CA2181485A1 - Glass fiber sizing compositions, sized glass fibers and methods of reinforcing polymeric materials using the same - Google Patents
Glass fiber sizing compositions, sized glass fibers and methods of reinforcing polymeric materials using the sameInfo
- Publication number
- CA2181485A1 CA2181485A1 CA002181485A CA2181485A CA2181485A1 CA 2181485 A1 CA2181485 A1 CA 2181485A1 CA 002181485 A CA002181485 A CA 002181485A CA 2181485 A CA2181485 A CA 2181485A CA 2181485 A1 CA2181485 A1 CA 2181485A1
- Authority
- CA
- Canada
- Prior art keywords
- sizing composition
- aqueous
- composition according
- aqueous sizing
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2938—Coating on discrete and individual rods, strands or filaments
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2962—Silane, silicone or siloxane in coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
Abstract
An aqueous glass fiber sizing composition is provided which provides high strength and wet-out to composites prepared using glass fibers having the sizing composition of the present invention applied thereto. When used to reinforce a thermosetting polymeric material, the glass fibers sized with this composition provide a composite useful in making pultrusion profiles having high compressive, shear and flexural strengths. The composition includes a nonionic urethane-modified epoxy thermosetting copolymer, a water-soluble, dispersible or emulsifiable epoxy film-forming polymer; an emulsifying agent; and organo-functional silane coupling agent; a fiber lubricant; and water in an amount sufficient for application of the sizing composition to at least one glass fiber.
Description
8 1 ~5 .... . - .. .
rT,~qC FIRT~P sI7lTNr~ rnMposIT}nNe~ ST7-n rt.~cc FIRT'Pq ANn Mlz~htone OT.~ RTtTNT.~nDrTNr. pnT.YMT~T Tr M~T13T TIIT.C ~STN~ 'rht~` c~
Field o rhn Tnv~on~
The present invellti.on relates to sizing compositions which may be app~ied to glass ~ibers sized glas6 fibers al-d methods of reinforcing poly~neric materials using the same and more particularly to aq~leous sizing compositions for application to glass ibers for use in reinfolcil~g t~lermosetting polymeric composites such as ilament wo~rld composit~s or pultrusiol~s.
R~ck~round of ~he~ rRn~loll Glass fibers are typically produced by drawing molten glass at a lligh rate of speed from tips of small orifices in a precious metal device or buslling. During the Eorlning and subsequent ani~-al and treatment processes the glass fibers may be brokel~ by contact with eacli ot~er and processing equipment (i.e. a process known as filamentation) . Tl~ese broken glass fibers (uzz) may accumulate on processing eq~lipm~nt and/or produce a~ desirable l~on-uniform surface on polymeric articles ~o which the glass i~ers are added .
To protect the glass fiberg from interfilament abrasion a si2ing compo6ition is applied to t~e surface of tl~e qla.ss fibers during the forming process. TyF)ical sizing compositions include ~ q such as film-formers lubricants coupling agents and emulsifiers. U.S. PAtent No. ~ 637 9S6 discloses a sizil~g compocition which includes an eF-oxy polyurethalle copolymer or a polyepoxlde resin with blocked F~olyisocyanate functionality ~I~d one or more organo coupling agents. Generally the sizil~g composition is applied to a glass riber strand subsequent to tlle drawing process and prior to gatl~ering of a pl~lrality of continuo~ls strallds on a formillg package. The forming packages are dried to remove moisture and cure tl~e slzlng ccmposition.
Gl.~ss ibers may be incorporated in~o polymeric materials by filament winding p~lltrusion and otl~er processes for orming ~ig~
strength glass fiber rei~orced ,Tolding composites. Pultruded profiles are commonly used in corrosion resistant applications in which lligl~ streng~l and weather-~bility are desired. Examples of AMENDED SHEET
.
pultruded products include arcl~itectural and a~ltomotive products, ladder rails, sucker rods, ant~nnas, railings, condllits, I-beams, Ei-beams, angles, insulator rods, floor gratings and roadway delineators .
Tlle strength of ~no].ded products Eormed Erom materials produced by tlle Allove processetl is dependent in pArt ~Ipon tl~e degree of contact betwee~l tlle polyl~er And fiber glass. Tlle meASUre of tlle flowability of tl~e pol~meric mAtriX material tllrougl~ tl~e glAss Eiber mass to obtais~ e.sse2lti;l~1y comi~lete encapsulatioll oE tlle ~llt~ire surface of eacl~ glas.s stLall~ ti~e polymeric material is re~erred to as "wet-out'' . If t l~e wet-o~lt i .s incomplete during tl~is il~itial processing, subseq~lel~t processi.ng and tlle surfAce cllarAct~ristics of the final composite InAy be Adv~!rsely effected. For example, poor wet-out may malli~est itself as low composite strel~gtlls Alld tile appearance of wl~ite fibers.
It is desirable to have high degrees of wet-out alld compatibility witll tlle thermosetting matrix resin in applications such as those discussed above.
S of t h~ ~nV~ntion The present invention overcomes many drawbacks of conventional sizing compositions by providing an aq-leolls sizing composition wi~ich may be readily applied to at least one glass Eiher to provide at least olle of tile following advantages: good solubility in the thermosetting matrix resin for high wet-out, good compatibility witi~ the tl~ermosetting matrix resin, good clarity in cured polymer pultlusions, as well as other advantages.
One Aspect of t~le present invention is an Aqueous sizil~g compo6ition for at least one glass fiber comprising a non-ionic urethane-modified epoxy thel;mosetting copolymer; a water soluble, dispersible or emulsifiable epoxy film-forming polymer; an emulsifyil~g agellt; an orgAIlo ful~ctional silAne coupling agent; a fiber lubricanti and wAter in an amount sufEiciellt for application of the sizing composition to at least one glass fiber.
Anotl~er aspect of the present invel~tion is a method oE
making a reinforcement for a variety of thermosetting resins, sucll as epoxy, polyester al~d villyl ester resins, having improved strel-gtl~.
Tl~e above-discusse(i ~Eueous sizil~g compositiol~ is applied to at le~st ANiENDED S~lEEr a portion of a surface of eacil of a plurality of glas6 fibers, which are then dried to form a reinforcement for a thermosetting polymer.
Brio Dc~criDtion of t h- Draw; rlg The foregoing s~1mmRry~ as well RS the following detailed description of tile preferred ernbodiment, will be better ullderstood when read in con~unction wi t~l ~ he appended drRwing. In the drawing:
Fig. 1 is a proton nuclear maglletic resonance ~ NMR) curve or an aqueous emulsion of a non-ionic uretll~ne-moclified epoxy thermosetting copolylner wllic~l :is commerciRlly availal~le ~Inder the trade designation Epi-Rez CMD l~60-5520 from Shell Chemical, in accordance with tl~e present in~ention.
D~t~;led Descri~tion of tho Preforred F~
The aqueous sizil~g composition oE the present illven~ion provides glass fiber strRnds l~lving high wet-out characteristics.
Articles formed from thermosetting polymeric materials incorporating glass fibers treated witll tile ~;izing composition of the present invention have improved strengt:h and clarity.
The aqueous sizing composition of t~le present invention comprises a non-ionic uretl~ane modified epoxy tllermosettillg copolymer, preferably present 1n the form of an aqueous emulsion or dispersion. Generally, t~o llol~-ionic urethane-modified epoxy thermosetting copolymer llas a~l epoxide equivRlent weigllt of abo~lt 175 to about 760 and may comprise ahout 50 to about 99 weight percent and, more prcferably, about 60 weight percent of a water-based emulsion whicll preEerably collt.lins no organic solvents.
The presently preferred non-ionic emulsion of a uret~lane-modified epoxy t~lermosett1llg copolymer is Epi-Rez CMD W60-5s20, wllic is commercially available rom S~lell Chemical. Tl-is material is a non-ionic, aqueous dispersioll c~f a urethane-modified epoxy resin having an epoxide equivRlellt w~!ight of 540 and 60 weigllt percent solids. The dispersion is t}lixotropic and contains no organic solvents. CMD W60-5s20 ca~l be cured through epoxy fullctiollality and/or hydroxyl f~lnctionality Tlle dispersion llas a viscosity of about 12,000 centipoise at 25C as measured usillg a Brookfield Model RVT, No. 5 spindle at 10 rpm. The dispersion has a density of about 1.1 g/cm"9.2 lb./gal~, an ~verage particle size of about 2 l~icrons, a p~ of about 4.0 alld a vapor ~Iressure Rt 20C of less t~lall abo~lt ~.0 AMENDED SHEET
4 ,~ 8 1 ~
mm Hg. A proton nuclear magnetic resonance ('HNMx) curve for Epi-Rez CMD W60-5520 ls show~ Fig. 1. Tlle 'ilNMI~ was perEormed oll a Bruker 300 MHz proton NMR spectrometer witll a zero referellce o tetramethylsilane ~TMS), an ambient sample temperature and Wit~l CDCL3 solvent .
As presently preferred, tile llon-ionic uretlla~le-modifieù
epoxy thermosetti~lg resill comprises abo~lt 10 to abo~lt 60 weigllt percent of the sizing composition on a non-aq~leous hasis and, more preferably, about 36 to abo~lt 55 weight percent. O~e oE ordinary skill in the art would ~luderstand t~at one or a plurality oE llon-ionic urethane-modified epoxy tl~ermosettillg resil~s or em~llrions tllereof may be used ill keeping witll the spirit a:ld scope of tlle present invention.
