CN100436357C - Polyurethane-based anhydrous sizing composition for glass fibres, glass fibres thus obtained and composite materials comprising said fibres - Google Patents
Polyurethane-based anhydrous sizing composition for glass fibres, glass fibres thus obtained and composite materials comprising said fibres Download PDFInfo
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- CN100436357C CN100436357C CNB038115646A CN03811564A CN100436357C CN 100436357 C CN100436357 C CN 100436357C CN B038115646 A CNB038115646 A CN B038115646A CN 03811564 A CN03811564 A CN 03811564A CN 100436357 C CN100436357 C CN 100436357C
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- glass fiber
- fiber strand
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- isocyanate
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Classifications
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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
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/326—Polyureas; Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/25—Non-macromolecular compounds
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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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Abstract
The invention relates to a sizing composition consisting of a solution comprising less than 5 wt.- % solvent and a polymerisable base system, said system containing at least 50 wt.- % components of a mixture of: component(s) having at least one isocyanate-reactive function; component(s) having at least one hydroxy-reactive function; and, optionally, component(s) having at least one amine-reactive function. The invention also relates to glass fibres which are covered with the aforementioned sizing composition. The glass fibres thus obtained can be used to reinforce organic or inorganic materials.
Description
The present invention relates to be used for glass fibre size compositions, gained glass fiber strand and introduced the matrix material of described glass fiber strand.More precisely, the present invention relates to react compound that has isocyanate-reactive functional group comprising of formation urethane and/or polyureas and anhydrous size compositions with compound of hydroxyl and/or amine functional group.
The production of enhanced glass fiber strand is that raw material carries out with effusive fused glass materials flow from die channel in known manner.These materials flows are stretched with the form of continuous filament yarn, and these long filaments concentrate at together as basic tow then, collect with various forms then: the bobbin of continuous tow, successive silk bunch or prescind thread bunch, the tow that prescinds etc.
Before their are assembled with the form of tow, by allow long filament on gluing member by and be coated with cementing agent.It is necessary using cementing agent, on the one hand, and in order to obtain tow, on the other hand, will be in order to produce as described tow and other organic and/or inorganic materials bonded matrix materials of toughener.
The abrasion that high-speed friction on the various parts that cementing agent is not at first run in aforesaid method by tow as lubricant and protection tow produces damage.Importantly, glass filament bundle has is enough to tolerate follow-up conversion operation, such as debatching from suitable support and be wrapped in suitable support or braiding on smooth property (or " smooth property ") reduce to minimum so that will break any friction of long filament easily.
Cementing agent also has gives the function of above-mentioned tow with assembly property, that is, and and the function that the long filament in the tow is bonded together.This assembly therein tow to suffer in the textile application of high machinery (especially stretching) stress be ideal more specifically.Therefore, when the long filament imperfect bonding, they have the proneness of easier fracture when stressed, have caused the formation of the fine hair of interference weaving loom running, or even have needed weaving loom to stop work fully.In addition, the non-integral tow is considered to be difficult to handle, especially when they are used to form bobbin, because occur the long filament of fracture then along each side.Except not satisfied attractive in appearance, more the difficulty be to get off from the tow debatching that these packages break away from.
Cementing agent also have by tow and want between the enhanced material to produce the bonding effect that promotes that tow is wetting by these materials and/or flood.This material and tow adherent quality and tow ability wetting by this material and/or dipping depends on the mechanical property of gained matrix material.In most of the cases, cementing agent can obtain to have the matrix material that improves mechanical property.
Size compositions also must adapt with the tow working condition that especially uses high long filament draw speed (it can up to tens meter per seconds).They also must tolerate by long filament passes through the shearing force of being brought out, and especially for viscosity, it must fluctuate not obviously, and the surface of wetting long filament rightly, so that obtain the uniform coating on their whole length.
Contain and after being deposited on the glass fibre, further to keep stable under the temperature below wortle (approximately 60-100 ℃) by the size compositions of polymeric component.Especially, wish to guarantee that polymerizable composition has low-steam pressure under described temperature, with any problem of the change in concentration avoiding occurring being caused by some composition volatilization.It is important that also the transformation efficiency that control is defined by the ratio of the number of the functional group of having reacted and the number of initial reactivity functional group is so that guarantee to obtain the glass fiber strand of the gluing of constant-quality in cementing agent.Transformation efficiency especially must change so that prevent cementing agent in time very near the theoretical value of expection.
Usually, select size compositions, so that satisfy above-mentioned function and in the room temperature storage process and under the hot conditions below the wortle, do not caused the chemical reaction that viscosity increases considerably.
The cementing agent of normal use is low viscous moisture cementing agent.Though be highly susceptible to using, they have shortcoming.Especially, these cementing agents contain the water of significant proportion, generally surpass 80%, and water is removed after must be on being deposited on glass fibre, because water causes tow and the bounding force reduction between the enhanced material wanted.Known mode comprises by the heat drying glass filament bundle, but this is the very long and expensive operation that need ideally mate with the tow working condition.And this processing is not adiaphorous for tow.Especially, when the gluing tow exists with the package form, the distortion by the painted and package of the variation of the distribution of irregular and/or the cementing agent composition that selective migration caused, tow can take place.
The someone has proposed to contain the water-based size compositions of urethane.Therefore, EP-A-0554173 discloses the cementing agent on the glass fiber strand that manufacturing that purpose is used for being coated on molded composites uses, and its binding agent is formed by one or more urethane resins, optionally combines with one or more polyepoxides.In JP-2000044793, proposed to strengthen the method for thermoplastic material by the glass fiber strand of handling with the size compositions of the urethane resin, coupling agent and the lubricant that contain emulsion form.
And the size compositions of known " anhydrous " promptly contains solvent that is less than 5%wt and those compositions of being made up of the foundational system that polymerisable component forms.
In FR-A-2 727 972, size compositions can polymerization under the effect of UV radiation or electron beam.Polymerisable foundational system contains at least a molecular weight and is lower than 750 component, and it has at least one epoxy-functional and contains at least, and the molecular weight with at least one epoxy group(ing), hydroxyl, vinyl ether, acrylic or methacrylic acid functional group of 60%wt is lower than one or more components of 750.
The size compositions that does not need the glass fiber strand of heat treatment step after FR-A-2 772 369 has disclosed on being deposited on tow.What it comprised 60%wt at least can the polymeric component, at least 60% of these components are that molecular weight is lower than 750 component and these polymerisable components contain one or more components with at least one vinylformic acid and/or methacrylic acid reactive functional groups and one or more have at least a mixture of at least one primary amine and/or secondary amine functional groups, and these components of 20%wt have at least two vinylformic acid, methacrylic acid, primary amine and/or secondary amine reactive functional groups at least.
