DE2853755A1 - SMOOTHED GLASS SPIDER THREAD AND ITS USE FOR REINFORCING OLEFIN POLYMERS - Google Patents

Description

The invention relates to a new sized fiberglass spun thread and its use to reinforce olefin polymers. The invention is directed in particular on fiberglass filaments which have been treated with a special aqueous size and which directly from so-called molded packs, which were wound up during the manufacture of the fiberglass filaments can be used.

It is known to use polyolefins with glass fibers in the form of continuous fiberglass filaments, staple fiberglass or to reinforce glass silk mats. It is also known that without an effective coupling agent, adhesion between the glass and the polyolefin is weak, so that under normal shear or tensile stresses a Separation takes place. It is also known that the affinity of the glass for water affects the adhesive strength between glass and polyolefin is further reduced if the polyolefin is not sufficiently bonded to the glass is.

A method has already been devised to control the adhesion between glass and essentially crystalline ones To improve polymers of "lower" olefins with three or more carbon atoms in the molecule. In the US Pat. No. 3,013,915 is stated in column 2, lines 38 to 46 that the adhesion of the polyolefins is improved by cleaning the glass surface, applying a coupling agent to it, a treatment

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with a chemical agent that has a source for dehydrating or oxidizing residues, which brings the polyolefin into contact with the glass and the polyolefin heated above its melting point to complete the connection. In column 4, lines 16 to 19, compounds with low decomposition points below 82 ° C are given as sources for the residues and in column 4, lines 69 to 71, it is stated that exposure to heat is to be avoided got to.

In US-PS 38 49 148 a method for sizing glass silk filaments with an aqueous size proposed, the size being a coupling agent, a heat-resistant organic peroxide, a non an ionic surfactant and a lubricant. Through this process, arbitrators are settled Obtained glass silk filaments that have a certain storage time, but the storage times are unsatisfactory and the sized filaments are still subject to degradation at high storage temperatures.

In US-PS 38 82 068 a sizing agent for glass thread, which is used to reinforce various plastic systems serve, described, this sizing agent being a coupling agent and a polyol " contains finemulsion.

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From US-PS 34 37 550 a method for improving the bonding of glass fibers to polyolefins is known, in which the fiber is treated with a crystalline polypropylene matrix. The preferred modifiers are maleic anhydride and acrylic acid.

In US-PS 38 83 333 a method and an apparatus for producing a continuous glass fiber mat is described, wherein sized fibers are used, which should have a satisfactory adhesion with polyolefins. The method and apparatus also show the filament being laid down immediately after the filaments are formed.

Some progress has been made in the sizing of glass fibers by the methods and compositions described, but there remains a desire to improve the bond between polyolefins and continuous glass filament with improved adhesion between these materials. In addition, there is a need for sized fiberglass filaments which allow practically unlimited storage of the sized filaments as molded packs. Sizes that contain peroxides as components have only a limited storage time and are very sensitive to temperature fluctuations when drying the threads and when high temperatures occur during storage. As a result, premature decomposition of the peroxides can occur, as a result of which the effectiveness of the size with regard to imparting the adhesive strength between the fiberglass spun thread and the polypropylene matrix is reduced. 030008/0554

The object of the invention is therefore a sized glass silk spun thread (strand) which has good adhesion with olefin polymers during drying
shows no thermal degradation of the size than
Molded pack has a long shelf life and can be used directly from the molded pack for reinforcing olefin polymers.

According to the invention, this object is achieved by
a sized fiberglass spun thread, which is characterized in that the size contains a coupling agent, a stabilizer, a lubricant, an uncrosslinked film-forming polymer and a crosslinked film-forming polymer.

Such a sized fiberglass spun thread is obtained by adding a sizing agent, which the components mentioned, preferably in an aqueous one
System contains, applies to a fiberglass filament in a known manner. The sized thread is then wound up into a molded pack and used for his
later used as a reinforcing agent for olefin polymers. After drying, the sized spun thread can be unwound from the molded pack at any point in time and laid down to form a mat, which is then, for example, with a
Foil or a plate made of polypropylene is brought into contact and processed into a fiber-reinforced article with the application of heat and pressure.

