conjugated and contain high degree of unsaturation preferably.In preferred embodiments, (many) ethyleneamines are that tetren and lipid acid are conjugated lipid acid.Between the synthesis phase of this fatty amide lubricant, fatty amide lubricant can by or can be not by elastomerics for example maleinization rubber or carboxylation modified rubber.Auxiliary lubricant, viscosity modifier, pH regulator agent, sterilant and coalescing agent for example glycols and glycol ethers also can be included in this size compositions.Reinforcing fiber materials can be one or more glass strands, natural fiber, carbon fiber or one or more synthetic polymers.In at least one exemplary, with the glass fibre gluing and be packaged into the chopped strand glass of wetting use, use it for subsequently and form for example roof boarding of enhanced building or roofing matrix material with size compositions.
Another object of the present invention provides a kind of composite roof material that is formed by many glass fibre with the size compositions gluing that comprises following material: one or more membrane-forming agents, at least a coupling agent and aforesaid by (many) ethyleneamines and C
5-C
20Unsaturated fatty acids synthetic fatty amide lubricant.
Another object of the present invention provides a kind of enhancing roof boarding product that is formed by the mat of the random orientation glass fibre of using the size compositions gluing that comprises following material: one or more membrane-forming agents, at least a coupling agent and aforesaid by (many) ethyleneamines and C
5-C
20Unsaturated fatty acids synthetic fatty amide lubricant.
An advantage of synthetic fatty amide: when forming the asphalt roofing product, this lubricant has itself and pitch inherent reactive behavior.Can set up covalent bonding between glass and the pitch by such sulfuration mechanism: wherein in the presence of the sulphur at elevated temperatures the unsaturated hydrophobic nature on the synthetic fatty amide terminal with the pitch reaction, and make glass and pitch crosslinked.In by the fibroplastic composite product with size compositions gluing of the present invention, this interface bonding has produced enhanced mechanical property and improved tear strength.
Another advantage of synthetic fatty amide lubricant is: the high hydrophobic of the hydrophobic nature end on the fatty amide lubricant and low surface energy have strengthened in the consistency between glass and the pitch during the formation asphalt roofing product, and have improved glass/pitch interaction by the interfacial tension that reduces.
Hereinafter, above-mentioned and other purposes, feature and advantage of the present invention will become obvious more completely from the consideration of following detailed.
Detailed description of the present invention and preferred embodiment
Unless otherwise indicated, all technology used herein and scientific terminology have with by one of them those of ordinary skill in the field under the present invention the identical implication generally understood.Although in practice of the present invention or test, can adopt and those any method and materials similar or of equal value of describing herein, describe preferable methods and material in this article.With what note is that phrase " sizing composition ", " size compositions " and " sizing material " exchange use in this article.
The present invention relates to be used for the size compositions of glass fiber bundle of the chopping of wetting use.This size compositions comprises one or more membrane-forming agents, at least a coupling agent and by (many) ethyleneamines and C
5-C
20Unsaturated fatty acids synthetic fatty amide lubricant.This fatty amide lubricant can by or can be not by elastomer-modified.Conventional lubricant, viscosity modifier, pH regulator agent, sterilant and coalescing agent for example glycols and glycol ethers also can be included in this size compositions.
The film-forming polymer component of described size compositions can be can be dispersed or dissolved in the water-bearing media and when with size compositions when dry its with the coalescent and film forming any suitable polymers of shape.In addition, wish to select this film precursor to have consistency with the matrix resin that wherein will use the glass fibre of gluing.The example that is used for the membrane-forming agent of this sizing composition comprises: the polyolefine of polyester polymers, urethane, acrylic polymers, vinyl polymer, these mixture of polymers, corresponding monomeric multipolymer, carboxylic acid or carboxylic acid anhydride modified, Mierocrystalline cellulose, polyvinyl alcohol (PVA) and its mixture.In a preferred embodiment, film-forming polymer is a polyvinyl alcohol, and in one even preferred embodiment, film-forming polymer is the polyvinyl alcohol that has the degree of hydrolysis of about 87-89% and be low to moderate the partial hydrolysis of intermediate molecular weight.The example that is used for the suitable polyvinyl alcohol of this sizing material comprises the Celvol 203,205 and 325 that is obtained from Celanese Chemicals.This membrane-forming agent can drying solid the quantity of about 30-80wt% be present in the sizing composition.
