NO861468L - CHROME-FREE GLASS FIBER BUNTER. - Google Patents
CHROME-FREE GLASS FIBER BUNTER.Info
- Publication number
- NO861468L NO861468L NO861468A NO861468A NO861468L NO 861468 L NO861468 L NO 861468L NO 861468 A NO861468 A NO 861468A NO 861468 A NO861468 A NO 861468A NO 861468 L NO861468 L NO 861468L
- Authority
- NO
- Norway
- Prior art keywords
- approx
- fiberglass
- fibers
- coated
- glass fiber
- Prior art date
Links
- 239000003365 glass fiber Substances 0.000 title claims description 35
- 239000000853 adhesive Substances 0.000 claims description 33
- 230000001070 adhesive effect Effects 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000011152 fibreglass Substances 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 claims 1
- 229920001225 polyester resin Polymers 0.000 claims 1
- 239000004645 polyester resin Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 101100343346 Drosophila melanogaster flz gene Proteins 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Glass Compositions (AREA)
Description
Foreliggende oppfinnelse vedrører feltet limsammensetninger for glassfibrer, og nærmere bestemt for glassfiber "gun roving", heretter betegnet glassfiberbunter, og glassfibrer belagt dermed. The present invention relates to the field of adhesive compositions for glass fibres, and more specifically for glass fiber "gun roving", hereinafter referred to as glass fiber bundles, and glass fibers coated therewith.
Glassfibrer som benyttes om forsterkningselementer i polymer- eller harpiksmatriks-materialer er vanligvis belagt med et limbelegg av svært lav vekt som tjener til å beskytte fibrene fra skade ved abrasjon under bearbeidelse, håndtering og/eller anvendelse, til å binde de individuelle fibrene i mer eller mindre tett integrerte multi-fiberbunter eller kjeder og/eller å forbedre forsterkningsvekselvirkningen mellom fibrene og harpiksmatriksen hvori de er innstøpt som forsterkningselementer. Slike limpreparater påføres ofte på glassfibrene ved tidspunktet for den innledende fremstillingen, som vanligvis foregår ved trekking av et stort antall tråder av smeltet glass fra et reservoar gjennom et i det vesentlige tilsvarende stort antall egnede åpninger, slik at disse trådene reduseres til den ønskede fiberdiameteren når de avkjøles og størkner. Limpreparatet påføres typisk på de individuelle fibrene i produksjons-rekken så snart de er tilstrekkelig avkjølt under størkningstemperaturen, denne avkjølingen kan akselreres ved å fukte de nystørknede, men fremdeles varme, fibrene med vann. Flytende limpreparater påføres i slike situasjoner ved spraying, ved trekking av fibrene over en egnet rull, belte, transportbånd, pute osv. som er fuktet med den flytende limsammensetningen, eller ved andre konvensjonelle væskebeleggings-fremgangsmåter. Etter at det flytende limpreparatet er påført på de individuelle glassfibrene som beveges fremover bringes de typisk sammen mens de fremdeles i det minste delvis er våte med det flytende limpreparatet i én eller flere multi-fiberbunter eller kjeder, som kan samles i en egnet forpakning for videre bearbeidelse, lagring og/eller for-sendelse, som f.eks. ved oppvikling på en roterende krave. De våte fibrene eller kjedene tørkes normalt før og/eller etter slik samling, for å avsette den ikke-flyktige resten av det flytende limpreparatet på overflatene av fibrene. Glass fibers used for reinforcing elements in polymer or resin matrix materials are usually coated with a very light weight adhesive coating which serves to protect the fibers from abrasion damage during processing, handling and/or use, to bond the individual fibers in more or less tightly integrated multi-fiber bundles or chains and/or to improve the reinforcing interaction between the fibers and the resin matrix in which they are embedded as reinforcing elements. Such adhesive preparations are often applied to the glass fibers at the time of initial manufacture, which is usually accomplished by drawing a large number of strands of molten glass from a reservoir through a substantially correspondingly large number of suitable openings, so that these strands are reduced to the desired fiber diameter when they cool and solidify. The adhesive preparation is typically applied to the individual fibers in the production line as soon as they have cooled sufficiently below the solidification temperature, this cooling can be accelerated by wetting the newly solidified, but still warm, fibers with water. Liquid adhesive preparations are applied in such situations by spraying, by pulling the fibers over a suitable roll, belt, conveyor belt, pad, etc., which is moistened with the liquid adhesive composition, or by other conventional liquid coating methods. After the liquid adhesive composition is applied to the individual glass fibers being moved forward, they are typically brought together while still at least partially wet with the liquid adhesive composition into one or more multi-fiber bundles or chains, which can be collected in a suitable package for further processing, storage and/or dispatch, such as e.g. by winding on a rotating collar. The wet fibers or chains are normally dried before and/or after such assembly, to deposit the non-volatile residue of the liquid adhesive composition on the surfaces of the fibers.
