GB2088386A - Sizing Composition to Yield Sized Glass Fibers with Improved UV Stability - Google Patents
Sizing Composition to Yield Sized Glass Fibers with Improved UV Stability Download PDFInfo
- Publication number
- GB2088386A GB2088386A GB8037537A GB8037537A GB2088386A GB 2088386 A GB2088386 A GB 2088386A GB 8037537 A GB8037537 A GB 8037537A GB 8037537 A GB8037537 A GB 8037537A GB 2088386 A GB2088386 A GB 2088386A
- Authority
- GB
- United Kingdom
- Prior art keywords
- sizing composition
- aqueous sizing
- glass fibers
- present
- glass fiber
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 137
- 238000004513 sizing Methods 0.000 title claims abstract description 123
- 239000003365 glass fiber Substances 0.000 title claims abstract description 84
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 claims abstract description 31
- 239000004814 polyurethane Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- 150000004756 silanes Chemical class 0.000 claims abstract description 26
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims description 50
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 28
- 229910000077 silane Inorganic materials 0.000 claims description 28
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- -1 polytetrafluoroethylene fluorocarbon Polymers 0.000 claims description 18
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920006267 polyester film Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 239000012783 reinforcing fiber Substances 0.000 claims 2
- 125000003368 amide group Chemical group 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 229920001225 polyester resin Polymers 0.000 claims 1
- 239000004645 polyester resin Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 229920006337 unsaturated polyester resin Polymers 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 7
- 239000007787 solid Substances 0.000 description 16
- 230000005855 radiation Effects 0.000 description 11
- 238000009472 formulation Methods 0.000 description 9
- 239000007822 coupling agent Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 229910001651 emery Inorganic materials 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000007539 photo-oxidation reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002176 Pluracol® Polymers 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical class OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000004383 yellowing 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
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/326—Polyureas; Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
This invention concerns an aqueous sizing composition for glass fibers, and reinforced polymeric material comprising such sized glass fibers. The aqueous sizing composition comprises (1) a thermoplastic, predominantly aliphatic, elastomeric, curable polyurethane polymer, (2) one or more ureidofunctional silanes and (3) one or more aminofunctional silanes. The reinforced polymeric material has improved UV stability while maintaining good physical properties.
Description
SPECIFICATION
Sizing Composition to Yield Sized Glass Fibers with Improved UV Stability
The present invention is directed to a sizing composition useful in producing sized glass fibres having improved stability to ultraviolet radiation. More particularly, the present invention is directed to a sizing composition and sized glass fibers produced therewith that when used in reinforced polymers yield reinforced polymers with improved color stability when subjected to light.
Light is electromagnetic radiation in the wave length range including infrared, visible, ultraviolet and X-rays. Only about five percent of the ultraviolet radiation emitted from the sun reaches the earth's surface and this five percent is usually radiation having wave lengths longer than 290 nanometers. The light produced from man-made sources such as fluorescent lights and the like can emit ultraviolet radiation (UV) that generally has wave lengths below 290 nanometers. Most organic substances including polymers or plastics are changed on long-term exposure to light including sun light and manmade light that contains ultraviolet radiation. Prolonged exposure of polymers to UV-containing light leads to photo oxidation and degradation of the polymer. This degradation is usually manifested in the discoloration of the polymer.
It is well known in the art to use additives for polymers that give some degree of UV stability to the polymer to retard the process of photo oxidation and degradation of the polymer upon exposure to light. There must be at least ten different classes of materials used as UV stabilizers for polymers. The principle classes of UV stabilizers are the benzophenones, benzotriazoles, the salicylates, metallic complexes, substituted acrylonitriles and certain colorants. Which class or particular stabilizer within a class that should be used with a particular type of polymer depends on the specific requirements relating to polymer compatibility, permanence, and the level of absorption needed for the particular polymer, because some polymers are more sensitive to UV radiation than others.For example, polyurethanes, which are produced by reacting polyols containing an active hydrogen with isocyanate, require stabilization against photo oxidation. It is known in the art in the case of polyurethanes that the hi o;l.ernd amine light stabilizers, for example bis(2,2,6-6-tetramethylpiperidenyl-4)sebacate and oxalic-anilide derivatives, in combination with benzotriazoles provide excellent UV stability. In addition to the use of UV stabilizers, it is also known to add functional groups to the backbone in order to retard the photo oxidation of the polymer caused by UV radiation.
Glass fibers used as reinforcement for polymers are formed by being drawn at a high rate of speed from molten cones of glass from tips of small orifices in a platinum device called a bushing. In order to protect the glass fibers from interfilament abrasion during formation and further processing and to make them compatible with the polymers they are to reinforce, a sizing composition is applied to the glass fibers during their formation. The sizing compositions conventionally contain lubricants, film formers, coupling agents, wetting agents, emulsifiers, and the like. Many of these components are polymeric materials that can degrade by photo oxidation when subjected to radiation. The degradation of the polymers in the sizing composition on glass fibers used to reinforce polymers may lead to the discoloration of the reinforced polymeric material.Such discoloration leads to an unaesthetic appearance of a reinforced polymeric material and lack of color uniformity over a period of time for the reinforced polymeric material.
By practice of the present invention there may be provided one or more of the following: (i) a sizing composition that has improved light stability;
(ii) a sizing composition for glass fibers that yields sized glass fibers having improved UV stability and a reduced tendency to discolor;
(iii) a polymeric material reinforced with sized glass fibers wherein the sizing composition on the glass fibers has improved light stability, so as to deter imparting of discoloration to the fiber and the reinforced polymeric material upon long exposure to ultraviolet light;
(iv) a sizing composition and sized glass fibers that lead to the production of polymeric materials reinforced with sized glass fibers that have improved light stability without the use in the sizing composition of conventional light stabilizing agents; and
(v) a sizing composition and sized glass fibers having improved UV stability and reduced tendency to discolor without deleteriously affecting other properties of sizing composition and sized glass fibers.
According to the present invention there is provided an aqueous sizing composition comprising one or more thermoplastic, predominantly aliphatic, curable polyurethane latices, appropriate silane coupling agents and, optionally, an appropriate lubricant system.
Broadly speaking, in one aspect, the sizing composition of the present invention comprises one or more thermoplastic, predominantly aliphatic, polyurethane latices, one or more ureidofunctional silanes and one or more aminofunctional silanes.
The sizing composition can be used to treat glass fibers that are processed into any form of glass fibers such as chopped strand; roving; woven product; continuous strand, chopped strand, or needled mat; and strands and the like. Depending on what form the treated glass fibers are to be used, a compatible lubricant can be used in the sizing composition along with the polyurethane dispersion and the ureidofunctional and aminofunctional silanes. The amount of the polyurethane dispersion and the ureidofunctional and aminofunctional silanes present in the sizing composition are generally those amounts conventionally used for film formers and coupling agents in sizing compositions for glass fibers.
Also, in accordance with this invention glass fibers are provided that have at least a portion of their surface in contact with the residue produced by removing water from the aqueous sizing composition having a curable thermoplastic, predominantly aliphatic (including cyclic aliphatic) polymer, ureidofunctional silane, aminofunctional silane, and usually one or more compatible lubricants.
In addition to the polyurethane polymer, ureidofunctional and aminofunctional silanes and usually present lubricant, the sizing composition may have present additional agents conventionally used in sizing compositions for glass fibers.
The sizing composition and the sized glass fiber strand of the present invention can be used to produce reinforced polymeric material, for example, polyamides, e.g. nylon, polybutyiene terephthalate, polyethylene terephthalate, polystyrenics, thermosetting esters and chemically coupled polypropylene.
These reinforced polymers have improved stability from the improved UV stability of the sized glass fibers while the sized glass fibers have good handleabilities, physical properties, thermal stability, and processing properties.
The sizing composition, sized glass fiber strands and glass fiber reinforced polymeric material of the present invention are believed to have excellent UV stability while maintaining good glass fiber properties of handleability, thermal aging, ambient aging and processability in accordance with the following theory, although the present invention is not limited by this theory.
The energy content of UV radiation is in the range of about 290 up to 400 nanometers which corresponds to about 95 to about 71.5 kilocalories per einstein. This energy level can rupture most of the chemical bonds in polymer structures, and lower amounts of energy can rupture some of the chemical bonds in polymers. It is known that not all polymers are equally affected by UV radiation and some are more resistant than others, for example, polymethylmethacrylates and fluorocarbons are more resistant than polyethylene. Some polymers in their pure forms, expected to be resistant to UV radiation, are actually degraded because of contaminants that act as sights for UV energy absorption. It is known that polyurethane resins based on aliphatic components are resistant to yellowing by UV light.When polyurethane resins based on aliphatic components are to be used in a sizing composition with other sizing components, particular coupling agents must be used in order not to act as contaminants and present sights for UV energy absorption.
The thermoplastic, curable, polyurethane resins that are based on predominantly aliphatic components useful in the present invention are aqueous emulsions or solutions of polyurethane polymers formed by the reaction of an organic; linear, branched, or cyclic aliphatic isocyanate with an organic; linear, branched or cyclic aliphatic polyhydroxylated compound or hydroxyl terminated ether or polyester polymer. By the term "predominantly aliphatic" it is meant that minor amounts of aromatic materials may be present so long as the minor amount is not sufficient to permit degradation of the polyurethane by light so as to cause an unacceptable or unaesthetic amount of discoloration. The aqueous emulsion or solution of polyurethane has present in it anionic or nonionic surfactants.
Particularly suitable aqueous emulsions of polyurethane polymers useful in the present invention include "Rucothane Latex 2010L, 2030L, 2040L, 2050L, and 2060L", available from Ruco Division of
Hooker Chemical Corporation, New York. The materials are thermoplastic polyurethane latices having a varying particle size of a high molecular weight isocyanate based thermoplastic elastomer in a water dispersion with an anionic or nonionic surfactant. The Rucothane latices are based on aliphatic isocyanates and have a polymer solids content of the stable emulsions ranging from 55 to 65 percent by weight where the urethane polymer has an ester backbone. The Rucothane latexes have a
Brookfield RVF 4 viscosity in centipoise at 2 RPM ranging from 7000 for the "2060L" up to 25,000 for the "2020L" latices.The preferred Rucothane latex used in the sizing composition of the present invention is the resin designated "201 0L" because of the improved processability obtained with glass fibers treated with a sizing composition containing this particular Rucothane resin. Also the polyurethane products made with isocyanates designated "hylene W" available from Dupont may be used. The amount of the thermoplastic polyurethane latex present in the sizing composition is generally a major amount of the solids in the sizing composition and is preferably in the range from about 40 to about 95 weight percent of the sizing composition based on the non-aqueous solids of the sizing composition and from about 2 to about 50 weight percent based on the aqueous sizing composition.
Any suitable ureidofunctional silanes can be used in the sizing composition of the present invention. Non-exclusive examples include compounds with the following formula:
wherein R and R' can be a hydrogen atom or methyl group and wherein R" is a methyl or ethyl group.
The ureidofunctional silanes are generally neutral and water soluble materials that have reduced reactivity at lower temperatures with many matrix resins. One particularly useful ureidofunctional silane for the sizing composition of the present invention is designated "A-1 1 60" and is available as 50 percent concentration in methanol solution from Union Carbide Corporation, New York. The "A-l 160" has a formula molecular weight of 264.1, a flash point of 43 as determined by ASTM method D-56 using a tag closed cup, and has a specific gravity at 25/250C of 0.988, and a refractive index at 250C of 1.386.The amount of ureidofunctional silane used in the sizing composition of the present invention is generally in the range of about 0.05 to about 2.0 weight percent based on the aqueous sizing composition and about 1 to about 4 weight percent of the non-aqueous solids in the sizing composition.
Any suitable aminofunctional silane can be used in the sizing composition of the present invention. These aminofunctional silanes range in composition from the single primary amino group of gamma-aminopropyltriethoxysilane to the primary-secondary diaminofunctional silane of Nbeta(aminoethyl) gamma-aminopropyltrimethoxysilane and polyaminofunctional silanes. One particularly useful aminofunctional silane for the sizing composition of the present invention is gammaaminopropyltrimethoxysilane available commercially under the designation "A-i 100" from Union
Carbide Corporation.The amount of aminofunctional silane used in the sizing composition of the present invention is in the range from about 0.05 to about 2.0 weight percent of the total aqueous sizing composition and from about 1 to about 5 weight percent of the sizing composition based on the non-aqueous solids in the composition.
Lubricants which are suitable for use in the sizing composition of the present invention can be any cationic, anionic, or nonionic lubricant or mixture thereof. Preferably, lubricants are used in the sizing composition and the particular lubricant used will vary with the particular form in which the sized glass fibers will be used, e.g., chopped strands, roving, woven strand, mat and the like. Particularly suitable lubricants are those designated "Emery 6717" and "Emery 67-U" both of which are amide substituted polyethylene amines commercially available from Emery Industries. In addition polytetrafluoroethylene fluorocarbon resin dispersions, for example "Teflon" (Registered Trade Mark) resin dispersion, can be employed as lubricants in the dispersion of this invention.Also, the lubricant can be a combination of lubricants such as Emery Lubes 671 7 and Emsorb 6901 available from Emery
Industries. When the sizing composition is used to treat glass fibers that will eventually be chopped to produce the preferred sized glass fibers strand form, i.e., chopped strand, it is preferred to use a combination of lubricants. This preferred combination of lubricants includes one or more polyoxyalkylene and/or polyalkylene polyol lubricants such as "Pluracol V-i 0 or V-7 polyols" both available from BASF Wyandotte Corporation from Michigan. The product, "Pluracol V-i 0 polyol", is a viscous, high molecular weight, liquid polyoxyalkylene polyol with a specific gravity at 600F./600F.
(600F=15.560C) by BWC test of 1.089 with a flash point by ASTM D92-52 of 51 00F (265.560C).
The product, "Pluracol V-7 polyol", is a water-soluble, high molecular weight, viscous, liquid polyalkylene polyol with a specific gravity at 250C./250C. of 1.090 and flash point of 51 00F. Also, this lubricant combination includes a lubricant modified aminosilane, for example, "Y-9702 lubricant modified A-i 100 silane" available from Union Carbide Corporation having a flash point of 1 450F (62.780 C) as determined by ASTM method D-93 using a Pensky closed cup with a specific gravity of 0.998 at 25/250C and a refractive index at 250C of 1.438. The use of this preferred combination of lubricants facilitates further processing and fabrication of glass fibers into chopped strand.
The amount of lubricant employed in the sizing composition of the present invention is within the range of about 0.2 to about 2 weight percent of the aqueous sizing composition. If more than one type of lubricant is employed then the total lubricant in the sizing composition can range from about 0.2 to about 5 weight percent of the aqueous sizing composition.
In addition to the linear or branched but preferred cyclic aliphatic polyurethane, and ureidofunctional silane and aminofunctional silane, and preferably lubricant components of the sizing composition, additional agents may be added to the sizing composition. Non-exclusive examples of additional agents that may be used are coupling agents, film formers, film former modifiers, lubricants, adhering agents such as Ruco Catalyst, available from Hooker Corporation, cross-linking agents such as "Cymel 370" available from American Cyanamid Corporation and other similar additives. It is preferred to have present in the sizing composition additional agents that perform the function of processing aids. The preferred processing aids include dibutylphthalate (DBP) that acts as a plasticizer for the polyurethane cured film.Another preferred processing aid present in the sizing composition of the present invention is a polyester film former such as "RD-1 1 35B" available from PPG Industries, Inc.
that reduces binder throw off and acts. as an antioxidant. In general the amounts of additional agents present in the sizing composition of the present invention are those amounts conveniently used to perform the function for which the agent is added to the sizing composition. The amounts of DBP added to the sizing composition are in the range of about 0.05 to about 5 weight percent based on the non-aqueous solids of the sizing composition. The amount of RD-1 1 35B added to the sizing composition is in the range of about 2 to about 1 5 weight percent based on the non-aqueous sizing composition.
A sizing composition of the present invention may be prepared by mixing the polyurethane dispersion with water in a mixing tank with agitation. To the polyurethane dispersion-water mixture there is added the dibutylphthalate (DBP) and it is dispersed well into the polyurethane with moderate agitation. In a separate vessel the ureidofunctional silane, the aminofunctional silane, and a lubricant modified silane, "A-l 100" silane, "A-l 160" silane and "Y-9072" silane respectively are premixed with water and hydrolized for a short period of time. After the silanes are premixed they are combined with the mixture of DBP, polyurethane and water. The lubricant is diluted with water, preferably hot water and cooled and then added to the combination of coupling agents and polyurethane mixture.
After this addition the processing aids can be added to the mixture. The mixture is then diluted to final volume with water. The mixture is checked for its pH characteristic, its solids content and viscosity.
Typically, the overall solids content of the sizing composition can vary from about 4 to about 20 percent by weight. It should be noted that the solids content can be adjusted in accordance with the desired solids content for the specific forming condition employed. Generally, the solids content will range from about 5 to about 10 percent by weight and preferably from 6.5 to 8.5 percent by weight. By solids content it is meant the residual solids remaining after drying the sizing composition at about 1 050C to constant weight. In all events, the solids content of the sizing composition should be adjusted so that the viscosity at 200C of said sizing solution does not exceed 100 centipoise. This viscosity restriction is necessary in order that the filaments do not break during the application of the sizing solution.
In applying the sizing composition of the present invention to glass fibers, the glass fiber strand is formed by a multitude of fine fiber glass filaments which are drawn at a high rate of speed through molten cones of glass located at the tips of small orifices in a bushing such as is shown in U.S. Patent
Specification No. 2,133,238. During formation, the filaments are coated while they are moving at speeds on the order of 5,000 to 20,000 fpm (1,524 to 6,096 metres per minute) with the forming size of the present invention. The sizing composition may be sprayed on the fibers as they are being drawn or in the preferred embodiment the fibers may be drawn across the surface of a roller applicator on which the sizing composition is placed.The fibers after sizing are grouped into strands which are then wound, typically, onto forming packages utilizing a winder and an associated paper or plastic or other type of forming tube located on the surface of the winder in the conventional manner.
The forming packages containing the glass fibers strand sized with the sizing composition of the present invention may then be formed into roving by unwinding a plurality of strands from several forming packages positioned on a creel and combining the strands into parallel form and winding the strands on tubular support in the conventional manner, or into chopped strands by feeding the sized glass fiber strands through a chopper in a conventional manner, or into a mat or woven glass fiber product. The preferred glass fiber form for which the sizing -composition of the present invention is used is the chopped glass fiber strand, which is preferably formed by chopping sized glass fiber strands that are obtained from a plurality of forming packages located on a creel rather than chopping a plurality of sized glass fibers during the glass fiber forming process.
The glass fiber strands in any form, but preferably in the form of chopped strand, sized with the sizing composition of the present invention can be used to reinforce any polymeric material and obtain a product that has better UV stability while still maintaining satisfactory physical properties. It is preferred to use the sized glass fibers of the present invention as reinforcement for polymeric material such as polyamide (nylon), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrenics (PS), thermosetting polyester, and chemically coupled polypropylene, for example the product of Hercules Chemical Corporation designated "PCO-72" which is a blend of homopolymer of polypropylene and a polypropylene polymer grafted with maleic anhydride. It is most preferred to use the sized glass fibers in the form of chopped strand as reinforcement of polyamide materials.
The present invention will now be further iilustrated by way of the following examples:
Examples
Sizing compositions were prepared from the formulations of Table I.
Table I
Sizing Compositions
Formulations in Grams of ingredient/Indicated kg of Sizing
Formulation Formulation Formulation Formulation Formulation (Wt.%)
Sizing Components 1 2 3 4 5
Quantity of Sizing (kg) 18.9 9.46 9.46 9.46 189.2-(41.6)
Polyurethane polymer dispersion 1760 925 925 925 18,500-(40.8) (Rucothane polymer dispersion 2010L)
Ureidofunctional Silane 165 66 33 66 1,320-(2.9) (A-1160 silane)
Aminofunctional Silane 61 33 66 33 660-(1.4) (A-1100 silane)
Dibutylphthalate (DBP) - 25 50 - 1.000-(2.2)
Lubricant (Emsorb 6901) 55 - - - 2 aminopropanol (2-AMP-95) 55 - - -
Amide Substituted 6 - - - polyethyleneamine lubricant (Emery 6717)
Polyalkylene polyol lubricant - - - 40 50-(0.1) (Piuracol V-10)
Lubricant modified Silane - - - - 20-(0.04) (Y-9072)
Polyester film former - - - - 5,000-(11.0) (RD-1135B)
Properties of Sizing Composition pH 9.5 9.3 9.6 9.0 10.
Solids 6.8 6.95 6.7 7.0 7.8
Sized Glass Fiber Properties
Percent LOI on K-37 strand 0.99 1.2 0.98 0.99 1.25 Table II
Physical Properties for Polyamide Reinforced with Chopped Strand Sized with Sizing
Composition of Invention or Commercial Sizing
Sunlamp Impact Strength
Color Flex Str. Flex Mod Ten Str.Notch Reverse
Chopped Strand Type %LOI %CS Stability1 (psi) (x 106psi) (psi) (fpi) (fpi) 3/16" (0.48 cm) 0.95 32 Good(5)3 34,800 1.28 21,100 2.86 11.8
Commercial2 1/4" (0.64 cm) Table 1.15 32.9 Excellent (1-2) 37,600 1.28 22,900 3.45 14.7 1 Form 1 (like) 1/8" (0.32 cm) Table 1.13 31.7 Excellent (1-2) 37,700 1.29 23,000 3.67 15.1 1 Form 1 (like) 1/8" (.32 cm) Table 1.25 32.4 Excellent (1-2) 38,400 1.25 22,600 2.89 15.1 1 Form 5 1. 24-Hour Sunlamp Exposure 2.Owens Corning Fiberglass Corp. product designated "419AA, TSL" 3.On a scale of 1 to 10 with 1 the best and 10 the poorest.
The sizing formulations shown in Table I were prepared by placing approximately 7.6 litres of water in a premix tank and stirring in the stated amount of polyurethane resin dispersion with low speed stirring. Following this mixing, the stated amount of the dibutylphthalate was dispersed well into the polyurethane polymer dispersion with moderate speed stirring. After this dispersion was prepared, the coupling agents, the ureidofunctional silane, aminofunctional silane, and, if any, the lubricant modified silane were premixed and hydrolized in approximately 75.7 liters of water. The dispersed polyurethane polymer mixture was then added to the hydrolized silane mixture.After this addition, the lubricant was dissolved in approximately 3.786 liters of hot water and cooled with approximately 1 1.4 liters of water which was then added to the mixture of coupling agent and polyurethane polymer. After this addition,
processing aids such as the polyester film former, RD-1 1 35B was diluted with an equal quantity of water and added to the mixture of lubricant, coupling agents and polyurethane polymer. After these additions, the mixture was diluted to approximately the quantity of sizing composition indicated with water and the pH and solids characteristics were obtained.
The sizing formulations of Table I were applied to glass fiber strands in the conventional manner
as described above to produce glass fiber strands of the K-37 dimension or G.67.5, although a sizing composition of the present invention can be used to treat glass fibers to produce glass fiber strand of
any dimension. After the glass fibers were treated with the sizing compositions of Table I and gathered
into glass fiber strand in the form of a forming package, the strands were prebaked for approximately
12 hours at approximately 2400 F. (11 60C.). The dried glass fiber strands were then chopped in a conventional manner to a chopped length of 1/8" (0.32 cms).
Sized, chopped glass fiber strands prepared with sizing compositions like those stated in Table I ,were tested for their UV stability and other physical properties when used to reinforce polyamides. The results of this testing are shown in Table II.
The results of Table II indicate that the polyamide material reinforced with chopped glass fiber strand having the sizing composition of the present invention produced a reinforced polyamide material that had excellent UV stability while maintaining good physical properties.
The foregoing has described sizing compositions, sized glass fiber strands and reinforced polymeric materials with sized glass fiber strand of the present invention. The invention involves the presence of sizing materials on glass fiber strands and in reinforced polymeric materials that lead to the properties of improved UV stability while maintaining good physical properties. This is accomplished by having a sizing composition, sized glass fiber strands, and polymeric materials reinforced with sized glass fiber strands wherein materials in the sizing include one or more polyurethane polymers, preferably in the form of a dispersion, one or more ureidofunctional silanes, one or more aminofunctional silanes and one or more appropriate lubricants depending on the form in which the glass fibers are to be used, preferably polyalkylene, polyol type lubricant with a lubricant modified aminosilane, and processing aids such as polyester film formers or film former modifiers and plasticizers.
Claims (30)
1. An aqueous sizing composition for glass fibers to produce sized glass fibers having improved
UV stability, comprising:
a) one or more thermoplastic, predominantly aliphatic, elastomeric, curable polyurethane polymers,
b) one or more ureidofunctional silanes, and
c) one or more aminofunctional silanes.
2. An aqueous sizing composition as claimed in claim 1 , wherein the ureidofunctional silane is selected from gamma-ureapropyl-triethoxysilane, gamma-methylureapropyltriethoxysilane and gamma-dimethylurea-propyltriethoxysilane
3. An aqueous sizing composition as claimed in claim 1 or claim 2, wherein the ureidofunctional silane is present in an amount of about 0.05 to about 2.0 weight percent of the total aqueous sizing composition.
4. An aqueous sizing composition as claimed in any of claims 1 to 3, wherein the aminofunctional silane is gamma-aminopropyltriethoxysilane.
5. An aqueous sizing composition as claimed in any of claims 1 to 4, wherein the aminofunctional silane is present in an amount of about 0.05 to about 2.0 weight percent of the total aqueous sizing composition.
6. An aqueous sizing composition as claimed in any of claims 1 to 5, wherein one or more glass fiber lubricants are present.
7. An aqueous sizing composition as claimed in claim 6, wherein the glass fiber lubricant is an
amide substituted polyethyleneimine.
8. An aqueous sizing composition as claimed in claim 6, wherein the glass fiber lubricant is one or
more polyoxyalkylene and/or polyalkylene polyols.
9. An aqueous sizing composition as claimed in claim 6, wherein the glass fiber lubricant is one or
more polytetrafluoroethylene fluorocarbon resin dispersions.
10. An aqueous sizing composition as claimed in any of claims 1 to 9, wherein the glass fiber lubricant is present in an amount of about 0.05 to about 5 weight percent of the total aqueous sizing composition.
ii. An aqueous sizing composition as claimed in any of claims 1 to 10 which has present dibutylphthalate.
12. An aqueous sizing composition as claimed in claim 11, wherein the dibutylphthalate is present in an amount of about 0.01 to about 2 weight percent of the total aqueous sizing composition.
13. An aqueous sizing composition as claimed in any of claims 1 to 12 having present one or more polyester resin film formers.
14. An aqueous sizing composition as claimed in claim 13, wherein the polyester film former is present in an amount of about 0.05 to about 1 5 weight percent of the total aqueous sizing composition.
15. An aqueous sizing composition as claimed in any of claims 1 to 14 having present one or more lubricant modified gamma-aminopropyltriethoxysilanes.
1 6. An aqueous sizing composition as claimed in claim 15, wherein the amount of lubricant modified gamma-aminopropyltriethoxysilane present is in the range of about 0.05 to about 2 weight percent of the total aqueous sizing composition.
17. An aqueous sizing composition as claimed in any of claims 1 to 16, wherein the polyurethane polymer is in the form of a dispersion wherein the polyurethane polymer is emulsified.
1 8. An aqueous sizing composition as claimed in any of claims 1 to 16, wherein the polyurethane polymer is present as a dispersion in the amount in the range of about 5 to 50 weight percent based on the aqueous sizing composition.
1 9. Glass fibers having on at least a portion of their surface a dried residue of an aqueous sizing composition comprising:
a) one or more thermoplastic, predominantly aliphatic elastomeric, curable polyurethane polymers,
b) one or more ureidofunctional silanes,
c) one or more aminofunctional silanes, and
d) a major amount of water.
20. Glass fibers as claimed in claim 19, wherein the aqueous sizing composition also comprises (e) one or more glass fiber lubricants.
21. Glass fibers having on at least a portion of their surface the dried residue of an aqueous sizing composition comprising:
a) one or more thermoplastic, predominantly aliphatic elastomeric, curable polyurethane polymers,
b) one or more ureidofunctional silanes,
c) one or more aminofunctional silanes,
d) one or more glass fiber lubricants,
e) one or more lubricant, modified silanes,
f) dibutylphthalate, g) one or more water dispersible, condensation, cross-linkable unsaturated polyester resins,
h) a major amount of water.
22. Glass fibers as claimed in claim 21, wherein the glass fiber lubricant is one or more amidopolyethyleneimines.
23. Glass fibers as claimed in claim 21, wherein the glass fiber lubricant is one or more polyoxyalkylene and/or polyalkylene polyols.
24. Glass fibers as claimed in any of claims 21 to 23, wherein the polyurethane is a water dispersion with the polyurethane resin emulsified therein.
25. Glass fibers as claimed in any of claims 21 to 24, wherein the aminofunctional silane is gamma-aminopropyltriethoxysilane.
26. A molded reinforced polymer material having improved UV stability, comprising:
a) polymeric material selected from polyamides, polyethyleneterephthalate, polybutyleneterephthalate, polystyrenics, and chemically coupled polypropylenes.
b) reinforcing fiber sized with an aqueous composition comprising predominantly aliphatic, thermoplastic, elastomeric, polyurethane polymers, one or more ureidofunctional silanes and one or more aminofunctional silanes.
27. A molded reinforced polymeric material as claimed in claim 26, wherein the composition used to size the reinforcing fiber also comprises one or more glass fiber lubricants.
28. An aqueous sizing composition as claimed in claim 1 and substantially as hereinbefore described with reference to any of the Examples.
29. Glass fibers as claimed in claim 1 9 and substantially as hereinbefore described with reference to any of the Examples.
30. A molded reinforced polymeric material as claimed in claim 26 and substantially as hereinbefore described with reference to any of the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8037537A GB2088386B (en) | 1980-11-22 | 1980-11-22 | Sizing composition to yield sized glass fibers with improved uv stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8037537A GB2088386B (en) | 1980-11-22 | 1980-11-22 | Sizing composition to yield sized glass fibers with improved uv stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2088386A true GB2088386A (en) | 1982-06-09 |
| GB2088386B GB2088386B (en) | 1984-05-23 |
Family
ID=10517503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8037537A Expired GB2088386B (en) | 1980-11-22 | 1980-11-22 | Sizing composition to yield sized glass fibers with improved uv stability |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2088386B (en) |
-
1980
- 1980-11-22 GB GB8037537A patent/GB2088386B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2088386B (en) | 1984-05-23 |
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| Date | Code | Title | Description |
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| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 20001121 |