In addition, described size compositions contains one or more coupling agents.Preferably, at least a coupling agent is a silane coupling agent.Silane coupling agent has played such effect: strengthened film-forming polymer to the binding property of glass fibre and reduced the filametntary content of fine hair or fracture during processing subsequently.The example that can be used for the silane coupling agent in this sizing composition can have the feature of functional groups amino, epoxy group(ing), vinyl, methacryloxy, urea groups, isocyano and azepine amido.
The suitable silane coupling agent that is used for described sizing material includes but not limited to: γ-An Bingjisanyiyangjiguiwan (A-1100), just-trimethoxy-silylpropyl quadrol (A-1120), γ-glycidoxypropyltrimewasxysilane (A-187), γ-methacryloxypropyl trimethoxy silane (A-174), just-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120), METHYL TRICHLORO SILANE (A-154), methyltrimethoxy silane (A-163), γ-Qiu Jibingjisanjiayangjiguiwan (A-189), γ-r-chloropropyl trimethoxyl silane (A-143), vinyltriethoxysilane (A-151), vinyl-three-(2-methoxy ethoxy) silane (A-2171), vinyltriacetoxy silane (A-188), octyltri-ethoxysilane (A-137), Union carbide A-162 (A-162), methyltrimethoxy silane (A-1630), Silquest RC-I vinyl silanes and Silquest RC-2 polysulfur silane.The a kind of of the silane coupling agent of listing herein is can be from the Silquest product of GE Silicones acquisition.Preferably, sizing composition contains amino silicane coupling agent and vinyl silicane coupling agent.This coupling agent can drying solid the quantity of 5-30wt%, and preferably be present in the size compositions with the quantity of 10-20wt%.
Described size compositions also contains by (many) ethyleneamines and unsaturated C
5-C
20Lipid acid is linolic acid or oleic acid synthetic fatty amide lubricant for example.In addition, (Cargill, Inc.) (Cargill Inc.) can be used to the synthetic fat amide lubricant with Agri-Pure 150 such as but not limited to Agri-Pure 130 based on the unsaturated fatty acids of plant.Preferably, unsaturated fatty acids is the lipid acid that contains conjugated double bond, for example linolic acid, Edenor UKD 5010 (CognisCorp.), Edenor UKD 5020 (Cognis Corp.) and Edenor UKD 6010 (CognisCorp.).The nonexcludability example that can be used for forming (many) ethyleneamines of fatty amide lubricant comprises: tetren (TEPA), diethylenetriamine (DETA), four ethylidene triamines (TETA), quadrol, diethylenetriamine, Triethylenetetramine (TETA) and penten.In preferred embodiments, (many) ethyleneamines are tetrens.Synthetic fatty amide compound is formed by the wetting ability middle portion and the end of the hydrophobic nature on arbitrary tail end of amine-class.This hydrophobic nature end is conjugated and contain high degree of unsaturation preferably.This fatty amide lubricant can drying solid the quantity of 5-30wt%, and more preferably be present in the sizing material with the quantity of the 10-20wt% of drying solid.
Can be by between the synthesis phase of fatty amide lubricant, mixing maleinization rubber or carboxylation rubber with elastomerics with the fatty amide lubricant modification.Hydrophobic nature rubber or elastomerics are mixed the synthetic fatty amide help to reduce the surface energy of glass fibre and the interaction between reinforcing glass and the pitch.In addition, when making the asphalt roofing product experience a shock power, described elastomerics can play energy snubber or obstruct so that the energy dispersive effect of passing through between firm glass of high-modulus and low modulus viscid bitumen.The example of suitable maleinization rubber comprises the adducts of maleic anhydride and polyhutadiene, and the adducts of maleic anhydride and Polybutadiene-styrene multipolymer.Maleinization rubber or carboxylation rubber can fatty amide lubricant the quantity of 5-40wt%, even more preferably exist with the quantity of the 10-30wt% of fatty amide lubricant.