An object of the present invention is to propose to be used for the hot polymerisable anhydrous size compositions of coated glass fibre bundle, it comprises that compound and optional one or more that one or more compounds that contain one or more isocyanate functional groups and one or more contain one or more hydroxy functional groups contain the reaction product of the compound of one or more amine functional groups.
Another object of the present invention is to propose size compositions, wherein in order to adapt to application conditions, but thereby the reaction times that can change the dimerization system make system can be crosslinked relatively lentamente 1 or several hrs to about 10 minutes gelation time of reactive high system.
Another object of the present invention be propose can the feed glass fibre bundle quality, i.e. the size compositions of their hardness and their assembly.
Another object of the present invention is to propose to increase the glass fiber strand of the coating cementing agent of the operation of their volume (" expansionization " operation) with they are suitable for.
Size compositions according to the present invention is by containing solvent that is less than 5%wt and the solution composition that contains polymerisable foundational system, and described system contains the mixture of the following component of 50%wt at least:
One or more contain the component of at least one isocyanate-reactive functional group;
One or more contain the component of at least one hydroxyl reactive functional group;
Optional one or more contain the component of at least one amine reactive functional groups.
In the present invention, following statement has implication given below:
-" solvent " is understood that to refer to can be used in the water and the organic solvent of some polymerisable component of dissolving.The existence of limited amount one or more solvents removes them without any need for specific processing.In most of the cases, do not contain solvent fully according to cementing agent of the present invention.
-" polymerization ", " polymerisable " etc. are considered to be meant respectively " polymerization and/or crosslinked ", " polymerisable and/or crosslinkable " etc.
-" reactive functional groups " is understood that to refer to the functional group that can work in the polyreaction of cementing agent, it can make and be aggregated in common tow production temperature (approximately 20-100 ℃) generation down, (thermopolymerization) perhaps takes place in energize under up to about 150 ℃ higher temperature in addition; With
-" polymerisable foundational system " is understood that to refer to the combination of essential component of the polyurethane/polyurea structure of the cementing agent that can obtain to expect.
Hereinafter, statement " one or more isocyanate components ", " one or more hydroxy components " and " one or more amine components " is considered to be meant respectively " one or more components that contain at least one isocyanate-reactive functional group ", " one or more components that contain at least one hydroxyl reactive functional group " and " one or more components that contain at least one amine reactive functional groups ".
Adapt according to size compositions of the present invention and the working condition that adopts direct method to obtain glass fiber strand, the viscosity of said composition is adjusted according to draw speed and the diameter that passes the long filament of size compositions.Usually, wish that viscosity is no more than 400mPa.s, be preferably 150mPa.s, make size compositions can be evenly distributed on the surface of filament of glass fiber.Also has the tow wetting speed that adapts to the tow draw speed according to composition of the present invention.
Usually, polymerisable foundational system accounts for the 50-100%wt according to size compositions of the present invention, accounts for the 60-100%wt of said composition substantially, in most of the cases accounts for the 75-90%wt of said composition.
This foundational system main (preferred 75%wt and in most of the cases 100%wt) at the most is made up of one or more isocyanate components and one or more hydroxy components and one or more amine components of depending on the needs, uses the reaction of various isocyanic ester, hydroxyl and amine functional group that the mixture of this component can be by initial composition to obtain urethane or gather (ammonia ester-urea) polymkeric substance.These polymkeric substance mainly participate in the structure of cementing agent, and this structure has directly caused the performance of the glass fiber strand of gluing.
In addition, one or more molecular weight that this foundational system comprises major part (preferably 70%wt and preferably 80%wt at least at least) are lower than 750 component, and these one or more components have in most of the cases formed the part of above-mentioned isocyanic ester, hydroxyl and amine component usually.
Preferred and according to the present invention common situation is, above-mentioned molecular weight is lower than 750 component to have and is lower than 600 molecular weight.
When this foundational system contained molecular weight and is lower than 750 component, it advantageously comprised molecular weight and is higher than 1000 one or more isocyanic ester and/or hydroxyl and/or amine component (prepolymer).The total content of these components is usually less than the 20%wt of size compositions, preferably is lower than 15%wt, and when when this content is above, it is too high that the viscosity of composition and reactivity become, thus can not make cementing agent in above-mentioned processing condition deposit on glass fiber strand.
Usually, change the reactivity of foundational system, so that adapt to application conditions.Especially, gelation time has significant effects to the deposition quality of cementing agent and the structure of package when tow is collected with the bobbin form.Gelation time must be no less than about 10 minutes, so that make cementing agent be deposited on the below of wortle by upper glue roller, does not have cementing agent that the important risk of gelationization takes place on roller.And gelation time must be no more than 1.5 hours, so that can obtain the tow package that can handle when leaving winder.It is very gratifying that 15-45 minute gelation time is proved to be.
According to some embodiment, can randomly comprise the structure of the participation polymerization cementing agent that (is lower than 20%) on a small quantity according to foundational system of the present invention, but not have isocyanic ester, hydroxyl or amine functional group and/or more than or equal to one or more components of 1000 molecular weight.Preferably, the ratio of these components is lower than 15%.
According to the preferred embodiments of the invention that can obtain especially gratifying result, this foundational system is made up of isocyanate component, one or more hydroxy components that contain at least one hydroxyl reactive functional group and one or more optional components that contain at least one amine reactive functional groups that one or more contain two isocyanate-reactive functional groups at least.Especially advantageously, this foundational system is made up of isocyanate component and one or more hydroxy components that contain 1-3 hydroxyl reactive functional group that one or more contain three isocyanate-reactive functional groups, perhaps is made up of one or more isocyanate component, one or more hydroxy components that contain hydroxyl reactive functional group and one or more amine components that contain two primary amine reaction functional groups that contain three isocyanate-reactive functional groups.
According to the present invention, whole or some hydroxy components of this foundational system can contain one or more hydroxyl reactive functional groups and one or more amine reactive functional groups.