Flytende limpreparater som er egnede for slik påføring på glassfibrer er ordninært fortynnede oppløsinger, dispersjoner og/eller emulsjoner, og ofte i vandige media, av en film-dannende polymer eller harpiks, et smøremiddel og et koblingsmiddel. Andre komponenter, så som anti- statiske midler (spesielt der hvor de limte glassfibrene skal opphakkes til korte lengder mens de er tørre), emulgeringsmidler eller oppløselig - gjørende midler, viskositetsmodifiserende midler osv., har også i noen tilfeller vært inkorporert i slike flytende limpreparater. Liquid adhesive preparations which are suitable for such application to glass fibers are ordinarily dilute solutions, dispersions and/or emulsions, and often in aqueous media, of a film-forming polymer or resin, a lubricant and a coupling agent. Other components, such as antistatic agents (especially where the glued glass fibers are to be chopped into short lengths while they are dry), emulsifiers or solubilizing agents, viscosity modifying agents, etc., have also in some cases been incorporated into such liquid adhesive preparations .
En av anvendelsene for glassfibrer er som bunter, som ønskelig består av et stort antall kontinuerlige kjeder svakt bundet sammen, hvor hver kjede består av et stort antall individuelle glassfibrer som er sterkt sammenbundet ved hjelp av limbelegget på fibrene. Slike bunter anvendes ved at de tilføres gjennom en egnet hakke-innretning inkorporert i eller nært koblet med en egnet dyse for spraying av et flytende harpikspreparat sammen med den opphakkede bunten på en form eller et annet egnet mål, slik at den hakkede bunten eller stykkene av kjeder separert fra denne, blir innstøpt i den flytende harpiksen, som deretter størknes ved avkjøling og/eller ved herding ved kjemisk reaksjon. Eksempel på utstyr og tilsvarende fremgangsmåter for slik anvendelse av glassfibrer i glassfiberbunter er beskrevet i U.S patent nr. 3,111,440 med tittelen "Devices and Methods for applying Strands", utstedt 19. november 1963, for en oppfinnelse av William H. Prentice. Typisk har de opphakkede stykkene en lengde fra ca. 1,27 cm til ca. 5,08 cm. One of the uses for glass fibers is as bundles, which preferably consist of a large number of continuous chains loosely bound together, where each chain consists of a large number of individual glass fibers strongly bound together by means of the adhesive coating on the fibers. Such bundles are used by feeding them through a suitable chopping device incorporated in or intimately connected with a suitable nozzle for spraying a liquid resin preparation together with the chopped bundle onto a mold or other suitable target, so that the chopped bundle or pieces of chains separated from this, are embedded in the liquid resin, which then solidifies by cooling and/or by hardening by chemical reaction. Examples of equipment and corresponding methods for such application of glass fibers in glass fiber bundles are described in U.S. Patent No. 3,111,440 entitled "Devices and Methods for applying Strands", issued November 19, 1963, for an invention by William H. Prentice. Typically, the chopped pieces have a length of approx. 1.27 cm to approx. 5.08 cm.
