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
  • C03C25/40—Organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
  • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres

Definitions

• the present invention relates to sizing compositions, sized glass fibers and their use.
• compositions of water, polymeric binders (the so-called film formers), adhesion promoters, lubricants, antistatic agents and other auxiliaries are used as sizes.
• Organic, water-dispersible or soluble polyvinyl acetate, polyester, polyester epoxy, polyurethane, polyacrylate, polyolefin resins or mixtures thereof are generally used as binders.
• film formers and adhesion promoters are selected such that there is an affinity between the polymer matrix and the film formers and / or adhesion promoters located on the glass fiber surface, and so a mechanical bond between glass fiber and polymer matrix is produced.
• This process is particularly characterized by its economical production method.
• the object of the present invention was therefore to provide glass fibers which, regardless of the method for producing cut glass fibers, have equally good properties, in particular mechanical and thermal properties, in the polymer composite.
• the properties of the glass fibers produced in the polymer composite using the “direct chop method” should not be worse than the properties of the glass fibers produced in the polymer composite using the “chopped strand method”.
• the invention relates to size compositions for glass fibers with a pH between 3 and 10 consisting of a) 0.1 to 20% by weight, preferably 4 to 10% by weight, of polyepoxide, polyether, polyolefin, polyvinyl acetate, polyacrylate or polyurethane resins or mixtures thereof as film formers,
• silane- compounds with more than one alkoxysilane group per molecule with one, two or three alkoxy groups per silane (alkoxy is preferably C j -Cg- alkoxy and C 5 -C cycloalkoxy Q) and an average Molecular weight of> 500 g / mol,
• the ratio of component b) to component c) is preferably 2: 1.
• the pH of the size is preferably adjusted to pH 5-9.
• a pH of 7 is particularly preferred.
• the customary organic or inorganic acids or bases can be used to adjust the pH.
• Formic acid is preferably used as the acid.
• the use of oligomeric alkoxysilanes is described, for example, in US 3746738 (Union Carbide, Pepe et al.) For glass laminates and in US 4244844 (Saint-Gobain, Molinier et al.) Specifically for textiles in starch-containing size compositions which, owing to the conditional thermal properties, differ from Starch is generally not for processing thermoplastics at processing temperatures
• Another subject of the invention is sized glass fibers which are coated with the dried residue of the size compositions according to the invention.
• the sized glass fibers according to the invention are used to reinforce thermoplastic and thermosetting polymers.
• E-glass fibers are of the greatest importance for the reinforcement of plastics due to their freedom from alkali, their high tensile strength and their high elastic modulus.
• the size can contain further components such as emulsifiers, further film-forming resins, further adhesion promoters, lubricants, pH buffer substances and auxiliaries such as wetting agents or antistatic agents.
• the glass fibers can be sized using any method, for example with the aid of suitable devices, such as spray or roller applicators. Sizing can be applied to the glass filaments drawn from the spinnerets at high speed, for example, immediately after they have solidified, ie before winding or cutting. But it is also possible to use the fibers in the
• Water-dispersed, emulsified or water-soluble epoxy resins are suitable as polyepoxide film formers. These are unmodified or modified by amines, acidic groups or hydrophilic nonionic groups based on diglycidyl ethers of dihydric phenols such as pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyldimethylmethane (bisphenol A), 4,4'-dihydroxy -3, 3 '-dimethyl-diphenylpropane, 4,4' -dihydroxydiphenylsulfone,
• Glycidyl ethers of dibasic, aromatic, aliphatic and cycloaliphatic carboxylic acids such as, for example, phthalic anhydride bisglycidyl ether or adipic acid bisglycidyl ethers, glycidyl ethers of dibasic, aliphatic alcohols such as butanediol bisglycidyl ether, hexanediol bisglycidyl ether or polyoxyalkylene glycols of poly (bis) alkylene glycol or polyoxyalkylene glycols such as poly (bis) alkylene glycols in particular formaldehyde, in the presence of acidic catalysts), tris (4-hydroxyphenyl) methane or l, l, 2,2-tetra (4-hydroxyphenyl) ethane, epoxy compounds based on aromatic amines and epichlorohydrin, for example from Glycerin, trimethylolpropane, pentaerythri
• Suitable chemical modifications are, for example, the addition of amines or the addition of hydrophilic polyethers, for example polyethylene glycols.