One or more isocyanate components of this foundational system especially can be selected from following compounds:
-aliphatic series or alicyclic isocyanate, such as hexyl isocyanate, isocyanic acid dodecyl ester, isocyanic acid cetyl ester, NSC 87419, isocyanic acid 1-adamantane esters, 1,6-hexamethylene diisocyanate (HDI), 1,2-ten dimethylene diisocyanates, isophorone diisocyanate (IPDI), 1,1-methylene-bis (4-isocyano hexanaphthene) (HMDI), trans cyclohexane 1,4-vulcabond (CHDI), the ester class is such as isocyano butylacetate and isocyano propionic acid 3-ethyl ester, or ethers, such as the trifluoroacetyl based isocyanate;
-aromatic isocyanate, such as isocyanic acid 3,5-3,5-dimethylphenyl ester, isocyanic acid 4-methoxy-benzyl ester, isocyanic acid 4-dimethylaminophenyl ester, isocyanic acid 4-p-methoxy-phenyl ester, isocyanic acid 4-ethoxyl phenenyl ester, Xylene Diisocyanate (XDI), tolylene diisocyanate (TDI), naphthalene-1,5-vulcabond (NDI), 4,4 '-diphenylmethanediisocyanate (MDI) and tetramethylxylene diisocyanate (TMXDI); With
The prepolymer of-isocyanic ester terminal (NCO-prepolymer), for example TOLONATE
HDT and TOLONATE
HDB (NCO content: 20-25%; Sell by Rhodia), the reaction product between polyethers and the isocyanic ester, such as polytetramethylene glycol/TDI prepolymer, for example CASTOMER
E 1009 and CASTOMER
(NCO content is respectively 4.2 and 9.3% to E 1004; Sell by Baxenden); Polypropylene glycol/TDI prepolymer, for example TRIXENE
DP9B/1534 (NCO content: 4.4%; Sell by Baxenden) and polyester and isocyanic ester, the especially reaction product between the TDI, for example CASTOMER
DP9A/956 (NCO content: 4%; Sell by Baxenden).
In the middle of the isocyanic ester of mentioning just now, some are arranged is the higher relatively monomers of vapour pressure, makes them poisonous to human body potentially.Here it is why preferred molecular weight equal 400 and preferably equal the reason of the isocyanic ester of 450 prepolymer form at least at least.Advantageously, molecular weight is less than or equal to 2000, preferably is less than or equal to 1200, because surpass this molecular weight, prepolymer has high-melting-point or high viscosity, and this makes that size compositions is difficult to be applied on the filament of glass fiber.Advantageously, this prepolymer has and equals 3% at least, preferably is less than 25% and advantageously be greater than or equal to 5% free isocyanate reactive functional mass contg (NCO content).
Usually, according to the present invention, the ratio of the isocyanate component in foundational system accounts for 15-75%wt, preferred 30-60%wt.Preferably, at least 10% isocyanate component is a polyisocyanates, and advantageously, 100% isocyanate component is a polyisocyanates.
The content of the isocyanate component in composition generally is 10-50%wt, preferably 20-40%wt.
One or more hydroxy components of this of foundational system can be selected from following compounds:
-aliphatic series or alicyclic alcohol, such as hexanol, octanol, dodecanol, hexalin, 1,2-propylene glycol, 2-ethyl-2-methylol-1, ammediol, butyleneglycol, butylene glycol, pentanediol, hexylene glycol, cyclohexane diol, 1,4 cyclohexane dimethanol, glycerine, TriMethylolPropane(TMP) and tetramethylolmethane;
-tertiary alkanol amine, such as 2-(diisopropylaminoethyl) ethanol, 3-dimethylamino-1-propyl alcohol, 3-diethylamino-1,2-propylene glycol, 3-diisopropylaminoethyl-1,2-propylene glycol, N butyl diethanol amine, trolamine and tri-isopropanolamine,
-contain the monohydroxylated component of the polyester type of terminal hydroxy group, it obtains by the reaction between lipid acid and poly-(oxirane), such as polyethylene glycol isostearate or polypropylene glycol isostearate, polyethers component by the acquisition of the reaction between Fatty Alcohol(C12-C14 and C12-C18) and oxyethane and/or the propylene oxide with terminal hydroxy group, the lauryl alcohol that for example has 4 ethylene oxide units, or, for example has the nonylphenol of 8 ethylene oxide units by the polyethers component that the reaction between alkylphenol and oxyethane and/or the propylene oxide obtains with terminal hydroxy group; With
-poly-(oxyalkylene) polyvalent alcohol, for example poly-(oxygen ethylidene) polyvalent alcohol, poly-(oxygen propylidene) polyvalent alcohol, poly-(oxygen ethylidene) (oxygen propylidene) polyvalent alcohol, poly-(tetrahydrofuran (THF)) polyvalent alcohol, preferred molecular weight is lower than poly-(caprolactone) polyvalent alcohol of 1500.
In the hydroxylated compound of mentioning just now, it is preferred containing those that surpass 5 carbon atoms.When needs reduce the viscosity of foundational system and/or the chain length in the limit polymerization process, can use to have the still less compound of carbonatoms.
Preferably, according to the present invention,, preferably select hydroxy component in the alcohol of two or three hydroxy functional groups from containing at least two hydroxyl reactive functional groups.
As mentioned above, hydroxy component can comprise one or more amine functional groups.The example of these components provides in the back.
In the present invention, can also use the component that contains one or more epoxy-functionals as hydroxy component, its oxirane ring can be opened by the effect of catalyzer, so that produce secondary hydroxyl.The catalyzer that can be used in this purpose can be those any catalyzer well known by persons skilled in the art as hereinafter described.
As the example of this type of component, can mention that the ratio of component that contains epoxy-functional is as a cyclohexene oxide, glycidyl ether, especially C
4-C
20Alkyl glycidyl ether, phenyl glycidyl ether, the alkyl phenyl glycidyl ether, the derivative of dihydroxyphenyl propane, especially the monoglycidyl ether of acryloxy dihydroxyphenyl propane, and the component that contains several epoxy-functionals, such as polyglycidyl ether, especially 1, the 4-butanediol diglycidyl ether, neopentylglycol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, resorcinol diglycidyl ether, dihydroxyphenyl propane or Bisphenol F diglycidylether, the polyhutadiene diglycidylether, the polyoxyethylene glycol diepoxide, the polyglycidyl ether of trihydroxymethylpropanyltri diglycidyl ether and alkyl polyester.
Usually, according to the present invention, the ratio of hydroxy component is the 15-60wt% of this foundational system, preferred 25-50wt%.Preferably be at least 15%, advantageously at least 20% hydroxy component is the component that comprises at least two hydroxyl reactive functional groups.
The content of the hydroxy component in the composition generally is 15-55%wt, preferably 25-45%wt.
The number of the reactive site of the hydroxy component that can react with the reactive site of isocyanate component can alter a great deal.Generally, the ratio of the number of isocyanate reaction reactive site and hydroxyl reaction reactive site is 0.1-6, preferred 0.3-4, much less, an isocyanate functional group calculates as a hydroxyl reaction reactive site as an isocyanate reaction reactive site calculating and a hydroxy functional group.