Glassfiberbunter har hittil blitt belagt med flytende limpreparater inneholdende kromkomplekser av Werner-typen, så som metylakrylat og kromklorid, som antas å fungere i det minste delvis som et glass-harpiks-koblingsmiddel, selv om slike kromkomplekser i noen tilfeller har vært benyttet sammen med konvensjonelle organosilanglass-harpikskoblings-midler. Før foreliggende oppfinnelse var det ikke ansett som mulig å oppnå en tilfredsstillende balanse av ønskelige egenskaper i glassfiberbunter uten innbefatning av et kromkompleks i limpreparatet for de oppbygende fibrene derav, og spesielt å oppnå en ønsket letthet og fullstendighet av opphakkingen i konvensjonelt utstyr, samtidig som man også oppnår den ønskelige raske og fullstendige fuktningen av den opphakkede forsterkningen ved hjelp av den flytende matriksharpiks-sammensetningen og å tilveiebringe en forønsket forbedring av de fysikalske egenskapene for harpiksmatriksen, samtidig som dannelsen av fnugg, fra brekkasje av fibrer under bearbeidelsen av den kontinuerlige kjeden eller bunten, og "støv", dvs. statisk-dispergerte stykker av opphakket buntkjede eller delvis eller fullstendig fibrilerte rester derav som ledsager opphakkingen og sprayingen ved dysen, holdes på et ønsket lavt nivå. Fiberglass bundles have heretofore been coated with liquid adhesives containing Werner-type chromium complexes, such as methyl acrylate and chromium chloride, which are believed to function at least in part as a glass-resin coupling agent, although such chromium complexes have in some cases been used in conjunction with conventional organosilane glass-resin coupling agents. Prior to the present invention, it was not considered possible to achieve a satisfactory balance of desirable properties in glass fiber bundles without the inclusion of a chromium complex in the adhesive preparation for the building fibers thereof, and in particular to achieve a desired lightness and completeness of chopping in conventional equipment, while at the same time also achieves the desired rapid and complete wetting of the chopped reinforcement by means of the liquid matrix resin composition and to provide a desired improvement in the physical properties of the resin matrix, at the same time as the formation of fluff, from the breakage of fibers during the processing of the continuous chain or the bundle, and "dust", i.e., statically-dispersed pieces of chopped bundle chain or partially or fully fibrillated remnants thereof which accompany the chopping and spraying at the nozzle, are kept at a desired low level.
Et i det vesentlige kromfritt, vandig limpreparat for glassfiberbunt som innbefatter (A) en blanding av emulgerte film-dannede polymerer innbefattende en polymer av vinylacetat og etylen, en polymer av vinylacetat og en epoksy-funksjonell vinylmonomer, og en umettet polyesterharpiks; (B) titanacetylacetonat; (C) et silylert polyamino-polyamidhydroklorid eller hydrolysat derav; (D) et kationisk smøremiddel; og (E) 3-metakryloksypropyltrimetoksysilan eller hydrolysat derav. A substantially chromium-free aqueous glass fiber bundle adhesive composition comprising (A) a mixture of emulsified film-forming polymers including a polymer of vinyl acetate and ethylene, a polymer of vinyl acetate and an epoxy-functional vinyl monomer, and an unsaturated polyester resin; (B) titanium acetylacetonate; (C) a silylated polyamino-polyamide hydrochloride or hydrolyzate thereof; (D) a cationic lubricant; and (E) 3-methacryloxypropyltrimethoxysilane or hydrolyzate thereof.
De emulgerte filmdannende polymerkomponentene ifølge foreliggende oppfinnelse kan være hvilke som helst av emulgerte polymerer av de aktuelle typene som vil vokse sammen slik at det dannes koherente filmer, og som fortrinnsvis vil vokse sammen på dennen måten ved normale romtemperaturer. En liten mengde av egnede myknere for å fremme slik smmenvoksning, hvorav mange er kjente og tilgjengelige, kan blandes eller ko-emulgeres med én eller flere av polymerene, om ønsket, men det er vanligvis mulig og foretrukket å velge polymerer som ikke krever slike additiver for å vise de fordelaktige egenskapene ved bruk, slik at denne til sist reagerer med denne umettede polyesteren og med en umettet polyester-matriksharpiks, slik at glassfibrene bindes nærmere til hverandre og til matriksen hvori de er innstøpt som forsterkningselementer. The emulsified film-forming polymer components according to the present invention can be any of the emulsified polymers of the relevant types which will grow together so that coherent films are formed, and which will preferably grow together in this way at normal room temperatures. A small amount of suitable plasticizers to promote such intergrowth, many of which are known and available, may be mixed or co-emulsified with one or more of the polymers, if desired, but it is usually possible and preferred to select polymers that do not require such additives to show the beneficial properties in use, so that it finally reacts with this unsaturated polyester and with an unsaturated polyester matrix resin, so that the glass fibers are bonded more closely to each other and to the matrix in which they are embedded as reinforcing elements.