Tlle aqueo~ls sizirlg composition of the presellt illvention also comprises a water soluble, dispersible or emulsiiable epoxy film-forming pol~-mer. Suitable epoxy film-forming polymers cont~i at least one oxiralle rillg, as set Eortll below in Eorm~lla (I):
o (C- - - -- -C) ( I ) Examples o such epoxy film-forming p=olymers include reaction products of a halohydrin and a hydroxyl compound, sucll as a phenol or polyhydroxy alcohol. One group of suitable epoxy compounds may be obtained by tl~e reaction of a stoichiometric excess of an epihalohydrin, such as epichlorohydrin, with a polyhydric phenol such as 2,2-bis(4-hydroxypllenol)propane (bisphenol-A) to form a diglycidyl ether of bisphenol-A. Otller examples of suitable polyhydric pilenols include bis (llydroxy phenyl) metllane, hydroquinone alld resorcinol .
Examples of useul hydroxyl compounds include glycol, polyoxyalkylelle glycol, sorbitol, glycerol, 4~isopropylidene bis(2,6-dibromopllenol), dillydroxybellzene, 1,1,2,2-tetra~p-hydroxy pilenyl)-eti~ane, 1,4-butane diol, linoleic dimer acids and 1,1,3-tris~p-~lydroxy p~lellyl)-propane.
Noll-limiting examples of suitable bisphenol-A alld bispllerlol-F
compounds are Epi-Rez CMD 35201 alld Araldite~ XU GY ?.~31, respectively .
Otller epox~ f ilm- forming polymers which may be used in the sizing compositioll of tlle present invention may be produced Erom aliphatic glycidyl etllers, tile reaction of monoepoxy compo~lllds witll AMENDED SHEET
s :
themselves, or otller epoxy generating compounds, or example unsaturated monoepoxy compounds w~ich may be l~omopolymerized to produce a polyepoxy polymer such as a poly(allyl glycidyl etl-er) .
Examples o suitable epoxy film-forming polymers include EPON 826 and EPON 880 epoxy resins prepared from bisp~lenol-~ ~nd epichlorohydrill, wllic:~ are commercially available from S~ell Chemical . Otl~er exampl~.s of ~Isef~ l eyoxy film-formi lg po] ymers are set forth in U.S. Pate~t No. ~, ~S2,527 of Sallzero et al., wllicll is hereby incorporated by reference. One of ordinary skill in tlle art would understalld ~lla~ olle or a pl~ .ty of epoxy ~ ro~-millq polymers may be used in tile F.izi~lg composition of tile pres~nt invention .
The epoxy film-formillg poiymer preferably has a~ epoxy equivalent weight of about 175 to about 760 and, more preferably, is an epoxy resin having a low epoxy equivalent weight of about L80 to about 220 The epoxy eq~livalent weig~lt or epoxide equivRleslt is defined as the weig~lt o r~sin in grams which contAi~ls one grFIm equivalent of epoxy.
As presently preferred, tl~e epoxy film-forminy polymer comprises about 10 to lbout 55 weight percent of the sizing composition on a non-aqueous basis and, more preferably, about 18 to about 37 weight percent The ratio on a non-aqueous basis of non-ionic urethane-modified epoxy tl~ermosetting copolymer to epoxy fil forming polymer is generally abc~lt 30:70 to about 80:20 by weig~lL
and, more preferably, about 50:50 to about 75:25.
Tlle aq~eous sizing compo~3itioll of tlle present illvelltion also comprises at least one emulsifying agent for emulsifying t}le epoxy film-forming polymer. Tlle epoxy film-forming polymer is preferably emulsified with a conlbination of suractants, whic~l n~ay include a polyoxyalkylene blook copolymer such as a polyoxypropylelle-polyoxyethylene copolyn~er, an et iloxylated alkyl phellol and/or a polyoxyethylated vegetable oil. Al~ example of a s~litable polyoxypropylene polyoxyet~ylelle copolymer is a condensate of etl~ylene oxide wit}l llydrophobic bases formed by condel-satioll Wit~
propylene oxide Witll propylene glycol commerciaIly av~ilable as Pi URONICTM F-108 from BASF Corporation of Parsippany, New ~ersey.
Examples of useul etiloxylated ~lkyl phenols i~lcl~ldF e~lloxy].~te i octylphenoxyetl-allol , p~le~oxy po~ yetllylene -oxy (etilallol ~, ~MENDED SHEET
phenoxy(ethyleneoxy) etl~atlol and nt~nyl phenoxy poly (ethyleneoxy) et11allol . An exarnple of a commercially available ethoxylated octylphenoxyetllanol is IGEPAL CA-630 from GAF Corporation oE Wayne, New ~Jersey. An example of a polyoxyethylated veyetable oil is EMULPHOR EL-719, wilich is comm~rcially available from GAF Corp.
Otl~er examples of suitable emulsiyil1g agents include ~lon-ionic epoxide polyols sucl- as NOVEPOX'`' or Prox E 117, which are commercially availab~e froln Syl~tllron, Inc.
As preselltly prefel~l~e~1, t }le em~llsifyillg agellt is a blend of about L:L to about 4:1 of a po:lyoxypropylene-po~yoxyetllylelle copolymer ~PLURONICI~' F-loa) alld ~1l etlloxylated octyLpilelloxyetll~tlol (IGEPAi. CA-630) . Mor~ preEerably, ttle ratio of PI,~RONIC'~' F-10a to IGEPAL CA-630 is about: ~.:1. Gellerally, t~le emulsifyi~lg agellt comprises about S to about 25 weigllt percent of tlle sizillg composition on a non-aq~leous basi~i and, more preferably, about 15 to about 20 weight percent.
The sizing compositioll of the present invention comprises at least one, and preferably a mixture of three, organo functional silane coupling agents. Tile orgallo functional silane coupling agent has a reactive moiety on the compound, such as an epoxy, vinyl, acrylate, methacrylate or amino group. As presently preferred, the organo functional silane coupling agent is a mixture of epoxy (preferably A-la7 gamma-glycidoxyL~ropyltri-metlloxysilane), metllacrylate (preferably A-174 gamma-metllacryloxy-propyltrimethoxysilane) alld amino silane (preferably A-1100 gamma-aminopropyltriethoxysilane) coupling agents, eacil of wilich is commercially available from Union Carbide Corporation. Otller examples of amino silane couplillg agents are set fort)1 in U.S. Patellt No. 4,374,177, which is hereby illcorporated by reference Other suitable organo silane couplirlg agents for use in tlle aqueous sizing composition of t~le present invelltion will be evide~1t to tl-ose of ordinary skill in tlle art in view of tlle foregoing disclosure. Also, one of ordinary skill in tile art ~,ould understand t~lat one, two or more than two organo functional silane coupling agents may be used in keeping with ti1e spirit tnd scope of ti1e present inve~1tiol1.
The orgal~o fllnctional silane coupling agent may comprise about S to about 25 weigl-t percel~t of the sizing colllposition on a non-aqueous basis. Preferably, tl~e sizing compoiitiol- comprises A~IENDED SHEET
~181~
7 . . . . ..
about 6 to about 13 weigl~t percent gamma-methacryloxypropyltrimethoxysilane, zero to about 8 weigl~t percent gamma-glycidoxypropyltrimethoxy6ili~ne and about 0 l to about 1 5 weight percent gamma-Aminopropyltriethoxysilal~e on a l~on-aq~leous basis More preerably, About 7 to about 11 weigi~t percent gilmmii-methacryloxypropyltrimetl~oxysilane, 3 to about 5 weigi~t E~ercent gamma-glycidoxypropyltrimethoxysil,il~e and about 0 3 to about l 0 weight percent gamma-a~ninopropyltriethoxysilane on a l~ol~-Aq~eous basis are included il~ t l~e sizi~g compositiol~
The iber ~llbricant may be any catiol~icr llon-ionic or anionic glass iber lubricant cPmpi~tible witil ti~e otller additives which reduces ti~e il~terfilsment abrAsion betweel- tlle ~iber~ inS
presently preferred, tlle fiber lllbricant is selected from an amine salt of a fatty acid ~wlllch may, for example, include a atty Acid moiety having 12 to 22 carbon atoms and/or tertiary amines llaving alkyl groups o l to 2-2 atoms attached to tlle llitr,ogen atoln ), alkyl imidazoline derivative (such AS may be ormed by the reactiol~ o atty acids witl~ polyalkylel~e polyamines), acid solubilized Eatty acid amide (or example, saturated or unsaturated atty acid amides having acid groups o 4 to 24 carbon atoms S~ICI- as stearic Amide) And acid solubilized polyunsaturated atty acid amide More preerred are tlle Eiber glass lubricAnts selected rom a condensate o a fatty acid and polyeti~ylel-eimil-e And An amide substituted polyetilyleneimil-e, sllcll a~ Emery 67~7, a pArt:ial~y amidated polyethylene imine commercially available from i~el-kel Corporation of Kankakee, Illil~ois Otl-er examples o s-litable iilnery iber lubricants are tlle products desig~lated 6760 and 4046D
Preerably, the iber lubricant comprises about 0 05 to about 0 5 weight percent, and more preerably about 0 05 to about 0 18 weigllt percent, o the sizing composit'ion on a non-aqueous basis The sizing composition ma)~ also include an i~qlleous- or l~on-aqueous-based plasticizer Examples o suitable l~on-aqueo~ls-based plasticizers incl~de pll~llalates, s~lch as di-n-butyl pl~tl~alate;
trimellitates, sucll as trioctyl ~rimellitate; alld adipates, s~lcil as dioctyl adipate /UI exsmple olE a~l aqlleous-based plas~icizer is Carbowax 400, a polyetllylene glyccl wi~ich is commercially available rom Union Carbide Co o Dallbury, Connecticut Tlle preferred plasticizer is di-ll-butyl piltllAlAte The amollnt oE E)lasticizer may A~/IENDED S~EEr ~187~5 . . . -- , . -- .
be about O to about 10 weight percent of tlle slzing composition on a non-aqueous basis. Preerably, the amount of plasticizer is about 3 to about 5 weight percqnt of tlle fiizing composition oll a non-aqueous bas is .