One or more amine components of this of foundational system can be selected from the component that contains one or more primary amine and/or secondary amine functional groups, such as having linearity, the component of branching or cyclic hydrocarbon chain component, N for example, the N-dibutylamine, N, the N-dicyclohexylamine, aminoethylpiperazine, 2-(2-amino ethoxy) ethanol, 3-amino-1-propyl alcohol, 2-amino-2-ethyl-1-propyl alcohol, N-(2-amino-ethyl) thanomin, 2-amino-2-ethyl-1, ammediol, aromatic component, for example 1,3-diphenylguanidine and 3, the 4-diaminotoluene, with contain the polymkeric substance of holding amine, for example poly-(divinyl) diamines.According to the present invention, as mentioned above, some of above-mentioned amine compound contain one or more hydroxy functional groups.
Preferably, amine component is selected from the component that contains at least two primary amine and/or secondary amine functional groups.In order to reduce the reactivity of amine compound, can consider to add a spot of (account for about 2 of composition and arrive 15%wt) ketone, especially diketone; such as diacetylmethane, phenyl phenacyl ketone, 2,2,6; 6-three fluoro-3,5-heptadione, 1,4-cyclohexanedione-2; 5-dicarboxylic acid dimethyl esters, 4; 4,4-three fluoro-1-(2-naphthyl)-1,3-dimethyl diketone, thenyltrifluoroacetone, 2; 2-dimethyl-6; 6,7,7; 8-seven fluoro-3; 5-acetyl caproyl, 3-methyl-2,4-diacetylmethane, 1-(2-furyl)-1,3-dimethyl diketone and 2; 6-dimethyl-3, the 5-heptadione.Diacetylmethane, phenyl phenacyl ketone, 3-methyl-2,4-diacetylmethane and 2,6-dimethyl-3,5-heptadione are preferred.
Usually, according to the present invention, the ratio of amine component accounts for the 0-30%wt of this foundational system and in most of the cases it is 5-30%.
The content of amine component in composition generally is 0-30%wt, preferred 0-20%wt.
The number of the reactive site of the amine component that can react with the reactive site of isocyanate component can alter a great deal.Usually, the ratio r of the summation of the number of the number of the number of isocyanate reaction reactive site and hydroxyl reaction reactive site and amine reactive site ' be 0.1-6, preferred 0.3-4, much less, an isocyanate functional group calculates as an isocyanate reaction reactive site, a hydroxy functional group calculates as a hydroxyl reaction reactive site, and a primary amine functional group calculates as an amine reactive site as two amine reactive sites calculating and a secondary amine functional groups.
Except this foundational system, size compositions can comprise at least a catalyzer of promotion cementing agent polymeric.This for example can be the special catalyst that is used for synthesis of polyurethane, such as 1,4-diazabicyclo [2.2.2] octane and 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, or be suitable for the catalyzer of epoxy component, such as three (N, N-dimethylaminomethyl) benzene, three (N, the N-dimethylaminopropyl) triazine, N, N-dimethyl benzyl amine and 2-propyl imidazole.
Only generally being lower than the 5%wt of size compositions as the component of the catalyzer of foundational system (promptly not participating in those of structure of polymerization cementing agent), preferably being lower than 3%wt, in most of the cases is about 0.5%wt.
In above-mentioned scope, this size compositions can also comprise the solvent of some components dissolved that promotes foundational system.As the example of this kind solvent, can mention ethyl acetate, N-Methyl pyrrolidone and tetrahydrofuran (THF).
This size compositions also can comprise except the said components of the structure of main participation polymerization cementing agent and one or more components catalyzer that depends on the needs and the solvent (being called additive hereinafter).These additives have been given cementing agent with specific performance properties, and when this matrix material deposited in two steps preferably, they can be provided by the cementing agent that one or both one-tenth is grouped into.
According to composition of the present invention can comprise as additive be used for cementing agent is bonded at least a coupling agent on the glass fibre.This coupling agent can be the component of foundational system, and in this case, it participates in polyreaction, or only as components of additives.
The ratio of coupling agent generally is the 0-30%wt of size compositions, in most of the cases is higher than 5%wt.Preferably, it accounts for the 10-25%wt of said composition.
This coupling agent generally is selected from silane, such as γ-glycidoxypropyl propoxy-propyl trimethoxy silicane; γ-acryloxy propyl trimethoxy silicane; γ-methacryloxypropyl trimethoxy silane; poly-(oxygen ethylidene/oxygen propylidene) Trimethoxy silane; γ-An Jibingjisanyiyangjiguiwan; vinyltrimethoxy silane; the phenyl amino propyl trimethoxy silicane; styryl aminoethylamino propyl trimethoxy silicane or tertiary butyl formamyl propyl trimethoxy silicane; type siloxane; titanate ester; the mixture of zirconate class and these compounds.The preferential silane of selecting.
Said composition can comprise at least a weaving processing aid as the main super fatting agent effect of additive, and it is necessary for the function that makes said composition have cementing agent in many cases.
The ratio of weaving processing aid generally is the 0-30%wt of composition, preferred 3-20%wt.
The weaving processing aid generally is selected from optional oxyalkylated fatty acid ester, such as the lauric acid decyl ester, Wickenol 111, palmitinic acid hexadecyl ester, isopropyl stearate, isobutyl stearate, three (sad) ester of TriMethylolPropane(TMP), three (capric acid) ester of TriMethylolPropane(TMP), the derivative of alkylphenol, nonylphenol such as ethoxylation, optional oxyalkylated Fatty Alcohol(C12-C14 and C12-C18), laurate or stearate such as polyoxyethylene glycol with methyl end, advantageously contain and be less than 10 unitary mixtures of oxygen ethylidene based on mineral oil, and the mixture of these compounds.Processing aid does not preferably contain can be preferential and the functional group of isocyanic ester, hydroxyl and/or amine functional group effect.
Can be on filament of glass fiber according to composition of the present invention according to one or more step deposition.
When they deposit in a step, all polymerisable components are included in the size compositions, then essential blocked isocyanate functional group or hydroxyl and amine functional group, to prevent composition polymerization prematurely before it is deposited on the filament of glass fiber.Preferred terms of settlement in this embodiment comprises the polyisocyanates that uses the protected group sealing of its isocyanate-reactive functional group, can be by adding the deblocking agent with this functional group's deblocking.As the example of this type of polyisocyanates, (for example with BI 7673, BI 7772 can to mention the derivative of TDI, HDI, IPDI and MDI, BI7950, BI7962, BI7983, the reference title of BI7960 is sold by Baxenden, and they can come deblocking with 3).