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By using the new sizing system, numerous advantages are achieved with the invention. The use of a storage-stable size without limitation of the storage time improves the flexibility of the fabrication. Before the invention, it was necessary to process the sized filaments shortly after their production or even immediately into mats and further into composite articles. In addition, drying of the sized fiber was difficult because the drying conditions were restricted because decomposition of the peroxide had to be avoided. By using the new sizing system, it is possible to produce molded packs from the sized fiberglass filaments at a central point. These can then be transported to various locations for further processing into composite bodies made of glass fibers and polyolefin without any restrictions in terms of temperature or atmosphere. Any suitable glasses can be used for the production of the glass threads, for example soda-lime glasses and borosilicate glasses ( ¹¹ E ") are particularly suitable.

One can typically use the fiberglass filaments used in the invention by the method of US-PS 21 33 238 produce. The fiberglass filaments consist of a large number of fine single glass filaments, the high speed of molten glass cones at the tips of small openings in a Spinneret to be pulled out. While the individual threads are being drawn out, they are mixed with the aqueous size

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coated. The single threads generally move at a speed of 305 to 7100 m / min. The sizing is in the immediate vicinity of the hot spinnerets and the glass furnace in which the glass is placed is melted, applied. After the single glass filaments have been coated with the size, they move a short distance to a collection facility. After the fiberglass filaments have been sized they can be dried to remove any remaining moisture.

The aqueous size contains a coupling agent, a stabilizer, a lubricant and an uncrosslinked one film-forming polymer and a cross-linking film-forming polymer.

The coupling agent can be any compound which is the bond between the fiberglass filament and the olefin polymer improved. Typical coupling agents of this type are metal salts of strong mineral acids, such as basic chromium chloride, basic chromium sulfide with a trivalent metal ion, such as chromium, cobalt, nickel, copper or lead, bound to at least a hydroxyl group of the metal and at least one anion of a strong mineral acid attached to the metal; Werner's complex salts with a trivalent nuclear atom, such as chromium, in coordination with an organic acid such as methacrylic acid, for example the complex salt of methacrylic acid and chromium III chloride, and other coupling agents that form complex salts according to Werner and vinylalkylamino, epoxy, mer

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capto, thioalkyl and phenol groups. Particularly suitable In the invention, the coupling agents used are silanes and siloxanes. Typically such coupling agents contain hydrolyzable vinyl, allyl, beta-chloropropyl, phenyl, thioalkyl, thioalkaryl, Aminoalkyl, methacrylate, epoxy and mercapto groups, the hydrolysis products and the polymers and Mixtures of such compounds come into consideration. A very particularly preferred coupling agent is gamma-aminopropyltriethoxysilane, as it is already at low levels Concentrations result in a coupling of high stability between the fiberglass filaments and the olefin polymers results.

Any secondary coupling agent which improves the stability of the size system, supports crosslinking and promotes the effectiveness of the coupling agent, in particular the silane, can be used as the stabilizer. Typical stabilizers for sizes in the present invention are the ethylenically unsaturated mono- or dicarboxylic acids or their anhydrides. Examples of such acids and their anhydrides are maleic acid, fumaric acid, itaconic acid, citraonic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, mesaconic acid, ^ll Himic "anhydride, maleic anhydride, itaconic anhydride, citraonic anhydride and mixtures thereof. A preferred stabilizer is maleic acid stable system results and supports the coupling action of the silane coupling agent.

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Any lubricants that promote film formation can be used as lubricants in the size and promote the clutch. Particularly suitable lubricants are chemically modified polypropylenes * Among these products are the malonized and Polypropylenes modified with acrylic compounds especially preferred as they have a filament with particularly good storage properties and particularly good Unwindability of the molded pack result.

As the uncrosslinked polymer in the invention, a any uncrosslinked polymer can be used that imparts the integrity of the filament and that Unwinding of the filament from the molded pack allows. The uncrosslinked polymer gives the size the desired Degree of plasticity, so that the sized thread has a longer storage time and itself can also be needled with good success in the form of a mat. Examples of uncrosslinked polymers are Homopolymers or mixtures of homopolymers suitable, those under the sizing conditions, the drying conditions and the deformation conditions, those the sized threads are subjected to not cross-linking. Preferred uncrosslinked film-forming Polymers are epoxy polymers, polyester polymers, polyurethanes, acrylic polymers, vinyl polymers, Mixtures of such polymers and copolymers of corresponding monomers. A particularly preferred one uncrosslinked film-forming polymer is the homo-

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polymer of vinyl acetate, which is not degraded at the temperatures in question, the spun thread imparts good integrity and is available at low cost,