The aqueous sizing composition may further comprise an organic acid.in all amount sufiicient ~o provide t}le aqueous sizing composition witll a pil oE Abollt 3 t~ about 5.5. Noll-limitlrlg exAmples o organic acids suitable for use il~ the present inventio~ incl~lde mono- and polycarboxyl i.c acids and ani~ydrides thereof, fi~lCi~ as acetic, formic, propionic, cAprioc, lactic, benzoic, pyr~lvic, oxalic acid, maleic, fulllaric, Acrylic, Illeti~acrylic acids allù mixtures thereof .
Water (preferably deio~ized) may be incl~lded in tlle aqueous sizing compositio~ all amount sufficient for application of the sizing compositio~ to at leAst o~e glass fiber. Preferably, ti~e weigllt percentage o solids is about 1 to about 10 weigl~t percent of tile aqueous sizing compositio~ and, more preerably, abo~lt 4 to about s weight percent. Tl~e total amou~lt in weigl~t perce~lt of tlle non-aqueous components using a basis excluding water generally equals about 100 percent. On a weigilt basis including water, the total amount of non-aqueous and aq~eous, , q is also about 100 percent .
The aq~eous sizil~g ~omposition of the present invention may be prepared by any suitAble metllod well known to thofie of ordinary skill in tl~e art. Pre~elably, eaci~ component is diluted in deionized water in a separAte t.allk and well miY.ed be~ore being combined with the otl~er compoll~llts in a nlain mixing tank. Tlle organo functional silane couplil~g agent ~s) may be at least partially hydrolyzed by reaction witll t~le organic hydrocarbon acid il~ tl~e presence of water. P.fter eacil of tl~e premixed ingredients is added to tile main mix tank, s~ficiel~t wAter is added to provide tl~e aqueous sizing composition witi~ a total solids conte~lt of abo~lt 1 to about 10 weight percent.
Tl~e aqueo~ls sizing composition of tile presellt inve~ltion may be applied to al~y t~pe of f ii~erizable glass composition k~lown to tilose of ordinary skill i~l tile art. Nonexclusive examples of suitable fiberizable glass compositions il~clude ''E-glass'', "621-glass'', ''~\-glass", "C-glass'', "S-glass" alld lower ree fluorine and or boron A~ENDED SHEET
9 ~1 8 1 ~5 derivatives thereo. "E-glass'' is tl~e preferred glass composition for use in the present il~vention.
PreEerably tl~e aqueous sizing compositiorl of tlle present invention is applied to green glass ~laving a refractive index of about 1.555 during tl~e formation of the glass fibers. The glass ibers typically ~l~ve diameters rang1ng from about 2. 5 x ~0 ~o about 2.5 x 10 rnillimeters (mm) ~ bout 10.3 x 10~5 to about 97 . 5 x 10-5 inches) or ~nore and preLerably a~out 1. 3 x lO to about 2.3 x 10 ' mm (about 50 x 10-5 to ~bout 90 x 10-5 i~lc~ler.) Lor fibers to be used in pultr~lded products. Tlle glass fibers may b~ prod~lced as direct draw or m~llti-e~ld rovings. The direct drAw process is generally used to prod~lce K t~roug~l r diameter fibers s~c~ as T-113 T-250 and K-675. Multi-e~ld rovings are formed from a pl~rality of fibers each fiber typically having a diameter of 1. 3 x 10-' nlm (about 50 x 10-5 i~ches) and are assembled by a conventional roving process to produce a roving ~laving tl~e desired n~mber of fibers therein .
The aqueous sizing conlposition may be applied by contacting at least a portion of eacll glass fiber emanating from a bushing with a roller-type applicator bearing tlle sizing composition or by any method well k~lown to t~lcse of ordinary skill i~- t~le art.
The fibers llavi~lg the sizing composition applied thereto may be gathered togetller to form a strand of a pl~rality of f ibers .
The strand may be wound onto a forming package placed on a rotati~lg collet. The forming package may be removed from tl~e collet a~ld dried in an oven at a temperature of about 104C (~20F) to about 149-C
(300F) for about 10 to about 13 ilo~lrs to prod~lce glass fi~er strallds having a dried residue of tlle sizil~g compositio~ t~lereupon. ~rtle drying temperature will depend upc~l~ such variables as tlle percentage of solids in t~le sizing composition components of tl~e sizing composition and type of glass fiber. The sizing composition provides glass fiber strand llav~l~g about 0.3 to about 2.0 weigllt percent oL
the dried sizing composition on the strand based upon total weigllt of t~le glass and dried si7i~g compositio~.
Tl~e stla~lds ~lay b~ trAIlsLerred frolll t~le LoL-Illing p~ckage and combined with a plurality of ctller strands to forln a rovi~lg. The roving may be used ill tlle form of continuous strands wove~ glas.s fiber strand mat or c~lopped gl~ss fibers to reinforce ~ t~ermosetting AIMENDED ~ir l gl 485 - . .
polymer, as desired, by any method known in t}le art, for example by pUltrusion, filament windillg and panel formation processes.
Glass fibers 1~aving tl1e sizing composition of tl-e present invention applied t}lereto may be used to reinforce any t}lermosetting polymer, including but not limited to polyesters, vinyl esters and epoxies. Nonexcl~sive examples o suitable t~lermo~eLting polymers include orthopi~t~alic a~ld isopilt}lalic polyesters; modified polyesters such as methyl metllacrylate, neopel1tylglycol and acrylic n~odiried derivatives thereof; villyl esters such as bisp~lellol-~ or epoxy novolak type; and epoxy polyn~els s~lch as EPON 826 (an epoxy prepared from bisphenol-A alld .~ omonomer ~ci- ar. epictllorol~yd~
For pultr~ioll App] ications, continuous rovings aL-e impregnated in t}le desired resin mix and pulled througi~ a heated die having a desired profile to cure tl1e composi.te. Generally, abo~lt 50 to about 80 weigl~t percent of glass iber is used to prepare pultruded products, based on the total weigllt of the resin matrix and glass fibers.
The present invention, will now be illustrated by tlle following specific, noll-limiting example.
Ea;~
Each of ti~e components in tl~e amoullts set forth in Table 1 was mixed. to for~ll an aqueous si2ing composition according to the present invention.
~E~
WEIGirT Ol' COMPONENT
(GRAMS) I?ER GALLON OF WEIGHT PERCENT OF
AQUEOUS SIZING COMPONENT OF SIZING
COMPOSIT:rON ON NON- COMPOSITION ON NON-COMPONENT AQUEOUS i~ASIS AQUEOUS r3ASIS
EPI-REZ CMD W60-55~0 126.36 38.77 EPON 880 67 . 94 34 . 75 PLURONIC F-108 10.07 S.lS
IGEPAL CA-630 5.08 2.60 A-174 21.9 9.30 A-187 9.1~ 3.78 A-1100 2.18 0.71 EMERY 6717 0.91 0.46 Di-n-i3utyl Pht}lal~te 8.75 4.47 Acetic Acid - 5 .
~MENDED Si~EET
Three hundred and seventy-nlne (379) liters (one hundred gallons~ of tl~e above aqueous sizing composition was prepared according to the following procedure. EPON 880, PLURONICr~' F-10a, IGEPAL CA-630 and di-n-butyl pht}lalate were combined in t}le amounts set forth above al-d }leated to about 60C to about 71~C (about 110F to about 160F) wit}l tl~orough mixing. W}Ien the desired temperature was obtalned, high s}leAr mixing was commenced using an Epp~nbach mixer.
Hot water o about 49C to about 60C (about 120F to about 140F) in about a 2 :1 volumetric rAtio of water to mixture w~ rlowl y added to the mixture to einulsi~y tl~e epoxy resin. The A-174 A-197 and A-1100 silanes were hydrolyzed sequentially in water acidiEied wit}~ acetic acid at a ratio o about 1:10 silane to water by weigllt and added to t}le main mixt~lre. To ~I~is mixt~Ire was added 3.8 liters (l gallon) of hot water of abo~lt ~9~C to about 60rC (about 120F to about 140F) premixed with RMERY 6717 and 75.7 liters (2Q gallolIs) of water premixed wit}l EPI-RF:% CMD W60-5520. The resulting ~q~leo~ls sizing composition had a p~ of about 4 . 5 to about 5. 5 weig}~t percent ~olids .
The sizing composition was applied to ~-17.3 glass fiber strands after conventional cooling and thermal conditioning by air and water sprays using a conventional roller-type applicator. Each forming package was dried at a temperature of about 104C to about 149C (about 220F to about 300F) for about 10-13 }~ours to fornl glass strand having about 0 . 3 to about 2 . 0 weight percent of dried sizing thereon. After drying t}Ie forming packages were mounted on creel and transforl,~ed into roving.
Pultruded composites wer-3 prepared ~Ising an isopht}lalic polyester resin mix aIId an epoxy resin formulatiol- e~cI~ described below, with t}le requir~d number of tows of roving I~avirlg tl~e sizilIg composition of t}le pr~sel~t illventio~ applied tllereto. TIle compoIlellts of t}le isophtl~alic polyester resin mix are set ort~1 iIl TAble 2 alld tlle components of tlle ~poxy resin formulatiol- are set ~ort}I ill Table 3.
AMENDED S~iEr,T
COMPONENT WEIGHT OF COMPONENT (GRAMS) AROPOL 2036 ~Ø 000 ZELEC UN mold release 100 ASP(13 400P ClRy 1800 Eenzoyl Pero:clde initiator 50 PERCADOX 16N il~itiator 50 t-~3utyl Perbenzoate il~itiator 50 Styrene 50 AROPOL 2036 polyeste2: resin formulation (a~ isopi~thalic polyester resin) is colllmercially ~vailable from Ashlalld Chemical Inc.
of Columbus, Ollio. ZELEC UN mol~ release is commercially available from E. I . du Pont de Nemours & Co. of E~1ilmingtoll, Delaware . PERCADOX
16N is a peroxycarl~onate initi~tor commercially available froln AE~ZO
Chemical Inc. of Dobbs Ferry, Ne~ York.