Preferably deposit according to composition of the present invention, for example under the condition of the method described in the FR-A-2 763328 according to several steps.In the method, be drawn into one or more pieces successive long filaments from the glass materials flow of the effusive fusing in hole of the bottom that is positioned at one or more wortles, long filament concentrates at together as one or more tow then, collects on one or more mobile supports.By with viscosity being first stable composition of 0.5-300mPa.s and to separate the viscosity of supplying with this first stable composition be that at least a second stable composition of 0.5-250mPa.s puts on and deposits cementing agent on the long filament.
Can after having deposited first composition, second composition be deposited on the long filament as early as possible, perhaps in the process of collecting, it be deposited on the tow as far as possible behindhand with support.Differences in viscosity between these compositions generally is lower than 150mPa.s.
Preferably apply according to composition of the present invention by two steps, first composition preferably comprises polyisocyanate component and one or more optional additives, and second composition comprises hydroxy component and/or amine component and optional one or more additives, especially one or more polymerizing catalysts.
By two step deposition cementing agents is particularly advantageous.This makes that controlled polymerization reacts and therefore makes cementing agent have uniform quality on the whole length of tow better, has guaranteed high productivity simultaneously, has reduced the danger of tow fracture.
Usually, the cementing agent that is deposited on the tow does not need other energize to come polymerization.Yet, can allow fibrosis silk each stage in this technology afterwards through heat-treated, so that quicken polyreaction.This processing can be applied to tow, successive tow of collecting with the package form or the tow that prescinds, or combines the tow of the organic materials that is used to produce matrix material.For example, for the rove of heavily about 20kg, under about 120-140 ℃, handle and proved gratifying in about 8 hours.For the tow that prescinds, the treatment time is no more than 10 minutes under equal temperature.
When the amount of the cementing agent on tow was hanged down relatively, the actual assembly that bonds together the tow of formation after the cementing agent polymerization by the composition long filament that will obtain was a particularly important.In fact loss on ignition with the tow of size compositions according to the present invention coating is no more than 3%wt, is preferably 1.5%wt and advantageously is 0.8%wt.
The tow of gluing is generally collected with the form of the package on the support that rotates, and collects such as the form with spinning cake, rove, cop.Regardless of the polymerization state and the crossing angle of cementing agent,, also be easy to from the package the debatching tow and handle them even when the latter very little (being lower than 1.5 °).The straight flange package keeps their dimensional characteristic for a long time, can not be out of shape.Tow can also be used to produce silk screen, fabric, braid, band etc. subsequently.
Tow can also be collected on parallel mobile receiving tray.Especially, they can become very thin member to the collection surface afterturn with respect to the direction transverse movement of afterturn tow, so that obtain the coiled material of doping continuous tow or pillar by also being used to make their.Can also before use also is used to make the very thin component collection of their changes simultaneously, tow be cut off.
Urethane or the poly-existence of (ammonia ester-urea) polymkeric substance in cementing agent provide some handiness in bonding, make long filament relative to each other to move.Like this, the assembly of glass fiber strand is modified.Be proved to be for making maybe needs application that they are prescinded of fabric with the tow of cementing agent according to the present invention coating, such as being particularly advantageous in the spray mo(u)lding technology at the same time.Being this tow owing to another advantage of the existence of above-mentioned polymkeric substance directly has better shock strength than the tow of other gluings, and maintenance is compatible with many enhanced thermoplastic materials of wanting simultaneously.
Gluing glass fiber strand according to the present invention is noteworthy, because it can be handled, is used for increasing its volume and obtains usually said " expansion " tow.This processing comprises the system that makes the nozzle of tow by comprising one or more airflow warps, collects tow with suitable equipment with the form of package then.Can weave this tow then, especially being used for forming will painted wall cloth.
The filament of glass fiber that constitutes these tow has the diameter that can change significantly, usually 5-30 μ m.They can be made by any glass, and strengthening the most frequently used in the tow field is E glass and AR glass.
The tow that obtains according to the present invention can be advantageously used in and strengthen various materials, so that obtain to have the matrix material of high-mechanical property.This matrix material obtains by combining with at least a organic and/or inorganic materials to major general's glass fiber strand according to the present invention, glass content in final matrix material generally is 1-5%wt (cement matrix) and 20-80%wt, preferred 30-70%wt (organic substrate).
Following examples are used for illustrating the present invention, yet do not limit the present invention.In these embodiments, use following analytical procedure to measure physicals.
For size compositions:
-utilize SOFRASER MIVI 4000 devices of selling by Sofraser to measure viscosity.It is represented with mPa.s;
-utilize TROMBOMAT equipment (selling) to measure by minute gelation time of expression at the mixture of composition A and B by Prodemat S.A., this equipment has been drawn the viscosity and the time relation curve of size compositions.In this curve, at the intersection point of the tangent line at flex point place and X-axis corresponding to gelation time.
For using the tow that is coated with according to size compositions of the present invention:
-loss on ignition is according to ISO 1887 standard tests.It is represented with %.
-estimate the wear resistance of tow with the amount of fine hair.Allow tow pass through the cylindrical revolving roll of 8 series ceramics, these 8 revolving rolls are measured the amount of fine hair afterwards so that tow equals 90 ° mode in the deflection angle of each revolving roll to be arranged by the amount of weighing and the isolating material of tow.The amount of fine hair provides by the unit of mg/1kg test tow.
-hardness or rigidity under by the condition of ISO 3375 standard codes at before carrying out above-mentioned wear test and 10 samples afterwards measure.Hardness is unit with mm, represents with x (y), and x and y are illustrated respectively in tow by value of measuring before the revolving roll and the value of measuring after tow passes through revolving roll.Value y preliminary assessment the assembly of tow, and indirectly preliminary assessment the tow material, the polymer-type organic materials ability of flooding more particularly.Generally, its y value preferably is used for the application of the good performance of being infiltrated by matrix of needs more less than 100mm near the gluing tow of 60mm (Schwellenwert that can obtain).The x value more than or equal to 120 and the y value be suitable for the application of the high strand integrity of requirement more than or equal to 100 tow, for example be used for braiding, and choose wantonly under the situation of prescinding:
-tensile strength is measured under the condition by ISO 3341 standard codes.It is represented with the g/ tex.
For the matrix material that contains with the glass fiber strand of size compositions coating:
-under condition, wear out by dipping 24 hours (polyester resin composite material) and 72 hours (epoxy resin composite material) in 100 ℃ water before and measuring flexural strength and modulus in flexure afterwards by ISO 178 standard codes.It is represented with MPa;
-under condition, wear out by dipping 24 hours (polyester resin composite material) and 72 hours (epoxy resin composite material) in 100 ℃ water before and measuring shearing resistance afterwards by ISO 4585 standard codes.It is represented with MPa.