• Suitable polyepoxide dispersions are described, for example, in EP-A 27 942, EP-A 31 1 894, US 3,249,412, US 3,449,281, US 3,997,306 and US 4,487,797.
• Polyester epoxides based on bisphenol A and novolaks which are dispersed, emulsified or dissolved in water are preferred.
• Polyurethane film formers are reaction products dispersed, emulsified or dissolved in water of preferably difunctional polyisocyanates with preferably difunctional polyols and optionally preferably difunctional polyamines.
• the synthesis of polyurethane dispersions, usable building blocks, the production process and their properties are known to the person skilled in the art and are described, for example, in
• Suitable isocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates or any mixtures of these polyisocyanates, such as e.g. 1,6-hexamethylene diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-tolylene diisocyanate, diphenylmethane 2,4'- and / or -4,4 ' -diisocyanate.
• 1,6-hexamethylene diisocyanate l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane
• 2,4- and 2,6-tolylene diisocyanate diphenylmethane 2,4'- and / or -4,4 ' -diisocyanate.
• Suitable polyols are polyesters, e.g. Reaction products of preferably dihydric polyalcohols such as e.g. Ethylene glycol, propylene glycol, butylene glycol and hexanediol with preferably dibasic polycarboxylic acids or their esterifiable derivatives such as e.g. Succinic acid, adipic acid, phthalic acid, phthalic anhydride, maleic acid and maleic anhydride. Lactone polyester, e.g. ⁇ -caprolactam can be used. Polyesters can also contain trivalent alcohols or carboxylic acid components such as e.g. Trimethylolpropane or glycerin included.
• dihydric polyalcohols such as e.g. Ethylene glycol, propylene glycol, butylene glycol and hexanediol with preferably dibasic polycarboxylic acids or their esterifiable derivatives such as e.g
• Branched or unbranched polyethers are also suitable, e.g. by polymerizing epoxides such as e.g. Ethylene oxide, propylene oxide or tetrahydrofuran with itself or by attachment of the epoxides to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines.
• epoxides such as e.g. Ethylene oxide, propylene oxide or tetrahydrofuran with itself or by attachment of the epoxides to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines.
• chain extenders ie preferably difunctional polyols or polyamines with a molecular weight of less than 400
• dihydric polyalcohols such as ethylene glycol, propylene glycol, butyl alcohol are particularly preferred.
• lenglycol, amino alcohols such as ethanolamine, N-methyldiethanolamine and functional polyamines such as ethylene diamine, 1,4-tetramethylene diamine, hexamefhylene diamine, l-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, bis (3-aminopropyl) methylamine and hydrazine used.
• Polyurethane dispersions, emulsions or solutions containing epoxy groups or blocked isocyanate groups are also suitable.
• Polyester dispersions are preferably reaction products from the aforementioned polyepoxides with the aforementioned polycarboxylic acids or polyesters containing carboxyl groups (see, for example, EP-A 27 942), which no longer contain epoxy groups.
• Suitable monomeric organofunctional silanes (b) are, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltris-methoxyethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methyl-2-aminoethyl-3-aminopropyltrimethoxysilane -2-aminoethyl-3-aminopropyl-methyl-dimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltriethimethoxysilane and vinyltriethoxysilane.
• Suitable oligomeric or polymeric amino-functional silane compounds as component (c) are e.g. uncrosslinked, soluble, linear urea oligomers and polymers with free terminal amino groups and lateral alkoxysilane groups, which are stable in storage in organic solution and which give stable solutions in aqueous solvents.