~I~'S L E 3 COMPONENT idEIGHT OF COMPONENT (GRAMS) EPON Resin 9310 11,000 EPON Curing Agerlt 9360 3630 Accelerator 537 73 . 7 INTEL 1850HT mold release 73.7 ASP~ 400P clay 2200 EPON 9310 is an epox~/ resin wilich is commercially available from Shell Chemical. E'PON curing agent 9360, also commercially available from Sl~el]., is a mixed aromatic amine syste modified with a reactive monomer. Accelerator 537 is a cure accelerant commercially available! from Shell Cllemical. INTEL 1350EET
mold release is commercially avai.lable from Axel Plastics Researcl Laboratories .
Tlle processing par~meters for preparing tlle pultr~lded composites are set fol-tl~ in Table 4.
AMENDED SHEET
L 8~ ~5 ~ 3 : . . ' .
~B~
POLYESTER EPOXY
PROCESSING PARI\METER FORMULATION FORMULATION
GLASS CONTENT (WT ~) 70-72 74-76 FIRST PLATEN TEMPERATURE C (F~ 135 (275) 199 (390) SECOND PLATEN TEMPERR~URE C (F) 149 (300) 210 (410) PULL SPEED cnn/min ~ C~ES/MIN) 46 (18) 30 (12) Pultluùed compo~sit~s ~Ising the polyester ~ormulatioll were evaluated to determ~lle i~l-plnne sl~ear strengt~ according to ASTM D-3846 short beam s~ear according to ~STM D-2344 flex~lral s~eAr strength and flexural modulus accordlng to ASTM Met~lod D-790 T~le results of each o t~ese tests are set forth in Table 5 GLASS IN-PLANE S~ORT BEAM FLEXUR~L
CONTENT SHEAR SHEAR SHEAR FLEXURAL
(WEIGHT STRENGTH STRENGTH STRENGTH MODULUS
PERCENT) (ksi) (ksi) (ksi) (ksi) Pultr~lded compo~ite~ ~Ising (1) glass fibers ~nving t~e sizing compositiol~ of t~le ~L~fiellt illvention ~pplied t~ereto (Sample A) or (2) the commerciall~ ~v~ le 712 a~ld 764 rovil~g prod~lcts of PPG Industries Il~c of Pitl ~ L(31l Pennsylvania (Samples B a~d C
respectiveLy) in t~e above l~ol~e~ter and epoxy form~llations were evaluated to determine aveLng~ in-plane shear strengt~l accordil~g to ASTM D-3846 before nnd nftel bei~l3 s~lbjected contill~o~ly for 43 ~lours to boiling water T~le glass content Eor eac~l of t~le samples using the polyester formulatiol~ was 70-72 weight percent T~e glass colltent for each of t~le samples ~lsing t~le epoxy orm~1atioll was 76-77 weight percellt T~le average vnll~es of in-plane sllear strerlgth (derived from multiple r~ s) are presented in Table 6 or samples usil~g tlle polyester formulatio~l nnd Table 7 for samples usillg t~le epoxy formulatioll AMENDED SHEET
~
~R ' -li- -~!;-- S:~} h'ET IN-PLh1~E S:iE~-S-'PE`~GTE (}:s_) STP~ENGT:~ ~}:si~
SA.' ;PLE
E;.~ 3 9 C 6 ~ 5 ., _ _ _ ~
3R~ L~--- S-:_~ 'vt'E~ Il~-PLAN} S:~E~P.
S'~,-~`i~-Tr: 'ks~ ' STP~rNGT:~ (}:s:) S~ 'P_E
C . . C
~ s sn~ r. ~a'~` es 5, 6 ani ~, ;he pul~ruaé._ c~rapcs: ,es prepare~ ~s- n5 s_ass C:be-s c:~a=e h-: .k ;he r;zing com.p~s:~ ~ o- cc _ O
presen_ :rver.~ or e~ ~ b__ r,:S:r :r.--~ane, sho-_ beam a?, d ':e}:~_~a:
shear s~re:lg.i:, as we:: as ;lg~ -'exural mod.:lus ~he p~_l_ruiec composi~es Cormei usln~ coa~ed glass fibers o' the presen~ :nve~ or _. .' e p-',ves-er 'C-m~A- C-- ha~e superior dry and wet :n-~lan~ shear s=reng-r =c ~hose com~s:=es ~-emarec' us;ng conven-:or.a_ ~~a-~~ g:ass ~
- :bers, as r~hOhT _.. Table 6, a~c com:parable performance :.. -h~= ep~
'orm~_~a~-or, as sh~ T. _r~ ~ab~e ~
The ac~ous s:.:ng c~mpo~ lo-. 0c .he rresen_ :r~e ~_o procuces g`'ass ~'~be- s-,-ar~s ra-~ 'gh we_-ou= psr'orma:lcs _c produce composi~es ha-;:~._ g~o- =:ar~ a-c rlgh s=rer.~.; -~ 9=
incorpo~a.ed as reinfo-ces-n-s ~cr =hs~m~se;~i~g pc'~rlsrs It will be a~p~ecla~el b~ those s3~illed in -ho ar- .ka~
changes could be made to the embodiment descrlbed above h~:,hou;
departins from the brcac :nvent:ve concept th~reof I~ is understood, thereCore, ;at tk1s ~n~.~ention 15 not limited to ~he par~icular ~ ~ mAnt àlsc1osec, r,u- ~ t is intended ~o c~ver modlf lcatlons hhich are h ~ =hln =he spirl_ anc scope of th6 ' -vs? _l0r, as def ~ ned by the appende~ clalms AMENDE~ S '---
rT,~qC FIRT~P sI7lTNr~ rnMposIT}nNe~ ST7-n rt.~cc FIRT'Pq ANn Mlz~htone OT.~ RTtTNT.~nDrTNr. pnT.YMT~T Tr M~T13T TIIT.C ~STN~ 'rht~` c~
Field o rhn Tnv~on~
The present invellti.on relates to sizing compositions which may be app~ied to glass ~ibers sized glas6 fibers al-d methods of reinforcing poly~neric materials using the same and more particularly to aq~leous sizing compositions for application to glass ibers for use in reinfolcil~g t~lermosetting polymeric composites such as ilament wo~rld composit~s or pultrusiol~s.
R~ck~round of ~he~ rRn~loll Glass fibers are typically produced by drawing molten glass at a lligh rate of speed from tips of small orifices in a precious metal device or buslling. During the Eorlning and subsequent ani~-al and treatment processes the glass fibers may be brokel~ by contact with eacli ot~er and processing equipment (i.e. a process known as filamentation) . Tl~ese broken glass fibers (uzz) may accumulate on processing eq~lipm~nt and/or produce a~ desirable l~on-uniform surface on polymeric articles ~o which the glass i~ers are added .
To protect the glass fiberg from interfilament abrasion a si2ing compo6ition is applied to t~e surface of tl~e qla.ss fibers during the forming process. TyF)ical sizing compositions include ~ q such as film-formers lubricants coupling agents and emulsifiers. U.S. PAtent No. ~ 637 9S6 discloses a sizil~g compocition which includes an eF-oxy polyurethalle copolymer or a polyepoxlde resin with blocked F~olyisocyanate functionality ~I~d one or more organo coupling agents. Generally the sizil~g composition is applied to a glass riber strand subsequent to tlle drawing process and prior to gatl~ering of a pl~lrality of continuo~ls strallds on a formillg package. The forming packages are dried to remove moisture and cure tl~e slzlng ccmposition.
Gl.~ss ibers may be incorporated in~o polymeric materials by filament winding p~lltrusion and otl~er processes for orming ~ig~
strength glass fiber rei~orced ,Tolding composites. Pultruded profiles are commonly used in corrosion resistant applications in which lligl~ streng~l and weather-~bility are desired. Examples of AMENDED SHEET
.
pultruded products include arcl~itectural and a~ltomotive products, ladder rails, sucker rods, ant~nnas, railings, condllits, I-beams, Ei-beams, angles, insulator rods, floor gratings and roadway delineators .
Tlle strength of ~no].ded products Eormed Erom materials produced by tlle Allove processetl is dependent in pArt ~Ipon tl~e degree of contact betwee~l tlle polyl~er And fiber glass. Tlle meASUre of tlle flowability of tl~e pol~meric mAtriX material tllrougl~ tl~e glAss Eiber mass to obtais~ e.sse2lti;l~1y comi~lete encapsulatioll oE tlle ~llt~ire surface of eacl~ glas.s stLall~ ti~e polymeric material is re~erred to as "wet-out'' . If t l~e wet-o~lt i .s incomplete during tl~is il~itial processing, subseq~lel~t processi.ng and tlle surfAce cllarAct~ristics of the final composite InAy be Adv~!rsely effected. For example, poor wet-out may malli~est itself as low composite strel~gtlls Alld tile appearance of wl~ite fibers.
It is desirable to have high degrees of wet-out alld compatibility witll tlle thermosetting matrix resin in applications such as those discussed above.
S of t h~ ~nV~ntion The present invention overcomes many drawbacks of conventional sizing compositions by providing an aq-leolls sizing composition wi~ich may be readily applied to at least one glass Eiher to provide at least olle of tile following advantages: good solubility in the thermosetting matrix resin for high wet-out, good compatibility witi~ the tl~ermosetting matrix resin, good clarity in cured polymer pultlusions, as well as other advantages.