En spesielt velegnet, emulgert polymer av vinylacetat og etylen er tilgjengelig som "Airflex 410" (varemerke/Air Products and Chemicals Co.), en vandig emulsjon inneholdende ca. 55 vekt-% ikke-flyktige komponenter innbefattende en vinylacetat-etylen kopolymer som har en glassovergangstemperatur på ca. 2°C, ikke-ionisk emulgert som partikler med gjennomsnittlig diameter på ca. 0,3 pm. A particularly suitable emulsified polymer of vinyl acetate and ethylene is available as "Airflex 410" (trademark/Air Products and Chemicals Co.), an aqueous emulsion containing approx. 55% by weight non-volatile components including a vinyl acetate-ethylene copolymer having a glass transition temperature of approx. 2°C, non-ionic emulsified as particles with an average diameter of approx. 0.3 pm.
En spesielt velegent, emulgert polymer av vinylacetat og en epoksy-funksjonell vinylmonomer er tilgjengelig som "Resyn 25-1971" (vare-merke/National Starch and Chemical Corp.), en vandig emulsjon inneholdende ca. 54,5±1 vekt-% ikke-flyktige bestanddeler innbefattende en kopolymer av vinylacetat ca. 2 vekt-% glysidylmetacrylat ikke-ionisk emulgert. A particularly suitable emulsified polymer of vinyl acetate and an epoxy-functional vinyl monomer is available as "Resyn 25-1971" (trademark/National Starch and Chemical Corp.), an aqueous emulsion containing approx. 54.5±1% by weight non-volatile components including a copolymer of vinyl acetate approx. 2% by weight glycidyl methacrylate non-ionic emulsified.
En spesielt velegnet, umettet polyesterharpiks er tilgjengelig som "MR70C" (varemerke/United States Steel Corp.), en ca. 60:40 vekt-blanding av en umettet polyester og dialylftalat, en latent reaktiv mykner, som var ikke-ionisk emulgert, slik at det ble dannet en vandig emulsjon inneholdende ca. 59 vekt-% ikke-flyktige bestanddeler og betegnet "PE-700". A particularly suitable unsaturated polyester resin is available as "MR70C" (trademark/United States Steel Corp.), an approx. 60:40 weight mixture of an unsaturated polyester and diallyl phthalate, a latently reactive plasticizer, which was non-ionic emulsified to form an aqueous emulsion containing approx. 59% by weight non-volatile components and designated "PE-700".
Et spesielt velegnet titanacetylacetonat er tilgjengelig som "Tyzor AA" A particularly suitable titanium acetylacetonate is available as "Tyzor AA"
(varemerke/E.I. duPont de Nemours, Inc.), en 75 vekt-% oppløsning eller dispersjon av bis(2,4-pentandionat-0,0')bis(2-propanolato)titan i isopropanol. (trademark/E.I. duPont de Nemours, Inc.), a 75% by weight solution or dispersion of bis(2,4-pentanedionate-0,0')bis(2-propanolato)titanium in isopropanol.
Et spesielt velegnet, silylert polyamino-polyamid-hydroklorid er tilgjengelig som "Y-9567" (varemerke/Union Carbide Corp.), en 80 vekt-% dispersjon eller oppløsning i metanol av et saltsyresalt av A particularly suitable silylated polyamino-polyamide hydrochloride is available as "Y-9567" (trademark/Union Carbide Corp.), an 80% by weight dispersion or solution in methanol of a hydrochloric acid salt of
hvor x + y er et tall fra ca. 3 til ca. 10. Slike materialer og deres fremstilling er beskrevet i detalj i U.S. patent nr. 3,746,738 med tittelen "Silicon Coantaining Polyazimids" utstedt 17. juli 1973 for en oppfinnelse av Enrico J. Pepe og James G. Marsden. where x + y is a number from approx. 3 to approx. 10. Such materials and their manufacture are described in detail in U.S. Pat. patent No. 3,746,738 entitled "Silicon Containing Polyazimids" issued on July 17, 1973 for an invention by Enrico J. Pepe and James G. Marsden.