The crosslinked film-forming polymer of the sized fiberglass filament of the invention can be any Be polymer or copolymer that is used to generate the spun thread, its integrity and hardness ^ contributes to its laying and its needleability and is suitable for self-networking. These self-crosslinking Polymers have the ability to crosslink without adding any other material among the Conditions such as those for the drying of the sized fiberglass filament with the formation of the molded package appear. Typical self-crosslinking polymers have mutually reactive groups, such as Example epoxy polymers, polyester polymers, polyurethanes, acrylic polymers, vinyl polymers, mixtures of such polymers and copolymers from the corresponding monomers. A particularly preferred self-crosslinking copolymer is a copolymer of vinyl acetate and N-methylolacrylamide. This copolymer has the advantage that it is with olefin polymers, especially polypropylene, is well tolerated, good stability at the deformation temperatures of the olefin polymers owns and is available at low cost.

The sized fiberglass filaments can be produced and sized in the usual way. One

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' 285375S

/ IS

a typical procedure for the production and sizing of the fiberglass filaments is shown in FIG the US-PS 38 49 148 described. With this method of operation, individual glass threads emerge from the openings of the electrically heated spinneret. These threads are drawn out and made into a fiberglass spun thread respectively summarized in a bundle of fiberglass, which consists of numerous individual threads. The plain is on the threads are applied with the aid of conventional devices, for example by a doctor blade device or a roller device. Details for an application device for the size are described in US Pat. No. 2,728,972. After the threads have left the spinneret, they are with air or preferably with water chilled. The threads are gathered into bundles by a collecting shoe and then passed to an extractor supplied for the spun thread, as for example in US-PS 32 92 013 and in the already mentioned US-PS 38 49 148 is described. The glass silk filament or the glass silk filament, if the individual threads emerging from the spinneret have been divided into several spun threads, then on a forming tube (forming tube) wound on a spindle (collet), which moves at a speed rotates from 7500 rpm, whereby a speed of movement of the spun thread of about 3660th to 4570th m / min. The molded packages of the fiberglass filaments are then dried. This is generally done in that the molded packs are heated to a temperature and for a period of time that

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is sufficient to remove substantially all of the water. In general, the drying times are good for the sized filaments at 132 ° G for about 11 hours. After drying, the molded tube can are removed and one then obtains a molded pack of the sized fiberglass filament. These form packages can be stored practically indefinitely. If the intention is to use the molded packing for reinforcement To use a polyolefin composite, a group of molded packages is arranged so that the Filaments can be unwound from them and laid down as a fiber mat, for example after the Method according to US-PSS 33 83 333 and 36 64 909. The mat is then needled and coated with the olefin polymer combined or impregnated or laminated with a sheet or film of the olefin polymer. One warms up then this intermediate certificate is expedient to a temperature of 204 to 221 ° C and under elevated Pressure, for example 650 kg / cm, for about 5 to about 20 minutes, around the sized glass threads to connect with the olefin polymers. The laminated products made of olefin polymers and the fiberglass mat can then be pressed or deformed in various ways, for example according to US Pat. No. 3,664,909. It can be used to produce glass fiber reinforced polyolefin laminates that can be used as containers or other objects of high strength and low cost.

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The coupling agent is used in such amounts that there is good adhesion between deti and glass thread the olefin polymer mediates "silar coupling agent are in a concentration of about 0.2 to 18% by weight, based on the weight of the solids of the size ^ -particularly suitable. A preferred concentration <of the silane is in the order of magnitude of about 6% by weight the solids of the size, whereby maximum adhesion is achieved with minimal costs «

The amount of lubricant is not essential to the invention. Any amount can be used that gives the sizing system good resistance and the sizing system Gives threads the desired lubricity. Usable amounts are usually around 30 to about 80 weight percent of the solids of the size solution. In particular when using malonized amorphous polypropylene as a lubricant, amounts of approx 60% by weight of this lubricant, based on the solids of the size preparation, is particularly useful.

The amount of stabilizer used depends according to the desired properties of the fiberglass filaments. A suitable amount is usually around 1 to about 9% stabilizer, based on the solids of the size formulation. A preferred amount of the Stabilizer is about half the amount of the Sxlankupplungsmittel, with particularly good adhesion of the film former is achieved on the coupling agent.

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A *

The uncrosslinked film former and the self-crosslinkable crosslinking material are blended in such quantities that the sized spun thread has the desired Has manageability. The uncrosslinked polymer, particularly the vinyl acetate homopolymer, imparts to the fiber Plasticity and its proportion vary depending on the hardness or fragility of the self-crosslinkable Film maker. The self-crosslinkable film former contributes to the integrity of the fiberglass filament is preserved and that it does not disintegrate into individual threads during processing or cutting. Usually the uncrosslinked polymer is used in amounts of about 5 to 40% by weight of the solids of the size formulation used. A suitable amount of the self-crosslinkable film former is between about 10 and about 50 % Solids by weight of the size formulation. A preferred amount of the self-crosslinkable film former is at about 22% by weight of the solids of the size preparation, achieving particularly good filament integrity will. A preferred amount of the uncrosslinked vinyl acetate homopolymer which is particularly easy to handle of the spun thread is about 9% by weight of the solids of the size preparation.

The size preparations used to manufacture the sized fiberglass filaments contain the generally about 95 to 80% water. A doctor blade device is preferably used for application and for this purpose As a rule, size emulsions or size solutions with 83 to 93% by weight of water are suitable. Of the

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As a result, the solids content of the size preparation depends strongly depends on the type of application device used.

The sized filaments and their shaped packings are basically suitable for the reinforcement of any objects made of polymeric materials. However, they are particularly useful for reinforcing olefin polymers, including polyethylene and polymers of 5-methylpentene. A particularly preferred olefin polymer for the layered glass silk filament according to the invention is polypropylene, since this polymer adheres particularly well to the sized thread, has good strength properties when reinforced with the sized glass silk filament and is available at low rust rates. The ratio of the olefin polymer to glass can vary within wide limits. In general, from about 10 to about 60 % by weight in the reinforced olefin body is suitable. A preferred amount is from about 35 to about 45 weight percent in a reinforced polypropylene article having high strength, other good properties, and low cost.

The amount of size applied to the fiberglass filament depends on the desired strength of the composite with the olefin polymer, good integrity the fiber and its manageability. A suitable amount of size is from about 0.02 to about 1% by weight the size solids based on total weight

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of sized fiberglass filament. An order of magnitude of approximately 0.6% is preferred, with one particularly good integrity and manageability of the fiber is maintained.

The invention is explained in more detail in the following example. The data on parts and percentages are weight data, unless otherwise noted.

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example

Composition of the size S e stan d t e

Functional chemical identification identification Parts by weight% solids Plain fabrics of the plain

Coupling center 1

Stabilizer lubricant

non-networking he film-maker

self-crosslinking film former

water
(deionized)

gamma-arainopropyltriethoxysilane (Onion Carbide A-IlGO)

Maleic acid

Emulsion of malo-

nized amorphous

Fq propylene

22% active

10 % surfactant and KOH

68% water

surface active s

Medium = alkoxylated

phenol

Vinyl acetate homopoly-

meres

(Emulsion with 54% by weight

Solids) (National Starch

Resyn 25-1031)

Vinyl acetate-N-methylolacrylamide copolymer

54 wt% solids emulsion (National Starch Resyn 25-2828) 0.7

0, 7.3

1.1

2.6

87.95

3 60

22nd

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The size for the fiberglass filament is made by deionizing most of the required material Water is placed in a mixing tank and the lubricant is added to the water with stirring. Then the coupling agent is introduced: and afterwards the maleic acid, while the egg is constantly stirred. After the addition of the maleic acid, stirring is continued for about 20 minutes to dissolve the acid. Then the non-crosslinking one film-forming material is added to the tank and then the emulsion of the crosslinkable polymer, which is diluted with an equal amount of cold deionized water before addition. That to supplement required water is then added and the batch is checked to see if its pH is around 6 and its solids content is about 5%.

In a preferred embodiment, the aqueous size is applied to the glass threads, which are drawn out of a spinneret with 400 openings. The filaments are coated using a doctor blade device with an amount of the size such that they have about 0.6 % size solids on the coated glass filaments. The threads are then combined in four or more fiberglass filaments or fiberglass bundles and wound onto spindles, forming packs of about 9 kg or more. The molded packs are dried and cured at 132 ° C. for about 11 hours. Once cured, the molded packs can be stored indefinitely at ambient conditions. The molded packs are then used to produce a

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Mat from the continuous thread used and this Mat can be needled and combined with an olefin polymer will. For example, 60 parts of polypropylene can be used for this purpose and 40 pieces of the needled mat are used. The reinforcement of the olefin polymer and the mat can at 204 ° C and a pressure of 6.3 kg / cm ^ for about

5 minutes. Heating under pressure can be between High-grade steel ribbons take place. The laminate from the mat the sized fiberglass thread and the olefin polymer can then be cut into test specimens, as for example in US-PS 38 49 148 in the columns

6 and 7 to determine structural strength and structural modulus. When using polypropylene as olefin polymers, the flexural strength is at least about 1610 kg / cm and the flexural modulus is at least about 70,000 kg / cm. As a result, the example shows that with sized fiberglass filaments Reinforced polypropylene according to the invention has excellent properties even if the molded packs of the filaments stored for a long period of time have been.

Of course, there are numerous within the scope of the invention Modifications are possible, for example a pigment or a dye can be added to the Schlich solution. Except you can use a different application device for the size, which does not have such a large amount of water in the sizing is required. Furthermore, the fiberglass filament or its molded packs for reinforcement of polymeric materials other than

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Olefinpolyraeren can be used. You can also use combinations of sized fiberglass filaments or their shaped packages with other sized or unsized filaments Use spun threads or with staple fibers.

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Claims (1)

Dr. Michael Hann (1176) H / Ha / You Patent attorney 2953755 Ludwigstrasse 67
6300 casting PPG Industries, Inc., Pittsburgh, Pennsylvania, USA SIZED GLASS SILK SPIDER AND ITS USE IN REINFORCEMENT OF OLEFIN POLYMERS Priority: August 14, 1978 / USA / Ser. No. 933 claims: 1. Sized fiberglass spun thread, characterized in that that the size is a coupling agent, a stabilizer, a lubricant, an uncrosslinked film-forming polymer and a cross-linked film-forming polymer Contains polymer. 2. thread according to claim 1, characterized in that the coupling agent is a silane or a Is siloxane. 3β thread according to claim 1 or 2, characterized in that that the coupling agent is an aminosilane. 020008/0554 originally inspected " ² " 285375b 4. Thread according to one of claims 1 to 3, characterized in that that the stabilizer is an ethylenically unsaturated mono- or dicarboxylic acid or its anhydride is. 5. thread according to claim 4, characterized in that the stabilizer is maleic acid or its anhydride is. 6. Thread according to one of claims 1 to 5, characterized in that that the lubricant is an emulsion of chemically modified polypropylene. 7. Thread according to one of claims 1 to 6, characterized in that that the size 2 to 18% by weight coupling agent, 1 to 9% by weight stabilizer, 30 to 80% by weight lubricant, 5 to 40% by weight of the uncrosslinked film-forming polymer and 10 to 50% by weight of a crosslinked one contains film-forming polymers. 8. thread according to claim 6, characterized in that the lubricant is a malonized amorphous Is polypropylene. 030008/0554 9. The method according to any one of claims 1 to 8,
characterized in that the uncrosslinked film-forming polymer is an epoxy polymer, polyester polymer, polyurethane, acrylic polymer, vinyl polymer or a mixture thereof. 10. thread according to claim 9, characterized in that the uncrosslinked film-forming polymer is a Is homopolymer of vinyl acetate. 11. thread according to one of claims 1 to 10,
characterized in that the crosslinked film-forming polymer is a
Is epoxy polymer, polyester polymer, polyurethane polymer, acrylic polymer, vinyl polymer, a copolymer of these monomers or a mixture of these polymers. 12. thread according to one of claims 1 to 11,
characterized in that the crosslinked polymer is a vinyl acetate copolymer. 030008/0554 13. thread according to one of claims 1 to 12,
characterized in that the size contains gamma-aminopfopyltriethoxysilane, maleic acid, raalonized amorphous polypropylene, a vinyl acetate homopolymer and a vinyl acetate-N-methylolacrylamide copolymer. 14. thread according to claim 13, characterized in that the size is about 0.6% by weight of the size Thread. 15. thread according to claim 14, characterized in that the size is about 6% by weight of silane, about
3% by weight maleic acid, about 60% by weight malonized amorphous polypropylene, about 9% by weight of the vinyl acetate homopolymer and about 22% by weight of the vinyl acetate-N-methylolacrylamide copolymer. 16. thread according to claim 1, characterized in that the stabilizer is "Himic" anhydride. 030008/0654 17. Use of the sized fiberglass spun thread according to one of claims 1 to 16 for reinforcement of polyolefins. 18. Use according to claim 17,
characterized in that the polyolefin is a polypropylene, polyethylene, 5-methylpentene or a mixture thereof, _o 030008/0554