Embodiment 1
To be coated with the first composition A by the long filament of stretching from the diameter 13.6 μ m of the tow acquisition of the effusive fusion E glass of wortle (800 holes), then with second composition B coating (representing) with %wt:
Composition A:
Triisocyanate
(1)35
γ-methacryloxypropyl trimethoxy silane
(2)10
γ-glycidoxypropyl propoxy-propyl trimethoxy silicane
(3)10
Palmitinic acid isopropyl esters 5
Composition B
1,5-pentanediol 15
3-dimethylamino-1-propyl alcohol 11.5
The isostearate of polyoxyethylene glycol
(4)13
1,4-diazabicyclo [2.2.2] octane 0.5
Composition A and B have the viscosity of 49mPa.s (21 ℃) and 58mPa.s (22.5 ℃) respectively.
When giving the long filament gluing, produce and contain the composition A of five equilibrium and the mixture of B.This mixture had the viscosity of 1000Pa.s and 21 minutes gelation time after 1 hour.
The ratio r of this size compositions has identical value with r ': 0.487.
Long filament is concentrated at together, form tow, be wrapped on the support of rotation, thereby obtain the straight rove of 14kg.This tow has the linear density of 297 tex and 0.65% loss on ignition.
This tow has the tensile strength that equals the 38.7g/ tex, equals the hardness and the fine hair amount that equals 8mg of 162mm (122mm).
Use two kinds of different resins, according to ISO 9291 standards, by the composition board with parallel strands of two kinds of series of tow production of such acquisition.First kind of resin is by 100 weight part Resins, epoxy
(5), 90 weight parts Tetra hydro Phthalic anhydride
(6)Tertiary amine with 0.5 weight part
(7)The Resins, epoxy of forming.Second kind of resin is the m-phthalic acid polyester by 100 weight parts
(8)Superoxide with 1.5 weight parts
(9)The unsaturated polyester resin of forming.
Provided the value of the mechanical property of these matrix materials below:
| Resins, epoxy | Vibrin | |
| Flexural strength (MPa) | ||
| Before the processing | 2555.6 | 2738.4 |
| After the processing | 2039.9 | 1718.2 |
| Modulus in flexure (MPa) | ||
| Before the processing | 39982 | 37051 |
| After the processing | 37957 | 35339 |
| Shearing resistance (MPa) | ||
| Before the processing | 67.3 | 45.4 |
| After the processing | 47.3 | 25.8 |
Though above-mentioned mechanical property is lower than those that can obtain with the known aqueous size compositions that is particularly suitable for epoxy or vibrin, yet they have significant values.Compare with most popular tow, their performance level is average, and under any circumstance, keeps satisfactory for contemplated application here.
Embodiment 2
In the present embodiment, under the condition of embodiment 1, use following composition:
Composition A:
Triisocyanate
(1)35
γ-methacryloxypropyl trimethoxy silane
(2)10
γ-glycidoxypropyl propoxy-propyl trimethoxy silicane
(3)10
Palmitinic acid isopropyl esters 5
Composition B
Polyoxyethylene glycol (molecular weight=1000)
(10)15
3-dimethylamino-1-propyl alcohol 11.5
The isostearate of polyoxyethylene glycol
(4)13
1,4-diazabicyclo [2.2.2] octane 0.5
When giving the long filament gluing, produce and contain the composition A of five equilibrium and the mixture of B.This mixture had the viscosity of 2000Pa.s and 20 minutes gelation time after 1 hour.
Composition A and B have the viscosity of 49cP (21 ℃) and 68cP (22.5 ℃) respectively.
The ratio r of this size compositions has identical value with r ': 0.998.
Long filament is concentrated at together, form tow, be wrapped on the support of rotation, thereby obtain the straight rove of 14kg.This tow has the linear density of 286 tex and 0.76% loss on ignition.
This tow has the tensile strength that equals the 34.5g/ tex, equals the hardness and the fine hair amount that equals 5mg of 157mm (110mm).
Embodiment 3
Under the condition of embodiment 1, use following composition A and B to carry out present embodiment:
Composition A:
Triisocyanate
(1)35
γ-methacryloxypropyl trimethoxy silane
(2)10
γ-glycidoxypropyl propoxy-propyl trimethoxy silicane
(3)10
Palmitinic acid isopropyl esters 5
Composition B
1,5-pentanediol 18
N butyl diethanol amine 11
Polyoxyethylene glycol (molecular weight MW=300) 10
1,4-diazabicyclo [2.2.2] octane 1
Composition A and B have the viscosity of 49cP (under 21 ℃) and 58cP (under 22.5 ℃) respectively.
The ratio r of this size compositions has identical value with r ': 0.375.
When giving the long filament gluing, produce and contain the composition A of five equilibrium and the mixture of B.This mixture had the viscosity of 60Pa.s and 26 minutes gelation time after 1 hour.
Form the tow of 287 tex linear densities, be collected on the serial bobbin.This tow carries out " expansion " under following condition handles: will concentrate at together from the tow that two bobbins are drawn, and make it continuously by first drawing godet (speed: 220m/min), (import and exit diameter are respectively 0.7 and 2.2mm to nozzle; Air pressure: 6-6.5 crust), second drawing godet (speed: 183.5m/min), be winding apparatus (pressure: 2.5 crust) at last.
The tow of gained has the linear density of 640 tex, the hardness before revolving roll of 110mm, 0.21% loss on ignition, and it does not stay the visible adherent deposit.
The tow of gained has and can be used in woven tensile strength fully.Formed fabric has the hydrophobicity of good " lining " (" being closed "), height, and can be flooded (loss on ignition is greater than 17%) well by polyvinyl acetate base ester.It can be used as last painting cloth.
Embodiment 4
Under the condition of embodiment 1, use following composition to carry out present embodiment:
Composition A:
Triisocyanate
(1)35
γ-methacryloxypropyl trimethoxy silane
(2)10
γ-glycidoxypropyl propoxy-propyl trimethoxy silicane
(3)10
Palmitinic acid isopropyl esters 5
Composition B
The isostearate of polyoxyethylene glycol
(4)9
The lauryl alcohol of etherificate (4 oxygen are through ethylene unit)
(12)9.5
Trolamine 17
1,4-diazabicyclo [2.2.2] octane 0.5
1-Methyl-2-Pyrrolidone 4
The ratio r of this size compositions has 0.589 identical value with r '.
When giving the long filament gluing, produce and contain the composition A of five equilibrium and the mixture of B.This mixture had the viscosity of 2800Pa.s and 32 minutes gelation time after 1 hour.
Long filament is combined into 51 tex tow, is wound in spinning cake again.The tow of being drawn by 24 spinning cakes has formed 1400 tex tow with loss on ignition of 1.28%.