Et spesielt velegnet, kationisk smøremiddel er et svakt syresalt av et delvis fettaktig amid av et polyamim så som "Emer 6760 U" (vare-merke/Emery Industries, Inc.), en 65 vekt-% vandig oppløsning eller dispersjon av et eddiksyresalt av et partielt amid av blandede fettsyrer som inneholder ca. 6 til 8 karbonatomer med et polyetylenamin. Det samme materialet finnes også tilgjengelig ufortynnet som "Emery 6717". A particularly suitable cationic lubricant is a weak acid salt of a partially fatty amide of a polyamide such as "Emer 6760 U" (trademark/Emery Industries, Inc.), a 65% by weight aqueous solution or dispersion of an acetic acid salt of a partial amide of mixed fatty acids containing approx. 6 to 8 carbon atoms with a polyethyleneamine. The same material is also available undiluted as "Emery 6717".
Et spesielt velegnet 3-metakryloksypropyltrimetoksysilan er tilgjengelig i blanding med en varmemerkeregistrert stabilisator som "A-174" (vare- merke/Union Carbiode Corp.). Silanet er fortrinnsvis hydrolysert i fortynnet vandig, svak syre før anvendelse. A particularly suitable 3-methacryloxypropyltrimethoxysilane is available in admixture with a heat-brand registered stabilizer such as "A-174" (trademark/Union Carbiode Corp.). The silane is preferably hydrolysed in dilute aqueous, weak acid before use.
Selv om andelene av de forskjellige komponentene av det vandige limpreparatet ifølge oppfinnelsen ikke er trangt kritiske, er det foretrukket at de ligger innenfor følgende områder: Although the proportions of the various components of the aqueous adhesive preparation according to the invention are not narrowly critical, it is preferred that they lie within the following ranges:
Andre komponenter kan, om ønsket, innbefattes, men for å sikre at fordelene ved oppfinnelsen realiseres er det foretrukket at andre komponenter utelates med mindre det finnes at ingen betydelig reduksjon av disse fordelene oppstår ved denne innbefatningen. Siden spesielt et viktig formål ved oppfinnelsen er å tilveiebringe et kromfritt limpreparat for glassfiberbunter, bør ingen kromforbindelser eller komplekser innbefattes i limpreparatene ifølge oppfinnelsen. Siden imidlertid noen av komponentene, f.eks. titanacetylacetonatet, det silylerte polyamino-polyamidet og det kationiske smøremiddelet oppløseliggjøres ved syrer og/eller lavere alkoholer, kan innbefatningen av mindre mengder alkoholer så som metanol, etanol, propanol, isopropanol, osv. og/eller syrer så som saltsyre eller eddiksyre, finnes ønskelig. Other components can, if desired, be included, but in order to ensure that the advantages of the invention are realized, it is preferred that other components are omitted unless it is found that no significant reduction of these advantages occurs from this inclusion. Since a particularly important purpose of the invention is to provide a chrome-free adhesive preparation for glass fiber bundles, no chromium compounds or complexes should be included in the adhesive preparations according to the invention. However, since some of the components, e.g. titanium acetylacetonate, the silylated polyamino-polyamide and the cationic lubricant are made soluble by acids and/or lower alcohols, the inclusion of smaller amounts of alcohols such as methanol, ethanol, propanol, isopropanol, etc. and/or acids such as hydrochloric acid or acetic acid may be found desirable .