Except the synthetic fatty amide lubricant, described sizing composition can also contain auxiliary lubricant to promote production.Auxiliary lubricant can be the lubricant of any routine, such as but not limited to: the aliphatic amide of water-soluble glycol stearate (for example Stearinsaeure macrogol ester, butoxyethyl stearate and single oleic acid macrogol ester), oleic acid glycol ester, ethoxylation, glycerine, emulsive mineral oil, organic polysiloxane emulsion, stearic ethanolamide (under trade(brand)name Lubesize K-12, selling (Alpha/Owens Corning)), StantexG-8145 (Cognis Corp.), SF-8275 (Cognis Corp.) and Emery 6760 (Cognis Corp).Auxiliary lubricant can drying solid the quantity of 0-10wt% be present in the sizing material.
Randomly, described size compositions can contain viscosity modifier, for example polyacrylamide, Natvosol or polyamines viscosity modifier.The specific examples of viscosity modifier comprises: Nalco7530 (ONDEO Nalco), 01PF067 (ONDEO Nalco), Superfloc C-507 (Cytec Industries, Inc.), Superfloc MX 40 (CytecIndustries, Inc.), Superfloc MX 80 (Cytec Industries, Inc.), with Superfloc SD-2065 (Cytec Industries, Inc.).In sizing composition, viscosity modifier has played the effect of auxiliary dispersants.Viscosity modifier can drying solid the quantity of 0-5wt% be present in the size compositions.
In addition, described sizing composition can be randomly to be enough to that pH regulator to the quantity of desirable degree is comprised pH regulator agent for example acetate, citric acid, sulfuric acid or phosphoric acid.Can depend on the application of expection or regulate pH with the consistency of the composition that promotes sizing composition.Preferably, the pH of size compositions is 3-6, and more preferably pH is 4-5.
In addition, described sizing material can randomly contain conventional additives, for example dyestuff, oil, filler, thermo-stabilizer, defoamer, antioxidant, dust inhibitor, wetting agent and/or other conventional auxiliary agents.In addition, described sizing material can comprise coalescing agent for example glycols and glycol ethers promoting the fiber stability in storage, and/or sterilant for example Amerstad 250 (AshlandChemicals) and Nalco 9380 (ONDEO Nalco).
The surplus of described sizing composition is made up of water.Especially, can add entry and be suitable for it to the viscosity of the coating of glass fibre and obtain desirable solid content so that moisture size compositions is diluted to.This size compositions can contain about at the most 99.5% water.
Described sizing composition can be coated in by routine techniques for example by fused glass being drawn the superheated sleeve with on the glass strands that forms basic successive glass fibre and form.The glass of any kind for example A-class glass, C-class glass, E-class glass, S-class glass or its modifier is suitable for as filamentary material.For example, in a kind of modification of E-class glass, boron oxide is replaced with magnesium oxide.This class glass can be commercially available from Owens CorningFiberglass Corporation under trade(brand)name Advantex .
As selection, described size compositions can be coated in one or more synthetic polymers for example on the wire harness of polyester, polymeric amide, aromatic poly and its mixture.Described polymkeric substance wire harness can the private reinforcing fiber materials of doing of coverlet, and perhaps they can be used in combination with for example above-mentioned those glass strands.Select as another kind, can be with natural fiber as reinforcing fiber materials.The term that is used in combination with the present invention " natural fiber " is meant any part from plant, includes but not limited to the vegetable fibre that extracts in stem, seed, leaf, root or the bast.The example that is suitable for use as the natural fiber of reinforcing fiber materials comprises cotton, jute, bamboo wood, ramie, hemp, flax and its combination.Can also use carbon fiber.