• the combination of free amino groups, urea groups and more than one alkoxysilane group per molecule leads to outstanding properties of the size.
• Water-soluble, oligomeric or polymeric amino-functional urea-alkoxy-silane compounds are preferably obtainable by reaction of a) 1 to 1.8 equivalents of a diisocyanate
• Z C i -C 6 alkylene, C 5 -C ⁇ 0 cycloalkylene or arylene,
• R 1 H, C r C 6 alkyl or C 5 -C 10 cycloalkyl
• Y C 3 -C 6 alkylene
• R 2 C r C 6 alkyl or C 5 -C 10 cycloalkyl
• R 3 -C -C 6 alkyl or C 5 -C ⁇ o-cycloalkyl
• b2) 0 to 20% by weight of at least one nonionic, hydrophilic compound containing ether groups which has two groups which are reactive toward isocyanate groups, in particular hydroxyl and / or amino groups, per molecule.
• Aromatic, aliphatic, heterocyclic, monocyclic and polycyclic, bifunctional isocyanate compounds are preferred as diisocyanates.
• R C r C 6 alkylene, C 5 -C 15 cycloalkylene, C 6 -C 14 arylene, C 7 -C 20 arylalkylene or C7-C 2 -alkylarylene
• 1,6-Diisocyanatohexane and l-isocyanatomethyl-5-isocyanate-1,3,3-trimethylcyclohexane are particularly preferred.
• bis-functional isocyanates which have been prepared by reacting or oligomerizing diisocyanates can preferably be used on average.
• products containing allophanate, uretdione or biuret groups such as Desmodur ® N 100 from Bayer AG, Leverkusen
• partially trimerized polyisocyanates which have iminooxadiazinedione or isocyanurate rings such as Desmodur ® N 3400 from Bayer AG
• Particularly suitable diaminoalkoxysilanes bl) are N-ß- (am ⁇ noethyl) - ⁇ -aminopropyltrimethoxysilane (Dynasilan ® Damo from Hüls AG), N-ß- (aminoethyl) - ⁇ -aminopropylt ⁇ ethoxysilane, N-ß- (ammoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N-ß- (amino-ethyl) -N-ß- (aminoethyl) - ⁇ -aminopropyltrimethoxysilane:
• N- ⁇ - (ammoethyl) - ⁇ -ammopropyltrimethoxys ⁇ lan is particularly preferred.
• the polyether chains of these compounds preferably consist of at least 80
• Wt -%, particularly preferably 100 wt -%, of ethylene oxide units can being present in addition to these also Propylenoxidem situation
• Preferred nonionic hydrophilic compounds are for example polyethylene glycols having molecular weights from 300 to 6000 (for example Carbowax ® 300, 400, 1000, 1500, 2000, 6000 from Union Carbide), difunctional ether diamines, such as, for example, 4,7-dioxadecane-1, 10-dimoxion, 4,9-dimoxadodecane-1, 12-dimoxionane, 4,7, 10-trioxadecane-1, 13-dimoxane, bis - (3- aminopropyl) polytetrahydrofuran, bis (3-aminopropyl) polytetrahydrofuran, bis (3-aminopropyl) polytetrahydrofuran (Products Carbowax ® 750, 1100, 2100 of BASF), and polyether
• the following difunctional ether diamines are very particularly preferred: 4,7-dioxadecane-1,10-diamine; 4,9-dioxadodecane-1, 12-diamine; 4,7,10-trioxadecane-1,13-diamine; bis- (3-aminopropyl) -polytetrahydrofuran 750, bis- (3-aminopropyl) -polytetrahydrofuran 1 100, bis- (3-aminopropyl) -polytetrahydrofuran 2 100 from BASF and Jeffamine ® D 230, D 400, D 2000, XTJ 510 (D 4000), ED 600, ED 900, ED 2003 ED 4000, EDR 148 (XTJ504) of Texaco Chemical Company.