One Aspect of t~le present invention is an Aqueous sizil~g compo6ition for at least one glass fiber comprising a non-ionic urethane-modified epoxy thel;mosetting copolymer; a water soluble, dispersible or emulsifiable epoxy film-forming polymer; an emulsifyil~g agellt; an orgAIlo ful~ctional silAne coupling agent; a fiber lubricanti and wAter in an amount sufEiciellt for application of the sizing composition to at least one glass fiber.
Anotl~er aspect of the present invel~tion is a method oE
making a reinforcement for a variety of thermosetting resins, sucll as epoxy, polyester al~d villyl ester resins, having improved strel-gtl~.
Tl~e above-discusse(i ~Eueous sizil~g compositiol~ is applied to at le~st ANiENDED S~lEEr a portion of a surface of eacil of a plurality of glas6 fibers, which are then dried to form a reinforcement for a thermosetting polymer.
Brio Dc~criDtion of t h- Draw; rlg The foregoing s~1mmRry~ as well RS the following detailed description of tile preferred ernbodiment, will be better ullderstood when read in con~unction wi t~l ~ he appended drRwing. In the drawing:
Fig. 1 is a proton nuclear maglletic resonance ~ NMR) curve or an aqueous emulsion of a non-ionic uretll~ne-moclified epoxy thermosetting copolylner wllic~l :is commerciRlly availal~le ~Inder the trade designation Epi-Rez CMD l~60-5520 from Shell Chemical, in accordance with tl~e present in~ention.
D~t~;led Descri~tion of tho Preforred F~
The aqueous sizil~g composition oE the present illven~ion provides glass fiber strRnds l~lving high wet-out characteristics.
Articles formed from thermosetting polymeric materials incorporating glass fibers treated witll tile ~;izing composition of the present invention have improved strengt:h and clarity.
The aqueous sizing composition of t~le present invention comprises a non-ionic uretl~ane modified epoxy tllermosettillg copolymer, preferably present 1n the form of an aqueous emulsion or dispersion. Generally, t~o llol~-ionic urethane-modified epoxy thermosetting copolymer llas a~l epoxide equivRlent weigllt of abo~lt 175 to about 760 and may comprise ahout 50 to about 99 weight percent and, more prcferably, about 60 weight percent of a water-based emulsion whicll preEerably collt.lins no organic solvents.
The presently preferred non-ionic emulsion of a uret~lane-modified epoxy t~lermosett1llg copolymer is Epi-Rez CMD W60-5s20, wllic is commercially available rom S~lell Chemical. Tl-is material is a non-ionic, aqueous dispersioll c~f a urethane-modified epoxy resin having an epoxide equivRlellt w~!ight of 540 and 60 weigllt percent solids. The dispersion is t}lixotropic and contains no organic solvents. CMD W60-5s20 ca~l be cured through epoxy fullctiollality and/or hydroxyl f~lnctionality Tlle dispersion llas a viscosity of about 12,000 centipoise at 25C as measured usillg a Brookfield Model RVT, No. 5 spindle at 10 rpm. The dispersion has a density of about 1.1 g/cm"9.2 lb./gal~, an ~verage particle size of about 2 l~icrons, a p~ of about 4.0 alld a vapor ~Iressure Rt 20C of less t~lall abo~lt ~.0 AMENDED SHEET
4 ,~ 8 1 ~
mm Hg. A proton nuclear magnetic resonance ('HNMx) curve for Epi-Rez CMD W60-5520 ls show~ Fig. 1. Tlle 'ilNMI~ was perEormed oll a Bruker 300 MHz proton NMR spectrometer witll a zero referellce o tetramethylsilane ~TMS), an ambient sample temperature and Wit~l CDCL3 solvent .
As presently preferred, tile llon-ionic uretlla~le-modifieù
epoxy thermosetti~lg resill comprises abo~lt 10 to abo~lt 60 weigllt percent of the sizing composition on a non-aq~leous hasis and, more preferably, about 36 to abo~lt 55 weight percent. O~e oE ordinary skill in the art would ~luderstand t~at one or a plurality oE llon-ionic urethane-modified epoxy tl~ermosettillg resil~s or em~llrions tllereof may be used ill keeping witll the spirit a:ld scope of tlle present invention.
Tlle aqueo~ls sizirlg composition of the presellt illvention also comprises a water soluble, dispersible or emulsiiable epoxy film-forming pol~-mer. Suitable epoxy film-forming polymers cont~i at least one oxiralle rillg, as set Eortll below in Eorm~lla (I):
o (C- - - -- -C) ( I ) Examples o such epoxy film-forming p=olymers include reaction products of a halohydrin and a hydroxyl compound, sucll as a phenol or polyhydroxy alcohol. One group of suitable epoxy compounds may be obtained by tl~e reaction of a stoichiometric excess of an epihalohydrin, such as epichlorohydrin, with a polyhydric phenol such as 2,2-bis(4-hydroxypllenol)propane (bisphenol-A) to form a diglycidyl ether of bisphenol-A. Otller examples of suitable polyhydric pilenols include bis (llydroxy phenyl) metllane, hydroquinone alld resorcinol .
Examples of useul hydroxyl compounds include glycol, polyoxyalkylelle glycol, sorbitol, glycerol, 4~isopropylidene bis(2,6-dibromopllenol), dillydroxybellzene, 1,1,2,2-tetra~p-hydroxy pilenyl)-eti~ane, 1,4-butane diol, linoleic dimer acids and 1,1,3-tris~p-~lydroxy p~lellyl)-propane.
Noll-limiting examples of suitable bisphenol-A alld bispllerlol-F
compounds are Epi-Rez CMD 35201 alld Araldite~ XU GY ?.~31, respectively .
Otller epox~ f ilm- forming polymers which may be used in the sizing compositioll of tlle present invention may be produced Erom aliphatic glycidyl etllers, tile reaction of monoepoxy compo~lllds witll AMENDED SHEET
s :
themselves, or otller epoxy generating compounds, or example unsaturated monoepoxy compounds w~ich may be l~omopolymerized to produce a polyepoxy polymer such as a poly(allyl glycidyl etl-er) .
Examples o suitable epoxy film-forming polymers include EPON 826 and EPON 880 epoxy resins prepared from bisp~lenol-~ ~nd epichlorohydrill, wllic:~ are commercially available from S~ell Chemical . Otl~er exampl~.s of ~Isef~ l eyoxy film-formi lg po] ymers are set forth in U.S. Pate~t No. ~, ~S2,527 of Sallzero et al., wllicll is hereby incorporated by reference. One of ordinary skill in tlle art would understalld ~lla~ olle or a pl~ .ty of epoxy ~ ro~-millq polymers may be used in tile F.izi~lg composition of tile pres~nt invention .
The epoxy film-formillg poiymer preferably has a~ epoxy equivalent weight of about 175 to about 760 and, more preferably, is an epoxy resin having a low epoxy equivalent weight of about L80 to about 220 The epoxy eq~livalent weig~lt or epoxide equivRleslt is defined as the weig~lt o r~sin in grams which contAi~ls one grFIm equivalent of epoxy.
As presently preferred, tl~e epoxy film-forminy polymer comprises about 10 to lbout 55 weight percent of the sizing composition on a non-aqueous basis and, more preferably, about 18 to about 37 weight percent The ratio on a non-aqueous basis of non-ionic urethane-modified epoxy tl~ermosetting copolymer to epoxy fil forming polymer is generally abc~lt 30:70 to about 80:20 by weig~lL
and, more preferably, about 50:50 to about 75:25.
Tlle aq~eous sizing compo~3itioll of tlle present illvelltion also comprises at least one emulsifying agent for emulsifying t}le epoxy film-forming polymer. Tlle epoxy film-forming polymer is preferably emulsified with a conlbination of suractants, whic~l n~ay include a polyoxyalkylene blook copolymer such as a polyoxypropylelle-polyoxyethylene copolyn~er, an et iloxylated alkyl phellol and/or a polyoxyethylated vegetable oil. Al~ example of a s~litable polyoxypropylene polyoxyet~ylelle copolymer is a condensate of etl~ylene oxide wit}l llydrophobic bases formed by condel-satioll Wit~
propylene oxide Witll propylene glycol commerciaIly av~ilable as Pi URONICTM F-108 from BASF Corporation of Parsippany, New ~ersey.
Examples of useul etiloxylated ~lkyl phenols i~lcl~ldF e~lloxy].~te i octylphenoxyetl-allol , p~le~oxy po~ yetllylene -oxy (etilallol ~, ~MENDED SHEET
phenoxy(ethyleneoxy) etl~atlol and nt~nyl phenoxy poly (ethyleneoxy) et11allol . An exarnple of a commercially available ethoxylated octylphenoxyetllanol is IGEPAL CA-630 from GAF Corporation oE Wayne, New ~Jersey. An example of a polyoxyethylated veyetable oil is EMULPHOR EL-719, wilich is comm~rcially available from GAF Corp.
Otl~er examples of suitable emulsiyil1g agents include ~lon-ionic epoxide polyols sucl- as NOVEPOX'`' or Prox E 117, which are commercially availab~e froln Syl~tllron, Inc.
As preselltly prefel~l~e~1, t }le em~llsifyillg agellt is a blend of about L:L to about 4:1 of a po:lyoxypropylene-po~yoxyetllylelle copolymer ~PLURONICI~' F-loa) alld ~1l etlloxylated octyLpilelloxyetll~tlol (IGEPAi. CA-630) . Mor~ preEerably, ttle ratio of PI,~RONIC'~' F-10a to IGEPAL CA-630 is about: ~.:1. Gellerally, t~le emulsifyi~lg agellt comprises about S to about 25 weigllt percent of tlle sizillg composition on a non-aq~leous basi~i and, more preferably, about 15 to about 20 weight percent.