De vandige limpreparatene ifølge oppfinnelsen kan fremstilles ved å følge generelt aksepterte blandefremgangsmåter. Disse limpreparatene kan påføres på glassfibrene ved å benytte en hvilken som helst egnet frem-gangsmåte. Mengden av vandig limpreparat som påføres er ikke strengt kritisk, men er fortrinnsvis kontrollert slik at det på glassfibrene avsettes et limbelegg innbefattende den in situ tørkede resten av det vandige limpreparatet ifølge oppfinnelsen i en mengde fra ca. 0,5 til ca. 2 vekt-% av glasset, tatt i betraktning fortynningen av de ikke-flyktige komponentene i det vandige limpreparatet og det vanlige mekaniske tapet av noe av det vandige preparatet som først påføres på fibrene før det tørkes på disse. The aqueous adhesive preparations according to the invention can be prepared by following generally accepted mixing methods. These adhesive preparations can be applied to the glass fibers using any suitable method. The amount of aqueous adhesive preparation that is applied is not strictly critical, but is preferably controlled so that an adhesive coating including the in situ dried residue of the aqueous adhesive preparation according to the invention is deposited on the glass fibers in an amount from approx. 0.5 to approx. 2% by weight of the glass, taking into account the dilution of the non-volatile components in the aqueous adhesive composition and the usual mechanical loss of some of the aqueous composition which is first applied to the fibers before drying thereon.
Fortrinnsvis påføres det vandige limpreparatet på glassfibrene ettersom de fremstilles ved kontinuerlig trekking fra smeiten. Selv om det vandige limpreparatet på fibrene kan være i det minste delvis tørket før samlig i en forpakning, er det fullstendig tilfredsstillende å samle de våte fibrene til kjeder, fortrinnsvis med ca. 100 til ca. 300, og mer fortrinnsvis 200 individuelle fibrer i hver kjede, samle disse kjedene i forpakninger, f.eks. ved å rulle dem opp på en krage, som også tilveiebringer spenning for trekking av fibrene, og deretter oppvarme pakken i en konvensjonell, sirkulerende varmluftsovn for å drive av flyktige materialer og avsette de ikke-flyktige komponentene av limpreparatet som et limbelegg på fibrene som også vil binde de individuelle fibrene sammen i en tett sammenhengende kjede. Preferably, the aqueous adhesive preparation is applied to the glass fibers as they are produced by continuous drawing from the melt. Although the aqueous adhesive composition on the fibers may be at least partially dried before assembly into a package, it is perfectly satisfactory to assemble the wet fibers into chains, preferably with approx. 100 to approx. 300, and more preferably 200 individual fibers in each chain, collect these chains in bundles, e.g. by rolling them up on a collar, which also provides tension for pulling the fibers, and then heating the package in a conventional circulating hot air oven to drive off volatile materials and deposit the non-volatile components of the adhesive composition as an adhesive coating on the fibers which also will bind the individual fibers together in a tightly connected chain.
De intergrerte kontinuerlige glassfiberkjedene kan buntes sammen i svakt sammenhengende bunter, fortrinnsvis bestående av ca. 30 til ca. 70 kjeder hver, slik at det dannes en kontinuerlig glassfiberbunt. Selv om diameteren av de individuelle glassfibrene ikke er trangt kritisk, er diametre fra ca. 10 pm til ca. 13 pm foretrukket. The integrated continuous fiberglass chains can be bundled together in loosely connected bundles, preferably consisting of approx. 30 to approx. 70 chains each, so that a continuous fiberglass bundle is formed. Although the diameter of the individual glass fibers is not narrowly critical, diameters from approx. 10 pm to approx. 1 pm preferred.
Eksempel 1Example 1
Spesielt fordelaktige krom-frie, vandige limpreparater for glassfiberbunter, representative for foreliggende oppfinnelse, ble fremstilt med følgende sammensetninger: Particularly advantageous chrome-free, aqueous adhesive preparations for glass fiber bundles, representative of the present invention, were prepared with the following compositions:
Begge sammensetningene A og B hadde et innhold av ikke-flyktige bestanddeler på ca. 6,0±0,5 vekt-% og en pH på ca. 3,8 til 4,9. Both compositions A and B had a content of non-volatile components of approx. 6.0±0.5% by weight and a pH of approx. 3.8 to 4.9.