• Oligomeric or polymeric amino-functional silane compounds suitable as component (c) are furthermore oligoamino-amide silanes such as Al 387 from Witco or oligomeric or polymeric amino-functional urea alkoxysilane compounds.
• further size components (d) such as anionic, cationic or nonionic emulsifiers, further film-forming resins, lubricants such as e.g.
• Nitrogen compounds e.g. ethoxylated imidazolinium salts, mineral oils or waxes and auxiliary substances such as wetting agents or antistatic agents such as e.g. Lithium chloride or
• Ammonium chloride can be contained in the sizes. These further auxiliaries are known to the person skilled in the art and are described, for example, in K.L. Loewenstein, "The Manufacturing Technology of Continuous Glass Fibers", Elsevier Scientific Publishing Corp.,
• the glass fibers according to the invention are reinforcing fibers for thermoplastic polymers such as polycarbonates, polyamide-6 and polyamide-6,6, aliphatic, aromatic and mixed aliphatic / aromatic polyester amides, aliphatic, aromatic and mixed aliphatic / aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, Polyurethanes, polyarylene sulfides or polycycloolefins as well as thermosetting polymers such as unsaturated polyester resins, epoxy resins and phenol-formaldehyde resins are suitable.
• thermoplastic polymers such as polycarbonates, polyamide-6 and polyamide-6,6, aliphatic, aromatic and mixed aliphatic / aromatic polyester amides, aliphatic, aromatic and mixed aliphatic / aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, Polyurethanes, polyarylene sulfides or polycycloolefins as well as thermo
• the size (see Table 1) was applied to glass fibers with a diameter of 14 ⁇ m using a kiss roll applicator.
• the glass fibers were wound up into cakes and then dried at 130 ° C. for 10 hours. After drying, the glass fibers were cut into 4.5 mm long chops.
• Example 1 The same size as in Example 1 (see Table 1) was applied to the glass fibers with a diameter of 14 ⁇ m using a kiss roll applicator. The glass fibers were cut directly after the applicator in the direct chopper and then dried at 130 ° C. for 10 hours.
• the glass fibers according to Examples 1 and 2 were in an extruder at an extruder temperature of 250 ° C to a molding composition consisting of 70 parts by weight of polyamide 6 (Durethan R , commercial product from Bayer AG, Leverkusen) and 30 parts by weight of glass fiber extruded from Example 1 or Example 2 and granulated.
• polyamide 6 Durethan R , commercial product from Bayer AG, Leverkusen
• the sizes consisted of the components according to Table 3 and were applied to glass fibers with a diameter of 1 1 ⁇ m using a kiss roll applicator. The glass fibers were then cut in a direct chopper and then dried at 130 ° C. Table 3
• glass fiber-reinforced plastics were obtained which have better properties in terms of tensile and bending strength and impact resistance than corresponding plastics which were produced using conventional sized glass fibers and were cut using the more cost-effective direct chop process.

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• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
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• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Glass Compositions (AREA)

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Citations (3)

• 2000
  • 2000-05-17 TR TR2001/03402T patent/TR200103402T2/xx unknown
  • 2000-05-17 AT AT00943720T patent/ATE261408T1/de not_active IP Right Cessation
  • 2000-05-17 JP JP2000621305A patent/JP2003500562A/ja active Pending
  • 2000-05-17 ES ES00943720T patent/ES2216909T3/es not_active Expired - Lifetime
  • 2000-05-17 EP EP00943720A patent/EP1192113B1/de not_active Expired - Lifetime
  • 2000-05-17 AU AU58085/00A patent/AU5808500A/en not_active Abandoned
  • 2000-05-17 DE DE50005602T patent/DE50005602D1/de not_active Expired - Lifetime
  • 2000-05-17 WO PCT/EP2000/004461 patent/WO2000073235A1/de not_active Ceased

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