This tow has the assembly of appropriateness and the hardness of appropriateness, and can easily be cut off.Its ability of being flooded by vibrin is be evaluated as 1, based on (inferior from 0; No wetting) to 5 (excellences; Tow be cannot see in resin) standard estimate.
This tow can be used as the toughener in SMC (sheet molding compound) the class material.
Embodiment 5
To be coated with the first composition A by the diameter 14 μ m long filaments that obtain from the tow of the effusive fusion E glass of wortle (800 holes) that stretch, then with second composition B coating (representing) with %wt:
Composition A:
Triisocyanate
(1)35
γ-methacryloxypropyl trimethoxy silane
(2)15
Palmitinic acid isopropyl esters 5
1-Methyl-2-Pyrrolidone 3
Composition B
The lauryl alcohol of etherificate (4 ethylene oxide units)
(12)16
Polyhutadiene diamines (molecular weight=1200)
(13)15
Palmitinic acid isopropyl esters 8
1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene 1
The ratio r of this size compositions and r ' are respectively 4.71 and 3.01.
When giving the long filament gluing, produce and contain the composition A of five equilibrium and the mixture of B.This mixture had the viscosity of 716Pa.s and 10.5 minutes gelation time after 1 hour.
Long filament is concentrated at together, form tow, be wrapped on the support of rotation, thereby obtain the direct rove of 20kg.This tow has the linear density of 315 tex and 0.57% loss on ignition.It has the tensile strength that equals the 31.3g/ tex, equals the hardness and the fine hair amount that equals 1.6mg of 170mm (80mm).
With the tow braiding that obtains like this, this fabric is used for reinforced epoxy, polyester and resol matrix.
(1) sells by Rhodia with the reference title of TOLONATE HDT;
(2) sell by Witco-Crompton with the reference title of SILQUEST A 174;
(3) sell by Witco-Crompton with the reference title of SILQUEST A 187;
(4) sell by Seppic with the reference title of LDM 1018;
(5) sell by Ciba-Geigy with the reference title of LY 556;
(6) sell by Ciba-Geigy with the reference title of ARALDITE HY 917;
(7) sell by Ciba-Geigy with the reference title of ARALDITE DY 070;
(8) sell by DSM with the reference title of SYNOLIT 1717;
(9) sell by Ciba-Geigy with the reference title of HTM 60;
(10) sell by Clariant with the reference title of PLYGLYCOL 1000;
(11) sell by Rhodia with the reference title of TOLONATE HDB LV;
(12) sell by Seppic with the reference title of SIMULSOL P4;
(13) sell by Atofina with the reference title of PolyBd-diamine.
Claims (22)
1. use the glass fiber strand by the size compositions coating that contains solvent that is less than 5%wt and the solution composition that contains polymerisable foundational system, described system contains the mixture of the following component of 50%wt at least:
One or more contain the component of at least one isocyanate-reactive functional group;
One or more contain the component of at least one hydroxyl reactive functional group; With
Optional one or more contain the component of at least one amine reactive functional groups.
2. glass fiber strand as claimed in claim 1 is characterized in that polymerisable foundational system accounts for the 60-100%wt of composition.
3. glass fiber strand as claimed in claim 2 is characterized in that foundational system accounts for the 75-90%wt of composition.
4. as any described glass fiber strand of claim 1-3, it is characterized in that foundational system is made up of to one or more isocyanate components, one or more hydroxy components and one or more amine components of 100wt% 75wt%.
5. as any described glass fiber strand of claim 1-3, it is characterized in that foundational system comprises that the molecular weight of 70%wt is lower than one or more components of 750 at least.
6. as any described glass fiber strand of claim 1-3, it is characterized in that the ratio r of the number of the number of isocyanate reaction reactive site and hydroxyl reaction reactive site is 0.1-6.
7. as any described glass fiber strand of claim 1-3, it is characterized in that the ratio r of summation of the number of the number of the number of isocyanate reaction reactive site and hydroxyl reaction reactive site and amine reactive site ' be 0.1-6.
8. as any described glass fiber strand of claim 1-3, the content that it is characterized in that isocyanate component is the 10-50%wt of this size compositions.
9. glass fiber strand as claimed in claim 8, the content that it is characterized in that isocyanate component are the 20-40%wt of this size compositions.
10. as any described glass fiber strand of claim 1-3, the content that it is characterized in that hydroxy component is the 15-55%wt of this size compositions.
11. glass fiber strand as claimed in claim 10, the content that it is characterized in that hydroxy component are the 25-45%wt of this size compositions.
12. any described glass fiber strand as claim 1-3 is characterized in that the content of amine component is less than or equals the 30%wt of this size compositions.
13. glass fiber strand as claimed in claim 12 is characterized in that the content of amine component is less than or equals the 20%wt of this size compositions.
14. any described glass fiber strand as claim 1-3 is characterized in that said composition comprises the catalyzer of 0-5%wt.
15. any described glass fiber strand as claim 1-3 is characterized in that said composition comprises the coupling agent of 0-30%wt.
16., it is characterized in that said composition comprises the weaving processing aid of 0-30%wt as any described glass fiber strand of claim 1-3.
17., it is characterized in that foundational system is made up of isocyanate component, one or more hydroxy components that contain at least one hydroxyl reactive functional group and one or more optional amine components that contain at least one amine reactive functional groups that one or more contain two isocyanate-reactive functional groups at least as any described glass fiber strand of claim 1-3.
18. glass fiber strand as claimed in claim 17 is characterized in that foundational system contains the isocyanate component of three isocyanate-reactive functional groups by one or more and one or more hydroxy components that contain 1-3 hydroxyl reactive functional group are formed.
19. glass fiber strand as claimed in claim 17 is characterized in that foundational system is made up of isocyanate component, one or more hydroxy components that contain hydroxyl reactive functional group and one or more amine components that contains two primary amine reaction functional groups that one or more contain three isocyanate-reactive functional groups.
20. be used for the size compositions of glass fiber strand, it is by containing solvent that is less than 5%wt and the solution composition that contains polymerisable foundational system, described system contains the mixture of the following component of 50%wt at least:
One or more contain the component of at least one isocyanate-reactive functional group;
One or more contain the component of at least one hydroxyl reactive functional group; With
Optional one or more contain the component of at least one amine reactive functional groups.
21. comprise the matrix material of at least a organic and/or inorganic materials and gluing glass fiber strand, it is characterized in that the whole of this glass fiber strand or some are made up of any described glass fiber strand of claim 1-19.