The sizing compositioll of the present invention comprises at least one, and preferably a mixture of three, organo functional silane coupling agents. Tile orgallo functional silane coupling agent has a reactive moiety on the compound, such as an epoxy, vinyl, acrylate, methacrylate or amino group. As presently preferred, the organo functional silane coupling agent is a mixture of epoxy (preferably A-la7 gamma-glycidoxyL~ropyltri-metlloxysilane), metllacrylate (preferably A-174 gamma-metllacryloxy-propyltrimethoxysilane) alld amino silane (preferably A-1100 gamma-aminopropyltriethoxysilane) coupling agents, eacil of wilich is commercially available from Union Carbide Corporation. Otller examples of amino silane couplillg agents are set fort)1 in U.S. Patellt No. 4,374,177, which is hereby illcorporated by reference Other suitable organo silane couplirlg agents for use in tlle aqueous sizing composition of t~le present invelltion will be evide~1t to tl-ose of ordinary skill in tlle art in view of tlle foregoing disclosure. Also, one of ordinary skill in tile art ~,ould understand t~lat one, two or more than two organo functional silane coupling agents may be used in keeping with ti1e spirit tnd scope of ti1e present inve~1tiol1.
The orgal~o fllnctional silane coupling agent may comprise about S to about 25 weigl-t percel~t of the sizing colllposition on a non-aqueous basis. Preferably, tl~e sizing compoiitiol- comprises A~IENDED SHEET
~181~
7 . . . . ..
about 6 to about 13 weigl~t percent gamma-methacryloxypropyltrimethoxysilane, zero to about 8 weigl~t percent gamma-glycidoxypropyltrimethoxy6ili~ne and about 0 l to about 1 5 weight percent gamma-Aminopropyltriethoxysilal~e on a l~on-aq~leous basis More preerably, About 7 to about 11 weigi~t percent gilmmii-methacryloxypropyltrimetl~oxysilane, 3 to about 5 weigi~t E~ercent gamma-glycidoxypropyltrimethoxysil,il~e and about 0 3 to about l 0 weight percent gamma-a~ninopropyltriethoxysilane on a l~ol~-Aq~eous basis are included il~ t l~e sizi~g compositiol~
The iber ~llbricant may be any catiol~icr llon-ionic or anionic glass iber lubricant cPmpi~tible witil ti~e otller additives which reduces ti~e il~terfilsment abrAsion betweel- tlle ~iber~ inS
presently preferred, tlle fiber lllbricant is selected from an amine salt of a fatty acid ~wlllch may, for example, include a atty Acid moiety having 12 to 22 carbon atoms and/or tertiary amines llaving alkyl groups o l to 2-2 atoms attached to tlle llitr,ogen atoln ), alkyl imidazoline derivative (such AS may be ormed by the reactiol~ o atty acids witl~ polyalkylel~e polyamines), acid solubilized Eatty acid amide (or example, saturated or unsaturated atty acid amides having acid groups o 4 to 24 carbon atoms S~ICI- as stearic Amide) And acid solubilized polyunsaturated atty acid amide More preerred are tlle Eiber glass lubricAnts selected rom a condensate o a fatty acid and polyeti~ylel-eimil-e And An amide substituted polyetilyleneimil-e, sllcll a~ Emery 67~7, a pArt:ial~y amidated polyethylene imine commercially available from i~el-kel Corporation of Kankakee, Illil~ois Otl-er examples o s-litable iilnery iber lubricants are tlle products desig~lated 6760 and 4046D
Preerably, the iber lubricant comprises about 0 05 to about 0 5 weight percent, and more preerably about 0 05 to about 0 18 weigllt percent, o the sizing composit'ion on a non-aqueous basis The sizing composition ma)~ also include an i~qlleous- or l~on-aqueous-based plasticizer Examples o suitable l~on-aqueo~ls-based plasticizers incl~de pll~llalates, s~lch as di-n-butyl pl~tl~alate;
trimellitates, sucll as trioctyl ~rimellitate; alld adipates, s~lcil as dioctyl adipate /UI exsmple olE a~l aqlleous-based plas~icizer is Carbowax 400, a polyetllylene glyccl wi~ich is commercially available rom Union Carbide Co o Dallbury, Connecticut Tlle preferred plasticizer is di-ll-butyl piltllAlAte The amollnt oE E)lasticizer may A~/IENDED S~EEr ~187~5 . . . -- , . -- .
be about O to about 10 weight percent of tlle slzing composition on a non-aqueous basis. Preerably, the amount of plasticizer is about 3 to about 5 weight percqnt of tlle fiizing composition oll a non-aqueous bas is .
The aqueous sizing composition may further comprise an organic acid.in all amount sufiicient ~o provide t}le aqueous sizing composition witll a pil oE Abollt 3 t~ about 5.5. Noll-limitlrlg exAmples o organic acids suitable for use il~ the present inventio~ incl~lde mono- and polycarboxyl i.c acids and ani~ydrides thereof, fi~lCi~ as acetic, formic, propionic, cAprioc, lactic, benzoic, pyr~lvic, oxalic acid, maleic, fulllaric, Acrylic, Illeti~acrylic acids allù mixtures thereof .
Water (preferably deio~ized) may be incl~lded in tlle aqueous sizing compositio~ all amount sufficient for application of the sizing compositio~ to at leAst o~e glass fiber. Preferably, ti~e weigllt percentage o solids is about 1 to about 10 weigl~t percent of tile aqueous sizing compositio~ and, more preerably, abo~lt 4 to about s weight percent. Tl~e total amou~lt in weigl~t perce~lt of tlle non-aqueous components using a basis excluding water generally equals about 100 percent. On a weigilt basis including water, the total amount of non-aqueous and aq~eous, , q is also about 100 percent .
The aq~eous sizil~g ~omposition of the present invention may be prepared by any suitAble metllod well known to thofie of ordinary skill in tl~e art. Pre~elably, eaci~ component is diluted in deionized water in a separAte t.allk and well miY.ed be~ore being combined with the otl~er compoll~llts in a nlain mixing tank. Tlle organo functional silane couplil~g agent ~s) may be at least partially hydrolyzed by reaction witll t~le organic hydrocarbon acid il~ tl~e presence of water. P.fter eacil of tl~e premixed ingredients is added to tile main mix tank, s~ficiel~t wAter is added to provide tl~e aqueous sizing composition witi~ a total solids conte~lt of abo~lt 1 to about 10 weight percent.
Tl~e aqueo~ls sizing composition of tile presellt inve~ltion may be applied to al~y t~pe of f ii~erizable glass composition k~lown to tilose of ordinary skill i~l tile art. Nonexclusive examples of suitable fiberizable glass compositions il~clude ''E-glass'', "621-glass'', ''~\-glass", "C-glass'', "S-glass" alld lower ree fluorine and or boron A~ENDED SHEET
9 ~1 8 1 ~5 derivatives thereo. "E-glass'' is tl~e preferred glass composition for use in the present il~vention.
PreEerably tl~e aqueous sizing compositiorl of tlle present invention is applied to green glass ~laving a refractive index of about 1.555 during tl~e formation of the glass fibers. The glass ibers typically ~l~ve diameters rang1ng from about 2. 5 x ~0 ~o about 2.5 x 10 rnillimeters (mm) ~ bout 10.3 x 10~5 to about 97 . 5 x 10-5 inches) or ~nore and preLerably a~out 1. 3 x lO to about 2.3 x 10 ' mm (about 50 x 10-5 to ~bout 90 x 10-5 i~lc~ler.) Lor fibers to be used in pultr~lded products. Tlle glass fibers may b~ prod~lced as direct draw or m~llti-e~ld rovings. The direct drAw process is generally used to prod~lce K t~roug~l r diameter fibers s~c~ as T-113 T-250 and K-675. Multi-e~ld rovings are formed from a pl~rality of fibers each fiber typically having a diameter of 1. 3 x 10-' nlm (about 50 x 10-5 i~ches) and are assembled by a conventional roving process to produce a roving ~laving tl~e desired n~mber of fibers therein .
The aqueous sizing conlposition may be applied by contacting at least a portion of eacll glass fiber emanating from a bushing with a roller-type applicator bearing tlle sizing composition or by any method well k~lown to t~lcse of ordinary skill i~- t~le art.
The fibers llavi~lg the sizing composition applied thereto may be gathered togetller to form a strand of a pl~rality of f ibers .
The strand may be wound onto a forming package placed on a rotati~lg collet. The forming package may be removed from tl~e collet a~ld dried in an oven at a temperature of about 104C (~20F) to about 149-C
(300F) for about 10 to about 13 ilo~lrs to prod~lce glass fi~er strallds having a dried residue of tlle sizil~g compositio~ t~lereupon. ~rtle drying temperature will depend upc~l~ such variables as tlle percentage of solids in t~le sizing composition components of tl~e sizing composition and type of glass fiber. The sizing composition provides glass fiber strand llav~l~g about 0.3 to about 2.0 weigllt percent oL
the dried sizing composition on the strand based upon total weigllt of t~le glass and dried si7i~g compositio~.
Tl~e stla~lds ~lay b~ trAIlsLerred frolll t~le LoL-Illing p~ckage and combined with a plurality of ctller strands to forln a rovi~lg. The roving may be used ill tlle form of continuous strands wove~ glas.s fiber strand mat or c~lopped gl~ss fibers to reinforce ~ t~ermosetting AIMENDED ~ir l gl 485 - . .
polymer, as desired, by any method known in t}le art, for example by pUltrusion, filament windillg and panel formation processes.