Preferably by this way sizing composition is coated on the fiber: make sizing material serving as the quantity of the about 0.50wt% of about 0.02-, even more preferably be present on the fiber with the quantity of the about 0.30wt% of about 0.05-based on total weight of fiber.This can be determined by the loss on ignition (LOI) of WUCS fiber, and this loss on ignition is to be enough to organic sizing material weight of fiber experience after fiber burning or the pyrolytic temperature is reduced in that fiber is heated to.Sizing composition can be coated on the fiber of the about 6-23 micron of diameter, more preferably from about the fiber of 11-20 micron diameter.
The coating that mode that can any routine adopts any routine for example by fiber jet or stretching are passed with the wetting rotation of size compositions or fixedly roller size compositions is coated on the fiber by gluing.Preferably the quantity with the fiber that is enough to provide the about 15wt% of about 10wt%-that water-content is about the WUCS fiber is coated in sizing composition on the fiber.
In preferred embodiments,, use it for subsequently and form for example roof boarding of enhanced building or roofing matrix material with the glass fibre gluing and be packaged into the chopped strand glass of wetting use with size compositions.For example, the chopping of the glass fibre of gluing is wetting simultaneously and be distributed in the water slurry that can contain tensio-active agent, viscosity modifier or other chemical reagent.It is online that the slurries that will contain the dispersive fiber then are deposited on diaphragm, there most water removed.Application of adhesive (for example urea formaldehyde tackiness agent or polycarboxylic acid tackiness agent) then, and with the mat drying of gained to remove remainder water and tackiness agent solidified.The non-woven mat that forms is combination randomly-oriented, the single glass wire of dispersive.Can be by any usual manner for example by means of making mat pass through baking oven with the mat drying.Then with any known mode with bitumen coated on the mat of dried/cured, for example by means of the body lotion that makes mat by containing the asphalt mixture that can comprise molten asphalt, filler and optional sulphur with at least one side that brea bed is placed mat and fill space between the individual glass fibers.Mat with bitumen coated cuts into suitable shape and size to form roof boarding then.The mat that can make the heated bitumen coating then is below one or more particle coating machines, and this coating machine is coated in the protectiveness surface particles on the mat of part bitumen coated before cutting into desirable shape.
The synthetic fatty amide not only is designed to serve as lubricant and dispersion agent, and be designed to asphalt mixture in pitch interact.Therefore, an advantage providing of fatty amide is itself and other component inherent reactive behavior.For example, can set up covalent bonding (for example interface bonding) between glass and the pitch by such sulfuration mechanism: wherein in the presence of the sulphur at elevated temperatures the unsaturated hydrophobic nature on the synthetic fatty amide terminal with the pitch reaction, and make glass and pitch crosslinked.In this reaction, sulphur serves as catalyzer.Interface bonding between glass and the pitch has improved the physical strength of gained composite product.
In addition, the nitrogen that in the middle portion of the wetting ability amine-Ji of synthetic fatty amide, exists in case with the acid neutralization, then become cationic nitrogen.These cationic nitrogen can form ionic linkage with the anionic charge of glass fibre then, and this helps fatty amide lubricant is fixed on the glass fibre.
Another advantage that fatty amide provides is the surface energy that fatty amide has improved glass, makes glass compatible with pitch more.The high hydrophobic of the hydrophobic nature end on the fatty amide lubricant and low surface energy have strengthened the consistency between glass and the pitch, and have improved glass/pitch interaction by the interfacial tension that reduces.Therefore, new fatty amide has also played the effect of adhesion promotor.
The present invention briefly having been described, can be by obtaining further understanding with reference to some specific embodiment of setting forth below, unless otherwise indicated, these embodiment provide and are not intended to just to illustrative purposes and all included or limit.
Embodiment
Embodiment 1: traditional lubrication agent-Lubesize K-12's is synthetic
Lubesize K-12 is a kind of traditional lubrication agent, and it is tetren (TEPA) and stearic adducts.It does not have degree of unsaturation.The composition that is used for synthetic Lubesize K-12 is described at table 1.
Table 1
| Weight (g) | The % of total feed | |
| Stearic acid | 125.00 | 63.98 |
| Tetren (TEPA) | 46.75 | 23.93 |
| Acetate | 23.62 | 12.09 |
| Amount to | 195.37 | 100.00 |
Table 2 has been set forth the 1kg charging based on the composition described in the table 1.