22. be used to form the purposes of painting cloth as any described glass fiber strand of claim 1-19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR02/06197 | 2002-05-22 | ||
| FR0206197A FR2839968B1 (en) | 2002-05-22 | 2002-05-22 | POLYURETHANE-BASED ANHYDROUS-SIZING COMPOSITION FOR GLASS YARNS, GLASS YARNS OBTAINED AND COMPOSITES COMPRISING SAID YARNS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1656039A CN1656039A (en) | 2005-08-17 |
| CN100436357C true CN100436357C (en) | 2008-11-26 |
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ID=29414962
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038115646A Expired - Fee Related CN100436357C (en) | 2002-05-22 | 2003-05-21 | Polyurethane-based anhydrous sizing composition for glass fibres, glass fibres thus obtained and composite materials comprising said fibres |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20060099417A1 (en) |
| EP (1) | EP1506144A1 (en) |
| JP (1) | JP2005530668A (en) |
| CN (1) | CN100436357C (en) |
| AU (1) | AU2003258770A1 (en) |
| BR (1) | BR0310070A (en) |
| CA (1) | CA2486479A1 (en) |
| FR (1) | FR2839968B1 (en) |
| MX (1) | MXPA04011511A (en) |
| NO (1) | NO20045406D0 (en) |
| PL (1) | PL372750A1 (en) |
| RU (1) | RU2314374C2 (en) |
| WO (1) | WO2003097551A1 (en) |
| ZA (1) | ZA200409327B (en) |
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| FR2833002B1 (en) * | 2001-12-05 | 2004-07-23 | Saint Gobain Vetrotex | SIZING COMPOSITION FOR GLASS WIRES, GLASS WIRES THUS OBTAINED AND COMPOSITES COMPRISING SAID WIRES |
| FR2886299B1 (en) * | 2005-05-26 | 2010-08-20 | Saint Gobain Vetrotex | POLYMER DISPERSION IN A REACTIVE ORGANIC MEDIUM, PROCESS FOR PREPARATION AND USES |
| JP6066223B2 (en) * | 2011-09-23 | 2017-01-25 | オーシーヴィー インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Reinforcing fibers and their use to reinforce concrete |
| RU2565301C1 (en) * | 2014-10-28 | 2015-10-20 | Общество с ограниченной ответственностью "КомАР" | Lubricating agent for glass and basalt fibre |
| RU2616046C1 (en) * | 2015-10-12 | 2017-04-12 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) | Method of polymer coating producing on the surface cotton cloth |
| RU2616048C1 (en) * | 2015-10-12 | 2017-04-12 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) | Method of polymer coating producing on the surface cotton cloth |
| US10053596B2 (en) * | 2016-08-30 | 2018-08-21 | Prc-Desoto International, Inc. | Curable film-forming compositions demonstrating increased wet-edge time |
| CN109679056B (en) * | 2018-11-14 | 2021-06-25 | 万华化学集团股份有限公司 | Self-crosslinking polyurethane-polyurea water dispersion and preparation method and application thereof |
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| FR2809102B1 (en) * | 2000-05-17 | 2003-03-21 | Vetrotex France Sa | SIZING COMPOSITION FOR GLASS WIRES, PROCESS USING THIS COMPOSITION AND RESULTING PRODUCTS |
| US7056976B2 (en) * | 2002-08-06 | 2006-06-06 | Huntsman International Llc | Pultrusion systems and process |
| US20060177657A1 (en) * | 2005-02-08 | 2006-08-10 | Keith Weller | Sizing compositions for fibers utilizing low VOC silanes |
| DE102005018692A1 (en) * | 2005-04-22 | 2006-10-26 | Bayer Materialscience Ag | size composition |
-
2002
- 2002-05-22 FR FR0206197A patent/FR2839968B1/en not_active Expired - Fee Related
-
2003
- 2003-05-21 BR BR0310070-7A patent/BR0310070A/en active Search and Examination
- 2003-05-21 CA CA002486479A patent/CA2486479A1/en not_active Abandoned
- 2003-05-21 CN CNB038115646A patent/CN100436357C/en not_active Expired - Fee Related
- 2003-05-21 MX MXPA04011511A patent/MXPA04011511A/en unknown
- 2003-05-21 JP JP2004505287A patent/JP2005530668A/en active Pending
- 2003-05-21 AU AU2003258770A patent/AU2003258770A1/en not_active Abandoned
- 2003-05-21 EP EP03752846A patent/EP1506144A1/en not_active Withdrawn
- 2003-05-21 PL PL03372750A patent/PL372750A1/en not_active Application Discontinuation
- 2003-05-21 WO PCT/FR2003/001537 patent/WO2003097551A1/en active Application Filing
- 2003-05-21 RU RU2004137495/04A patent/RU2314374C2/en not_active IP Right Cessation
- 2003-05-21 US US10/512,864 patent/US20060099417A1/en not_active Abandoned
-
2004
- 2004-11-19 ZA ZA200409327A patent/ZA200409327B/en unknown
- 2004-12-10 NO NO20045406A patent/NO20045406D0/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4616043A (en) * | 1985-04-26 | 1986-10-07 | Thermocell Development, Ltd. | Aliphatic polyurethane sprayable coating compositions and method of preparation |
| US5389720A (en) * | 1990-05-25 | 1995-02-14 | Miles Inc. | Aqueous polyisocyanate dispersions |
| US5185200A (en) * | 1991-03-28 | 1993-02-09 | Miles Inc. | Aqueous polyisocyanate dispersions with reduced isocyanate contents and their use for the production of fiberglass mats |
| US5308679A (en) * | 1992-06-16 | 1994-05-03 | Nitto Boseki Co., Ltd. | Raveling-preventing agent for glass fiber woven fabric, and glass fiber woven fabric to which the agent is applied |
| CN1182409A (en) * | 1996-01-05 | 1998-05-20 | 法国韦特罗特克斯有限公司 | Glass yarn sizing composition, method using same and resulting products |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060099417A1 (en) | 2006-05-11 |
| RU2314374C2 (en) | 2008-01-10 |
| FR2839968B1 (en) | 2005-02-11 |
| EP1506144A1 (en) | 2005-02-16 |
| BR0310070A (en) | 2005-03-08 |
| MXPA04011511A (en) | 2005-02-14 |
| CN1656039A (en) | 2005-08-17 |
| RU2004137495A (en) | 2005-06-10 |
| NO20045406L (en) | 2004-12-10 |
| PL372750A1 (en) | 2005-08-08 |
| ZA200409327B (en) | 2005-05-19 |
| WO2003097551A1 (en) | 2003-11-27 |
| NO20045406D0 (en) | 2004-12-10 |
| CA2486479A1 (en) | 2003-11-27 |
| JP2005530668A (en) | 2005-10-13 |
| AU2003258770A1 (en) | 2003-12-02 |
| FR2839968A1 (en) | 2003-11-28 |
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