Glass fibers 1~aving tl1e sizing composition of tl-e present invention applied t}lereto may be used to reinforce any t}lermosetting polymer, including but not limited to polyesters, vinyl esters and epoxies. Nonexcl~sive examples o suitable t~lermo~eLting polymers include orthopi~t~alic a~ld isopilt}lalic polyesters; modified polyesters such as methyl metllacrylate, neopel1tylglycol and acrylic n~odiried derivatives thereof; villyl esters such as bisp~lellol-~ or epoxy novolak type; and epoxy polyn~els s~lch as EPON 826 (an epoxy prepared from bisphenol-A alld .~ omonomer ~ci- ar. epictllorol~yd~
For pultr~ioll App] ications, continuous rovings aL-e impregnated in t}le desired resin mix and pulled througi~ a heated die having a desired profile to cure tl1e composi.te. Generally, abo~lt 50 to about 80 weigl~t percent of glass iber is used to prepare pultruded products, based on the total weigllt of the resin matrix and glass fibers.
The present invention, will now be illustrated by tlle following specific, noll-limiting example.
Ea;~
Each of ti~e components in tl~e amoullts set forth in Table 1 was mixed. to for~ll an aqueous si2ing composition according to the present invention.
~E~
WEIGirT Ol' COMPONENT
(GRAMS) I?ER GALLON OF WEIGHT PERCENT OF
AQUEOUS SIZING COMPONENT OF SIZING
COMPOSIT:rON ON NON- COMPOSITION ON NON-COMPONENT AQUEOUS i~ASIS AQUEOUS r3ASIS
EPI-REZ CMD W60-55~0 126.36 38.77 EPON 880 67 . 94 34 . 75 PLURONIC F-108 10.07 S.lS
IGEPAL CA-630 5.08 2.60 A-174 21.9 9.30 A-187 9.1~ 3.78 A-1100 2.18 0.71 EMERY 6717 0.91 0.46 Di-n-i3utyl Pht}lal~te 8.75 4.47 Acetic Acid - 5 .
~MENDED Si~EET
Three hundred and seventy-nlne (379) liters (one hundred gallons~ of tl~e above aqueous sizing composition was prepared according to the following procedure. EPON 880, PLURONICr~' F-10a, IGEPAL CA-630 and di-n-butyl pht}lalate were combined in t}le amounts set forth above al-d }leated to about 60C to about 71~C (about 110F to about 160F) wit}l tl~orough mixing. W}Ien the desired temperature was obtalned, high s}leAr mixing was commenced using an Epp~nbach mixer.
Hot water o about 49C to about 60C (about 120F to about 140F) in about a 2 :1 volumetric rAtio of water to mixture w~ rlowl y added to the mixture to einulsi~y tl~e epoxy resin. The A-174 A-197 and A-1100 silanes were hydrolyzed sequentially in water acidiEied wit}~ acetic acid at a ratio o about 1:10 silane to water by weigllt and added to t}le main mixt~lre. To ~I~is mixt~Ire was added 3.8 liters (l gallon) of hot water of abo~lt ~9~C to about 60rC (about 120F to about 140F) premixed with RMERY 6717 and 75.7 liters (2Q gallolIs) of water premixed wit}l EPI-RF:% CMD W60-5520. The resulting ~q~leo~ls sizing composition had a p~ of about 4 . 5 to about 5. 5 weig}~t percent ~olids .
The sizing composition was applied to ~-17.3 glass fiber strands after conventional cooling and thermal conditioning by air and water sprays using a conventional roller-type applicator. Each forming package was dried at a temperature of about 104C to about 149C (about 220F to about 300F) for about 10-13 }~ours to fornl glass strand having about 0 . 3 to about 2 . 0 weight percent of dried sizing thereon. After drying t}Ie forming packages were mounted on creel and transforl,~ed into roving.
Pultruded composites wer-3 prepared ~Ising an isopht}lalic polyester resin mix aIId an epoxy resin formulatiol- e~cI~ described below, with t}le requir~d number of tows of roving I~avirlg tl~e sizilIg composition of t}le pr~sel~t illventio~ applied tllereto. TIle compoIlellts of t}le isophtl~alic polyester resin mix are set ort~1 iIl TAble 2 alld tlle components of tlle ~poxy resin formulatiol- are set ~ort}I ill Table 3.
AMENDED S~iEr,T
COMPONENT WEIGHT OF COMPONENT (GRAMS) AROPOL 2036 ~Ø 000 ZELEC UN mold release 100 ASP(13 400P ClRy 1800 Eenzoyl Pero:clde initiator 50 PERCADOX 16N il~itiator 50 t-~3utyl Perbenzoate il~itiator 50 Styrene 50 AROPOL 2036 polyeste2: resin formulation (a~ isopi~thalic polyester resin) is colllmercially ~vailable from Ashlalld Chemical Inc.
of Columbus, Ollio. ZELEC UN mol~ release is commercially available from E. I . du Pont de Nemours & Co. of E~1ilmingtoll, Delaware . PERCADOX
16N is a peroxycarl~onate initi~tor commercially available froln AE~ZO
Chemical Inc. of Dobbs Ferry, Ne~ York.
~I~'S L E 3 COMPONENT idEIGHT OF COMPONENT (GRAMS) EPON Resin 9310 11,000 EPON Curing Agerlt 9360 3630 Accelerator 537 73 . 7 INTEL 1850HT mold release 73.7 ASP~ 400P clay 2200 EPON 9310 is an epox~/ resin wilich is commercially available from Shell Chemical. E'PON curing agent 9360, also commercially available from Sl~el]., is a mixed aromatic amine syste modified with a reactive monomer. Accelerator 537 is a cure accelerant commercially available! from Shell Cllemical. INTEL 1350EET
mold release is commercially avai.lable from Axel Plastics Researcl Laboratories .
Tlle processing par~meters for preparing tlle pultr~lded composites are set fol-tl~ in Table 4.
AMENDED SHEET
L 8~ ~5 ~ 3 : . . ' .
~B~
POLYESTER EPOXY
PROCESSING PARI\METER FORMULATION FORMULATION
GLASS CONTENT (WT ~) 70-72 74-76 FIRST PLATEN TEMPERATURE C (F~ 135 (275) 199 (390) SECOND PLATEN TEMPERR~URE C (F) 149 (300) 210 (410) PULL SPEED cnn/min ~ C~ES/MIN) 46 (18) 30 (12) Pultluùed compo~sit~s ~Ising the polyester ~ormulatioll were evaluated to determ~lle i~l-plnne sl~ear strengt~ according to ASTM D-3846 short beam s~ear according to ~STM D-2344 flex~lral s~eAr strength and flexural modulus accordlng to ASTM Met~lod D-790 T~le results of each o t~ese tests are set forth in Table 5 GLASS IN-PLANE S~ORT BEAM FLEXUR~L
CONTENT SHEAR SHEAR SHEAR FLEXURAL
(WEIGHT STRENGTH STRENGTH STRENGTH MODULUS
PERCENT) (ksi) (ksi) (ksi) (ksi) Pultr~lded compo~ite~ ~Ising (1) glass fibers ~nving t~e sizing compositiol~ of t~le ~L~fiellt illvention ~pplied t~ereto (Sample A) or (2) the commerciall~ ~v~ le 712 a~ld 764 rovil~g prod~lcts of PPG Industries Il~c of Pitl ~ L(31l Pennsylvania (Samples B a~d C
respectiveLy) in t~e above l~ol~e~ter and epoxy form~llations were evaluated to determine aveLng~ in-plane shear strengt~l accordil~g to ASTM D-3846 before nnd nftel bei~l3 s~lbjected contill~o~ly for 43 ~lours to boiling water T~le glass content Eor eac~l of t~le samples using the polyester formulatiol~ was 70-72 weight percent T~e glass colltent for each of t~le samples ~lsing t~le epoxy orm~1atioll was 76-77 weight percellt T~le average vnll~es of in-plane sllear strerlgth (derived from multiple r~ s) are presented in Table 6 or samples usil~g tlle polyester formulatio~l nnd Table 7 for samples usillg t~le epoxy formulatioll AMENDED SHEET
~
~R ' -li- -~!;-- S:~} h'ET IN-PLh1~E S:iE~-S-'PE`~GTE (}:s_) STP~ENGT:~ ~}:si~
SA.' ;PLE
E;.~ 3 9 C 6 ~ 5 ., _ _ _ ~
3R~ L~--- S-:_~ 'vt'E~ Il~-PLAN} S:~E~P.
S'~,-~`i~-Tr: 'ks~ ' STP~rNGT:~ (}:s:) S~ 'P_E
C . . C
~ s sn~ r. ~a'~` es 5, 6 ani ~, ;he pul~ruaé._ c~rapcs: ,es prepare~ ~s- n5 s_ass C:be-s c:~a=e h-: .k ;he r;zing com.p~s:~ ~ o- cc _ O
presen_ :rver.~ or e~ ~ b__ r,:S:r :r.--~ane, sho-_ beam a?, d ':e}:~_~a:
shear s~re:lg.i:, as we:: as ;lg~ -'exural mod.:lus ~he p~_l_ruiec composi~es Cormei usln~ coa~ed glass fibers o' the presen~ :nve~ or _. .' e p-',ves-er 'C-m~A- C-- ha~e superior dry and wet :n-~lan~ shear s=reng-r =c ~hose com~s:=es ~-emarec' us;ng conven-:or.a_ ~~a-~~ g:ass ~
- :bers, as r~hOhT _.. Table 6, a~c com:parable performance :.. -h~= ep~
'orm~_~a~-or, as sh~ T. _r~ ~ab~e ~
The ac~ous s:.:ng c~mpo~ lo-. 0c .he rresen_ :r~e ~_o procuces g`'ass ~'~be- s-,-ar~s ra-~ 'gh we_-ou= psr'orma:lcs _c produce composi~es ha-;:~._ g~o- =:ar~ a-c rlgh s=rer.~.; -~ 9=
incorpo~a.ed as reinfo-ces-n-s ~cr =hs~m~se;~i~g pc'~rlsrs It will be a~p~ecla~el b~ those s3~illed in -ho ar- .ka~
changes could be made to the embodiment descrlbed above h~:,hou;
departins from the brcac :nvent:ve concept th~reof I~ is understood, thereCore, ;at tk1s ~n~.~ention 15 not limited to ~he par~icular ~ ~ mAnt àlsc1osec, r,u- ~ t is intended ~o c~ver modlf lcatlons hhich are h ~ =hln =he spirl_ anc scope of th6 ' -vs? _l0r, as def ~ ned by the appende~ clalms AMENDE~ S '---
Claims (24)
1. An aqueous sizing composition for at least one glass fiber for use in reinforcing a thermosetting polymer, the composition comprising:
(a) a non-ionic urethane-modified epoxy thermosetting copolymer;
(b) a water soluble, dispersible or emulsifiable epoxy film-forming polymer;
(c) about 5 to about 25 weight percent of a emulsifying agent on a non-aqueous basis;
(d) an organo functional silane coupling agent;
(e) a fiber lubricant; and (f) water in an amount sufficient for application of the sizing composition to at least one glass fiber.