Table 2
| Weight (g) | The % of total feed | |
| Stearic acid | 639.80 | 63.98 |
| Tetren (TEPA) | 239.3 | 23.93 |
| Acetate | 120.9 | 12.09 |
| Amount to | 1000.00 | 100.00 |
With the stearic acid adding and in fusion under frivolous nitrogen blanket under 200 .In case all stearic acid fusions, then under nitrogen blanket with its stirring.When temperature is controlled at 200 , with heat extraction.From dropping funnel, slowly add tetren (TEPA) then.After the heat release summit, restart heating.In case all TEPA is added into, then promptly temperature is raise as the foaming that allows.Under about 380 , determine that about 50% overhead product is removed.During this time, nitrogen blanket is removed and is applied few nitrogen spray.
After applying few nitrogen spray, reheat to the maximum temperature of 480 and stop up to overhead product.In case overhead product stops, then reaction mixture being cooled to the temperature of about 160-170 by ambient air.Determined about 12% of the total feed that is about of whole overhead products of from stearic acid and TEPA, removing.Added acetate at about 15 minutes in the clock time then.When adding acetate, notice the slight exotherm of about 10 .After all acetate are added into, with mixture stir about 10 minutes and be poured over then on the interleaving paper, make its cooling and curing there.
The pH of 1% the final product of Yu Shuizhong is 4.5-5.0.In addition, final product has 0.4% remaining acid number and can not detected iodine number before acid neutralization.It is Lubesize K-12 that this solidifying product is determined.
Embodiment 2: unsaturated fatty acids acid amides lubricant synthetic that contains the conjugated diolefine hydrocarbon structure
Repeat the experiment described among the embodiment 1, except being that benchmark is with the linolic acid place of magnesium stearate with the equivalent.The linolic acid that uses is Emersol 315 linolic acid that are obtained from Cognis Corp..Before the acid neutralization, the remaining acid number of final product is 0.29%, and iodine number is 24.8.The linoleic iodine number of Emersol315 is 27.4.Determining in the lipid acid about 90.5% degree of unsaturation is retained in the synthetic product.
Embodiment 3: unsaturated fatty acids acid amides lubricant synthetic that does not contain the conjugated diolefine hydrocarbon structure
Repeat the experiment described among the embodiment 1, except being that benchmark is with the oleic acid place of magnesium stearate with the equivalent.The oleic acid that uses is Emersol 213 oleic acid that are obtained from Cognis Corp..Before acid was regulated, the remaining acid number of sintetics was 0.18%, and iodine number is 21.8.Emersol 213 oleic iodine numbers are 24.3.Determining in the lipid acid about 90% degree of unsaturation is retained in the synthetic product.
Embodiment 4: the unsaturated fatty acids acid amides of modified rubber synthetic
Repeat the experiment described among the embodiment 1, except polyhutadiene (Sartomer) place of magnesium stearate that is benchmark with weight with the Ricon 130MA13 maleinization of 90% Emersol315 linolic acid (Cognis Corp.) and 10%.Before the acid neutralization, the remaining acid number of sintetics is 0.21%, and iodine number is 27.7.Before the condensation reaction, the iodine number of the original stock of the polyhutadiene of this linolic acid and maleinization is 36.3.Determining in the lipid acid 76.3% degree of unsaturation is retained in the synthetic product.
Embodiment 5: the unsaturated fatty acids acid amides that Polybutadiene-styrene is copolymer-modified synthetic
Repeat the experiment described among the embodiment 1, except Polybutadiene-styrene rubber (Sartomer) place of magnesium stearate that is benchmark with weight with the Ricon 184MA6 maleinization of 90% Emersol315 linolic acid (Cognis Corp.) and 10%.Before the condensation reaction, the iodine content of the mixture of starting material of this linolic acid and Polybutadiene-styrene rubber is 32.2.Before the acid neutralization, the remaining acid number of sintetics is 0.25%, and iodine number is 30.7.About 95.3% the degree of unsaturation that determines lipid acid is retained in the synthetic product.
Embodiment 6:Lubesize K-12 and the comparison that contains the unsaturated fatty acids acid amides lubricant of conjugated diolefine hydrocarbon structure
With the size compositions coated fiber sample that contains the fatty amide of preparation in above embodiment 1 and 2.On the sheet material former, make the fiber sample of gluing be shaped to the roofing pad.Change into breadboard roof boarding sample by filling up sample then with the asphalt mixture coating mat of the elementary sulfur that contains 0%, 0.2% or 0.8% back adding.The result is summarized in the table 3.
Table 3
| Sulphur content | 0％ | 0％ | 0.2％ | 0.2％ | 0.8％ | 0.8％ |
| Breadboard roof boarding performance | CD tears | All tear | CD tears | All tear | CD tears | All tear |
| Embodiment 1 saturated amide (contrast) | 1324 | 2278 | 1356 | 2519 | 1243 | 2335 |
| Embodiment 2 conjugation acid amides (the present invention) | 1510 | 2617 | 1554 | 2841 | 1649 | 2958 |
| The raising of tear strength | 14.0％ | 14.9％ | 14.6％ | 12.8％ | 32.7％ | 26.7％ |
Note: CD=is horizontal
On Elmendorf tear strength tester, measure tear strength according to the step described in the ASTM D-3462
The unit of tear strength is in g
Performance among this embodiment improves data and shows: contain in the bitumen coated preparation or do not contain under the situation of outside sulphur, by having improved tear strength with comprising the laboratory roof boarding that is formed by the fiber of the size compositions gluing of TEPA and conjugated fatty acids synthetic fatty amide.Although be not wishing to be bound by theory, it is believed that the performance of size compositions when not adding sulphur improves, this is because the surface energy of higher hydrophobic nature and the glass surface that reduced by fatty amide of the present invention.The reduction that also it is believed that surface energy has improved and has been added into the glass that forms the laboratory roof boarding and the interaction between the pitch.
Embodiment 7:Lubesize K-12 and do not contain the comparison of the unsaturated fatty acids acid amides lubricant of conjugated diolefine hydrocarbon structure
With the size compositions coated fiber sample that contains the fatty amide of preparation in above embodiment 1 and 3.On the sheet material former, make the fiber sample of gluing be shaped to the roofing pad.Apply mat by asphalt mixture then and will fill up sample and change into breadboard roof boarding sample with the elementary sulfur that contains 0% and 0.2% back adding.The result is summarized in the table 4.
Table 4
| Sulphur content | 0％ | 0％ | 0.2％ | 0.2％ |
| Breadboard roof boarding performance | CD tears | All tear | CD tears | All tear |
| Embodiment 1 saturated amide (contrast) | 1324 | 2278 | 1356 | 2519 |
| Embodiment 3 non--conjugation acid amides (the present invention) | 1440 | 2606 | 1470 | 2691 |
| The raising of tear strength | 8.8％ | 14.3％ | 8.4％ | 6.8％ |
Note: CD=is horizontal
On Elmendorf tear strength tester, measure tear strength according to the step described in the ASTM D-3462
The unit of tear strength is in g
Performance among this embodiment improves data and shows: contain in the bitumen coated preparation or do not contain under the situation of outside sulphur, by having improved tear strength with comprising the laboratory roof boarding that is formed by the fiber of the size compositions gluing of TEPA and non--conjugated polyunsaturated fatty acid synthetic fatty amide.
Briefly and with reference to specific embodiment the application's summary of the invention has been described in the above.Although in being considered to embodiment preferred, described the present invention, can in total disclosure content, select the surrogate of the broad variety that those skilled in the art know.Except the narration of claims of describing below, the present invention is not limited in addition.
Claims (34)
1. size compositions that is used for glass fibre, it comprises:
At least a film-forming polymer;
One or more silane coupling agents; And
By (many) ethyleneamines and unsaturated conjugated C
5-C
20Lipid acid synthetic fatty amide lubricant.
2. the size compositions of claim 1, wherein said (many) ethyleneamines are selected from: tetren, diethylenetriamine, four ethylidene triamines, quadrol, diethylenetriamine, methylene radical tetramine and penten.
3. the size compositions of claim 2, wherein said one or more silane coupling agents comprise amino silicane coupling agent and vinyl silicane coupling agent.
4. the size compositions of claim 2, it further comprises a member that is selected from following material: auxiliary lubricant, pH regulator agent, viscosity modifier, sterilant, glycols and glycol ethers.
5. the size compositions of claim 1, the modification of wherein said fatty amide lubricant by mixing resilient material.
6. the size compositions of claim 5, wherein said resilient material is selected from maleinization rubber and carboxylation rubber.
7. the size compositions of claim 1, wherein said at least a film-forming polymer is present in the described size compositions with the quantity of the 30-80wt% of total solids, described one or more silane coupling agents are present in the described size compositions with the quantity of the 5-30wt% of total solids, and described fatty amide lubricant is present in the described size compositions with the quantity of the 5-30wt% of total solids.
8. enhancing composite roof material that comprises with many glass fibre of size compositions gluing, said composition comprises:
At least a film-forming polymer;
One or more silane coupling agents; And
As (many) ethyleneamines and unsaturated C
5-C
20The fatty amide lubricant of the reaction product of lipid acid.
9. composite roof material as claimed in claim 8, wherein said lipid acid is conjugated fatty acids.
10. composite roof material as claimed in claim 8, wherein said one or more silane coupling agents comprise amino silicane coupling agent and vinyl silicane coupling agent.
11. composite roof material as claimed in claim 8, wherein said (many) ethyleneamines are selected from: tetren, diethylenetriamine, four ethylidene triamines, quadrol, diethylenetriamine, methylene radical tetramine and penten.
12. composite roof material as claimed in claim 8, the resilient material modification that is selected from maleinization rubber and carboxylation rubber of wherein said fatty amide lubricant.
13. the size compositions of claim 8, wherein said at least a film-forming polymer is present in the described size compositions with the quantity of the 30-80wt% of total solids, described one or more silane coupling agents are present in the described size compositions with the quantity of the 5-30wt% of total solids, and described fatty amide lubricant is present in the described size compositions with the quantity of the 5-30wt% of total solids.
14. composite roof material as claimed in claim 8, wherein said composite roof material are the forms of asphalt shingle.
15. composite roof material as claimed in claim 9, wherein said fatty amide lubricant have improved the surface energy of described glass fibre and have improved described glass fibre to being present in the bituminous consistency in the described asphalt shingle.
16. composite roof material as claimed in claim 8, it further comprises a member that is selected from following material: auxiliary lubricant, viscosity modifier, pH regulator agent, sterilant, glycols and ethanol ethers.
17. a roof boarding, it comprises:
By many randomly-oriented fibroplastic mats with the size compositions gluing, said composition comprises: at least a film-forming polymer, one or more silane coupling agents, and fatty amide lubricant, described fatty amide lubricant is (many) ethyleneamines and unsaturated C
5-C
20The reaction product of lipid acid; With
Bituminous coating at least a portion of an outside surface of described mat.
18. the roof boarding of claim 17, wherein said lipid acid is conjugated fatty acids.
19. the roof boarding of claim 17, wherein said (many) ethyleneamines are selected from: tetren, diethylenetriamine, four ethylidene triamines, quadrol, diethylenetriamine, methylene radical tetramine and penten.
20. the roof boarding of claim 19, wherein said one or more silane coupling agents comprise amino silicane coupling agent and vinyl silicane coupling agent.
21. the roof boarding of claim 17, wherein said at least a film-forming polymer is present in the described size compositions with the quantity of the 30-80wt% of total solids, described one or more silane coupling agents are present in the described size compositions with the quantity of the 5-30wt% of total solids, and described fatty amide lubricant is present in the described size compositions with the quantity of the 5-30wt% of total solids.
22. the roof boarding of claim 17, wherein said fiber is a glass fibre, and described fatty amide lubricant has been improved the surface energy of described glass fibre and improved described glass fibre to described bituminous consistency.
23. the roof boarding of claim 17, wherein by mixing resilient material between synthesis phase in fatty amide lubricant with described fatty amide lubricant modification.
24. the roof boarding of claim 17, wherein said fatty amide lubricant have improved the surface energy of described glass fibre and have improved described glass fibre to described bituminous consistency.
25. the roof boarding of claim 17, wherein the unsaturated hydrophobic nature on the synthetic fatty amide terminal with the pitch reaction and make glass and pitch crosslinked.
26. the roof boarding of claim 17, it comprises that further sulfur catalyst is to promote the interface bonding between glass and the pitch.
27. a method that forms roof boarding, it may further comprise the steps:
Formation is by the mat of forming with the randomly-oriented glass fibre of size compositions gluing, and said composition comprises:
At least a film-forming polymer;
One or more silane coupling agents; And
Fatty amide lubricant, described fatty amide lubricant are (many) ethyleneamines and C
5-C
20The reaction product of unsaturated fatty acids; With
Bituminous coating is coated at least one surface of described mat.
28. the method for claim 27, wherein said (many) ethyleneamines are selected from: tetren, diethylenetriamine, four ethylidene triamines, quadrol, diethylenetriamine, methylene radical tetramine and penten.
29. the method for claim 28, wherein said one or more silane coupling agents comprise amino silicane coupling agent and vinyl silicane coupling agent.
30. the method for claim 27, wherein said lipid acid is conjugated fatty acids.
31. the method for claim 27, it further may further comprise the steps: described mat is cut into suitable roof boarding shape and size.
32. the method for claim 27, it further may further comprise the steps: with the described pitch of protectiveness particle coated.
33. the method for claim 27, it further may further comprise the steps: the unsaturated hydrophobic nature end on the synthetic fatty amide is reacted so that glass and pitch are crosslinked with pitch.
34. the method for claim 33, it further comprises provides sulfur catalyst to promote the interface agglutinating step between glass and the pitch.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1968906A true CN1968906A (en) | 2007-05-23 |
Family
ID=34972202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200580019756XA Pending CN1968906A (en) | 2004-06-15 | 2005-06-03 | Fatty amide composition for wet use chopped strand glass fibers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20050276960A1 (en) |
| EP (1) | EP1765741A1 (en) |
| JP (1) | JP2008502573A (en) |
| KR (1) | KR20070015226A (en) |
| CN (1) | CN1968906A (en) |
| WO (1) | WO2006001984A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859158A (en) * | 2015-12-30 | 2016-08-17 | 巨石集团有限公司 | Glass fiber infiltration agent with low migration rate |
| 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 |
| CN114075350A (en) * | 2020-08-19 | 2022-02-22 | 彤程化学（中国）有限公司 | Carbon black coupling agent and preparation method and application thereof |
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| 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 |
| KR101659727B1 (en) * | 2014-12-24 | 2016-09-27 | 주식회사 케이씨씨 | Fiber pellet coated with thermoplastic resin for strength improvement of asphalt road |
| 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 |
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- 2005-06-03 CN CNA200580019756XA patent/CN1968906A/en active Pending
- 2005-06-03 WO PCT/US2005/019664 patent/WO2006001984A1/en not_active Application Discontinuation
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859158A (en) * | 2015-12-30 | 2016-08-17 | 巨石集团有限公司 | Glass fiber infiltration agent with low migration rate |
| CN105859158B (en) * | 2015-12-30 | 2019-01-29 | 巨石集团有限公司 | A kind of glass fiber infiltration agent of low mobility |
| 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 |
| CN114075350A (en) * | 2020-08-19 | 2022-02-22 | 彤程化学（中国）有限公司 | Carbon black coupling agent and preparation method and application thereof |
| CN114075350B (en) * | 2020-08-19 | 2023-07-25 | 彤程化学（中国）有限公司 | Carbon black coupling agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008502573A (en) | 2008-01-31 |
| KR20070015226A (en) | 2007-02-01 |
| WO2006001984A1 (en) | 2006-01-05 |
| US20050276960A1 (en) | 2005-12-15 |
| EP1765741A1 (en) | 2007-03-28 |
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Open date: 20070523 |