Disse preparatene ble påført på både H-fibrer (ca. 10,1 til ca. 11,4 pm i diameter) og J-fibrer (ca. 11,4 til ca. 12,7 pm diamter) med en konvensjonell applikator etter som de ble trukket fra smeiten, de våte fibrene ble samlet til kjeder på ca. 200 individuelle fibrer og oppvunnet i forpakninger på en roterende krage i grupper på 4 kjeder. Forpakningene ble tørket i en konvensjonell sirkulerende varmluftsovn, holdt ved ca. 130°C i ca. 12-14 timer, avhengig av størrelsen på forpakningen. Det tørkede limbelegget som derved var avsatt på glassfibrene utgjorde ca. 1,0 til ca. 1,3 vekt-% av glasset og bandt kjedene tett sammen. Kjedene fra 13 forpakninger av hver type av H-fibrer og 11 forpakninger av hver type av J-fibrer ble sammenbundet separat til svakt sammenhengende bunter ved hjelp av konvensjonelle fremgangsmåter. These compositions were applied to both H fibers (about 10.1 to about 11.4 µm in diameter) and J fibers (about 11.4 to about 12.7 µm in diameter) with a conventional applicator according to they were pulled from the smelter, the wet fibers were collected into chains of approx. 200 individual fibers and wound in packages on a rotating collar in groups of 4 chains. The packages were dried in a conventional circulating hot air oven, kept at approx. 130°C for approx. 12-14 hours, depending on the size of the package. The dried adhesive coating that was thereby deposited on the glass fibers amounted to approx. 1.0 to approx. 1.3% by weight of the glass and bound the chains tightly together. The chains from 13 bundles of each type of H-fibers and 11 bundles of each type of J-fibers were tied together separately into loosely connected bundles by conventional methods.
De slik fremstilte glassfiberbuntene ble funnet å vise eksepsjonelt fordelaktige kombinasjoner av egenskaper, spesielt tatt i betraktning at limpreparatene var kromfrie. Følgelig ble de funnet å opphakkes lett og rent, og gi fordelaktige lave nivåer av fnugg og støv, og utfuktes raskt og fullstendig med konvensjonelle, umettede polyestermatrikser (H-fiberbunten var spesielt nyttig med ufylte matrikssystemer og J-fiber-bunten med mer viskøse fylte matriksharpikssystemer, hvorav begge kan fortykkes kjemisk om ønsket). De tørkede kjedene kunne avvikles fritt fra forpakningene under buntingen med liten eller ingen nedbrytning av kjedene, og kjedene var tilstrekkelig sammenhengende ved buntingen, slik at etterherding av limbelegget etter bunting ikke var påkrevet, men ved opphakking og spraying ved dysen separerte bitene av bunten til stykker av kjeder som opprettholdt god inegritet. The glass fiber bundles thus produced were found to exhibit exceptionally advantageous combinations of properties, especially considering that the adhesive preparations were chromium-free. Consequently, they were found to chop easily and cleanly, yielding advantageously low levels of lint and dust, and wet quickly and completely with conventional unsaturated polyester matrices (the H fiber bundle was particularly useful with unfilled matrix systems and the J fiber bundle with more viscous filled matrix resin systems, both of which can be chemically thickened if desired). The dried chains could be unwound freely from the packages during bundling with little or no degradation of the chains, and the chains were sufficiently cohesive at the time of bundling, so that post-curing of the adhesive coating after bundling was not required, but when chopping and spraying at the nozzle, the pieces of the bundle separated into pieces of chains that maintained good integrity.
De umettede polyesterharpiks-laminatene dannet med disse buntene viste utmerket strekkstyrke og modul, bøyningsstyrke og modul både tørt og etter neddykking i kokende vann i 24 timer, støtstyrke og andre ønskelige egenskaper. The unsaturated polyester resin laminates formed with these bundles exhibited excellent tensile strength and modulus, flexural strength and modulus both dry and after immersion in boiling water for 24 hours, impact strength and other desirable properties.
Tallrike variasjoner og modifikasjoner av oppfinnelsen som spesielt er beskrevet heri vil fremgå for fagmannen, og slike variasjoner og modifikajsoner er omfattet av foreliggende oppfinnelse. Numerous variations and modifications of the invention which are particularly described herein will be apparent to the person skilled in the art, and such variations and modifications are covered by the present invention.
Oppfinnelsen som er beskrevet i det foregående kan lett anvendes innenfor glassfiberindustrien. The invention described above can easily be used within the glass fiber industry.
Claims (14)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1984/001525 WO1986001811A1 (en) | 1984-09-24 | 1984-09-24 | Chrome-free sizing for glass fiber gun roving |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO861468L true NO861468L (en) | 1986-04-15 |
Family
ID=22182268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO861468A NO861468L (en) | 1984-09-24 | 1986-04-15 | CHROME-FREE GLASS FIBER BUNTER. |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS62500242A (en) |
| FI (1) | FI861152A (en) |
| GB (1) | GB2177407B (en) |
| NO (1) | NO861468L (en) |
| SE (1) | SE8602166D0 (en) |
| WO (1) | WO1986001811A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649599B2 (en) * | 1988-12-12 | 1994-06-29 | ピーピージー・インダストリーズ・インコーポレーテッド | Heat-stable chemically treated glass fiber |
| WO2001049628A1 (en) * | 2000-01-05 | 2001-07-12 | Owens Corning | Catalytically polymerized fiber-reinforced composites |
| US6890650B2 (en) | 2002-07-23 | 2005-05-10 | Ppg Industries Ohio, Inc. | Glass fiber sizing compositions, sized glass fibers, and polyolefin composites |
| US7169463B2 (en) * | 2004-06-21 | 2007-01-30 | Owens Corning Fiberglas Technology, Inc. | Sizing composition for sheet molding compound roving |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3754971A (en) * | 1968-09-12 | 1973-08-28 | Union Carbide Corp | Urea silicon product and uses thereof |
| US3802953A (en) * | 1970-12-16 | 1974-04-09 | Owens Corning Fiberglass Corp | Glass fibers treated with alkaline compatible chromic complexes and reinforced elastomers produced therefrom |
| US3933711A (en) * | 1972-10-31 | 1976-01-20 | Ppg Industries, Inc. | Forming size of aqueous polyvinylacetate |
| US3968068A (en) * | 1974-06-07 | 1976-07-06 | Owens-Corning Fiberglas Corporation | Glass sizing |
| ZA766854B (en) * | 1975-12-31 | 1977-10-26 | Owens Corning Fiberglass Corp | Sizing for glass fibers |
| US4178412A (en) * | 1976-12-20 | 1979-12-11 | Owens-Corning Fiberglas Corporation | Glass size compositions and glass fibers coated therewith |
| FR2377982A1 (en) * | 1977-01-19 | 1978-08-18 | Saint Gobain | COMPOSITIONS FOR COATING FIBERS OF GLASS AND FIBERS SO OBTAINED |
| US4291136A (en) * | 1978-03-31 | 1981-09-22 | Union Carbide Corporation | Water-curable silane modified alkylene alkylacrylate copolymer and a process for its production |
| US4233809A (en) * | 1978-12-20 | 1980-11-18 | Ppg Industries, Inc. | Size composition for glass fibers |
| US4341877A (en) * | 1980-06-04 | 1982-07-27 | Ppg Industries, Inc. | Sizing composition and sized glass fibers and process |
| US4338233A (en) * | 1981-06-15 | 1982-07-06 | Ppg Industries, Inc. | Aqueous sizing composition and sized glass fibers and method |
-
1984
- 1984-09-24 JP JP50362884A patent/JPS62500242A/en active Pending
- 1984-09-24 WO PCT/US1984/001525 patent/WO1986001811A1/en active Application Filing
- 1984-09-24 GB GB08606702A patent/GB2177407B/en not_active Expired
-
1986
- 1986-03-19 FI FI861152A patent/FI861152A/en not_active Application Discontinuation
- 1986-04-15 NO NO861468A patent/NO861468L/en unknown
- 1986-05-13 SE SE8602166A patent/SE8602166D0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| GB2177407B (en) | 1987-10-28 |
| GB8606702D0 (en) | 1986-04-23 |
| WO1986001811A1 (en) | 1986-03-27 |
| SE8602166L (en) | 1986-05-13 |
| FI861152A0 (en) | 1986-03-19 |
| FI861152A (en) | 1986-03-25 |
| JPS62500242A (en) | 1987-01-29 |
| SE8602166D0 (en) | 1986-05-13 |
| GB2177407A (en) | 1987-01-21 |
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