(a) a non-ionic urethane-modified epoxy thermosetting copolymer;
(b) a water soluble, dispersible or emulsifiable epoxy film-forming polymer;
(c) about 5 to about 25 weight percent of a emulsifying agent on a non-aqueous basis;
(d) an organo functional silane coupling agent;
(e) a fiber lubricant; and (f) water in an amount sufficient for application of the sizing composition to at least one glass fiber.
2. The aqueous sizing composition according to claim 1, wherein the urethane-modified epoxy thermosetting copolymer is present in an aqueous emulsion.
3. The aqueous sizing composition according to claim 1, wherein the urethane-modified epoxy thermosetting copolymer has an epoxide equivalent weight of about 175 to about 760.
4. The aqueous sizing composition according to claim 1, wherein the urethane-modified epoxy thermosetting copolymer is about 10 to about 60 weight percent of the sizing composition on a non-aqueous basis.
5. The aqueous sizing composition according to claim 1, wherein the epoxy film-forming polymer is a reaction product of a halohydrin and a hydroxyl compound.
6. The aqueous sizing composition according to claim 5, wherein the halohydrin is selected from the group consisting of bisphenol A and bisphenol F compounds.
7. The aqueous sizing composition according to claim 5, wherein the hydroxyl compound is selected from the group consisting of a phenol and a polyhydroxy alcohol.
8. The aqueous sizing composition according to claim 5, wherein the epoxy film- forming polymer is selected from the group consisting of an epihalohydrin and a hydroxyl compound, epoxy resin formed from an aliphatic glycidyl ether and an epoxy resin formed from monoepoxy compounds.
9. The aqueous sizing composition according to claim 1, wherein the epoxy film-forming polymer is about 10 to about 55 weight percent of the sizing composition on a non-aqueous basis.
10. The aqueous sizing composition according to claim 1, wherein the ratio on a non-aqueous basis of non-ionic urethane-modified epoxy thermosetting copolymer to epoxy film- forming polymer is about 30:70 to about 80:20 by weight.
11. The aqueous sizing composition according to claim 1, wherein the emulsifying agent is selected from the group consisting of a polyoxyalkylene block copolymer, an ethoxylated alkyl phenol, a polyoxyethylated vegetable oil and mixtures thereof.
12. The aqueous sizing composition according to claim 11, wherein the ratio of the polyoxyalkylene block copolymer to the ethoxylated alkyl phenol is about 1:1 to about 4:1 by weight.
13. The aqueous sizing composition according to claim 1, wherein the organo functional silane coupling agent is selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and mixtures thereof, and the fiber lubricant is selected from the group consisting of an amine salt of a fatty acid, alkyl imidazoline derivative, acid solubilized fatty acid amide and acid solubilized polyunsaturated fatty acid amide.
14. The aqueous sizing composition according to claim 1, wherein the organo functional silane coupling agent comprises about 5 to about 25 weight percent of the sizing composition on a non-aqueous basis.
15. The aqueous sizing composition according to claim 1, wherein the fiber lubricant is about 0.05 to about 0.5 weight percent of the sizing composition on a non-aqueous basis.
16. The aqueous sizing composition according to claim 1, wherein the aqueous sizing composition has a weight percentage of solids of about 1 to about 10.
17. The aqueous sizing composition according to claim 1, further comprising an organic acid to give the aqueous sizing composition a pH of about 3 to about 5.5.
18. The aqueous sizing composition according to claim 1, further comprising a plasticizer selected from the group consisting of a polyethylene glycol, a phthalate, a trimellitate and an adipate.
19. The aqueous sizing composition according to claim 18, wherein the plasticizer is up to about 8 weight percent of the sizing composition on a non-aqueous basis.
20. An aqueous sizing composition for at least one glass fiber for use in reinforcing a thermosetting polymer, the composition comprising: (a) a non-ionic urethane-modified epoxy thermosetting copolymer; (b) a water soluble, dispersible or emulsifiable epoxy film-forming polymer, wherein the ratio on a non-aqueous basis of the urethane-modified epoxy thermosetting copolymer to the epoxy film-forming polymer is about 30:70 to about 80:20 by weight; (c) about 5 to about 25 weight percent on a non-aqueous basis of an emulsifying agent; (d) about 5 to about 35 weight percent on a non-aqueous basis of at least one organo functional silane coupling agent; (e) up to about 8 weight percent on a non-aqueous basis of a plasticizer; (f) about 0.05 to about 0.5 weight percent on a non-aqueous basis of a fiber lubricant; and (g) water in an amount sufficient to give the aqueous sizing composition a weight percentage of solids of about 1 to about 10.
21. A glass fiber having the dried residue of the sizing composition of claim 1.
22. A glass fiber reinforced polymeric article having the glass fiber of claim 21.
23. The glass fiber reinforced polymeric article according to claim 22, wherein the thermosetting polymer which is reinforced is selected from the group consisting of a polyester, vinyl ester and epoxy resin.
24. A method of making a reinforcement for a thermosetting polymer, the reinforcement having improved strength, comprising; (a) applying an aqueous sizing composition to at least a portion of a surface of each of a plurality of glass fibers, the aqueous sizing composition comprising:
(1) a non-ionic urethane-modified epoxy thermosetting copolymer;
(2) a water soluble, dispersible or emulsifiable epoxy film-forming polymer;
(3) about 5 to about 25 weight percent of an emulsifying agent on a non-aqueous basis;
(4) an organo functional silane coupling agent;
(5) a fiber lubricant; and (6) water in an amount sufficient for application of the sizing composition to at least one glass fiber.
(1) a non-ionic urethane-modified epoxy thermosetting copolymer;
(2) a water soluble, dispersible or emulsifiable epoxy film-forming polymer;
(3) about 5 to about 25 weight percent of an emulsifying agent on a non-aqueous basis;
(4) an organo functional silane coupling agent;
(5) a fiber lubricant; and (6) water in an amount sufficient for application of the sizing composition to at least one glass fiber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18696394A | 1994-01-27 | 1994-01-27 | |
| US08/186,963 | 1994-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2181485A1 true CA2181485A1 (en) | 1995-08-03 |
Family
ID=22687026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002181485A Abandoned CA2181485A1 (en) | 1994-01-27 | 1995-01-16 | Glass fiber sizing compositions, sized glass fibers and methods of reinforcing polymeric materials using the same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5605757A (en) |
| EP (1) | EP0741676B1 (en) |
| JP (1) | JPH09508347A (en) |
| CA (1) | CA2181485A1 (en) |
| DE (1) | DE69502699T2 (en) |
| ES (1) | ES2119391T3 (en) |
| WO (1) | WO1995020549A1 (en) |
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| US8129018B2 (en) | 2004-06-18 | 2012-03-06 | Ocv Intellectual Capital, Llc | Sizing for high performance glass fibers and composite materials incorporating same |
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| WO2019083769A1 (en) | 2017-10-27 | 2019-05-02 | Ocv Intellectual Capital, Llc | Sizing compositions including weakly-coordinating anion salts and uses thereof |
| EP3959281A1 (en) * | 2019-04-25 | 2022-03-02 | 3M Innovative Properties Company | Adhesion promoters for structural adhesive applications |
| CN115182200B (en) * | 2022-06-16 | 2023-05-16 | 浙江夏王纸业有限公司 | Controllable-expansion-rate facing raw paper and preparation method thereof |
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-
1994
- 1994-12-20 US US08/359,778 patent/US5605757A/en not_active Expired - Fee Related
-
1995
- 1995-01-16 JP JP7520087A patent/JPH09508347A/en active Pending
- 1995-01-16 WO PCT/US1995/000615 patent/WO1995020549A1/en active IP Right Grant
- 1995-01-16 ES ES95908059T patent/ES2119391T3/en not_active Expired - Lifetime
- 1995-01-16 EP EP95908059A patent/EP0741676B1/en not_active Expired - Lifetime
- 1995-01-16 DE DE69502699T patent/DE69502699T2/en not_active Expired - Fee Related
- 1995-01-16 CA CA002181485A patent/CA2181485A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8129018B2 (en) | 2004-06-18 | 2012-03-06 | Ocv Intellectual Capital, Llc | Sizing for high performance glass fibers and composite materials incorporating same |
Also Published As
| Publication number | Publication date |
|---|---|
| US5605757A (en) | 1997-02-25 |
| DE69502699D1 (en) | 1998-07-02 |
| EP0741676A1 (en) | 1996-11-13 |
| JPH09508347A (en) | 1997-08-26 |
| ES2119391T3 (en) | 1998-10-01 |
| WO1995020549A1 (en) | 1995-08-03 |
| EP0741676B1 (en) | 1998-05-27 |
| DE69502699T2 (en) | 1998-12-17 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |