A sizing composition for combined thread and its application

 

(57) Abstract:

The invention relates to the technology of composite yarns, coated with a sizing composition, and can be used for the production of composite materials. Combined thread of filamentary glass and thermoplastic fibers coated with a sizing composition, which consists of the basic mixture on the basis of at least 85 wt.% water and at least one additive in the form of ester fatty acids. Composite material based on at least one organic material and glass fiber contains, at least partially, these combined threads. During production of composite materials, yarn and fiber mix well, ensuring the satisfactory appearance of the surface of the material. 3 S. and 6 C.p. f-crystals, 3 tab., 2 Il.

The present invention relates to compositions for oiling the combined yarns and to the combined filaments with a coating of this composition.

Combined threads (or so-called mixed yarn) is a yarn consisting of filamentary organic and glass fibers and used for the production of composite materials. These threads Anyh fibers directly in filiere to get a good mix (deep mix). Methods of composite filaments directly in filiere described in particular in patents EP-A-0367661 (US 5011523), EP-A-0505275 (US 5328493), EP-A-0505274 (US 5316561), WO 93/15893, EP-A-0599695 and EP-A-0616055. Before combining in filiere filamentary thermoplastic and glass fibers, glass filaments cover of a sizing composition, in particular, to protect the threads from galling. Typically, this water composition (it contains more than 90 wt.% water), and water compositions more easy to use and is traditionally contained in the coating filamentary optical fibers (this type of songs has, in particular, greater ability to wetting the fiberglass).

However, thermoplastic materials have little or no compatibility with water and their hydrophobic properties lead to mutual repulsion oily filamentary optical fibers and thermoplastic filaments. This phenomenon of repulsion increases, as a rule, drying of the combined threads when using aqueous sizing composition (drying allows, in particular, to facilitate the use of combined yarns during the further processing, for example, in the extrusion method). Filamentary fiberglass tend to sruppirovannoye thread. Thus, instead of obtaining the desired "deep" mix filamentary glass and thermoplastic fibers in the combined threads marked segregation of thermoplastic fibers with partial or complete violation of the clutch in the threads of mixed fibers and thermoplastic filaments remain unprotected from potential abrasion or static electricity.

Segregation thermoplastic filamentary fibers and their vulnerability to abrasion make, in particular, problematic use of combined yarns in the textile industry, for example in weaving, where the braking threads are experiencing friction. In such cases, combined threads covered with water sizing tend to breakages and cause disruption looms. Poor mixing filamentary glass and thermoplastic fibers associated with segregation in the use of traditional aqueous sizing composition is observed at the level of the composite materials obtained from the combined threads that contains the above filamentary glass and thermoplastic fibers, and these composite materials have poor appearance of the surface the WMD aspect of the invention is achieved by a combined thread containing filamentary glass and thermoplastic fibers and coated with a sizing composition comprising the General mixture containing water and at least one binding agent, which according to the invention the thread is coated with a sizing composition comprising a basic compound containing at least 85% wt. water and optionally at least one additive in the form of ester fatty acids.

Preferably, the sizing composition contains at least one additive in the form of ester fatty acids in an amount of from 1 to 15% by weight of the basic mixture.

Preferably, the sizing composition contains at least one polyolefin.

It is expedient to provide a sizing composition contained in at least one of polypropylene, cross stitched, at least one acid or anhydride.

It is useful to have a sizing composition contained at least one neutralizing or stabilizing agent.

It is possible that an ester of fatty acids was complex ether alkoxysilanes fatty acids containing one or more hydroxy groups.

Preferably, loss prereactor a sizing composition for combined threads, containing the primary mixture of at least 85 wt.% water and at least one binding agent and at least one additive in the form of ester fatty acids.

This goal according to the third aspect of the invention is achieved by a composite material on the basis of at least one organic material and fiberglass, which according to the invention contains, at least partially, the composite yarn according to the first aspect of the invention.

Under the "main mix", according to the invention, is meant any aqueous sizing composition, usually used to cover filamentary optical fibers in filiere, and this composition usually has the form of an aqueous solution, aqueous emulsion or aqueous suspension. Examples of basic compounds are shown below.

The present invention relates also to the combined yarns, coated with a sizing composition according to the invention and obtained directly in filiere, and these combined threads have improved properties compared with the combined filaments obtained in filiere using traditional sizing.

A sizing composition according to Lovelace in the process of pulling in filiere; it is homogeneous and stable, in particular in filiere, and durable to shear at high-speed passage of the filament. In addition, the composition according to the invention is well wets the surface filamentary glass at high velocity hoods and provides good lubrication filamentary optical fibers, protecting them from abrasion.

In addition, the composition according to the invention has a very good ability to wetting not only filamentary optical fibers, and thermoplastic filaments. A sizing composition deposited on filamentary fiberglass, can be partially migrate into thermoplastic filaments after touching both of these filament. Thus, is the uniform distribution of a sizing substance throughout the obtained composite yarn, with filamentary glass and thermoplastic fibers perfectly wetted by the composition.

In the combined yarn, coated with the composition according to the invention, thermoplastic filaments lubricated, protected from abrasion and have a low tendency to accumulate static electricity, as well as filamentary fiberglass. In addition, nab the iti.

Advantages of combined yarns, coated with a composition according to the invention, many such threads are suitable for processing in weaving without the risk of breakages and have a high capacity for impregnation with organic substances. Composite materials obtained from these combined threads, if necessary, in combination with additional organic material, have a very good appearance of the surface, better than composite materials obtained in the same way, but from the combined yarns, coated with conventional oil, while the mechanical properties of the composite materials obtained from the yarns according to the invention, is as high as the mechanical properties of composite materials from traditional mixed threads.

The composition according to the invention may contain, as the main mix, any conventional sizing composition. Typically, the specialist selects the basic mixture of known compositions, in particular, depending on the type of thermoplastic filaments, used together with filamentary the optical fibers from the target using the obtained composite yarn, coated with the composition, and used organic , 5 wt.% and preferably at least 90 wt.% water and at least one compound that acts as a bonding agent.

In one of the embodiments of the invention the main mixture contains at least one binding agent, such as silane, titanium, etc. ensuring the adhesion of a sizing composition to the glass fiber. The basic mixture may also contain other binders, allowing after drying yarns, coated with a sizing composition, to improve the relationship between the glass fiber/ organic matter and, in particular, one or more binder of Magento" with additional functions in addition to those that have the above(s) binder(s) agent(s) and providing, for example, the interaction of the binder(s) agent(s) with an organic material. In particular, when the composite yarn according to the invention consist of filamentary optical fibers and thermoplastic filaments of the type of polyolefin and are designed to reinforce the material of the polyolefin, the main mixture may contain an emulsion of one or more polyolefins, similar to the polyolefin constituting thermoplastic filaments and/or reinforcing material, the polyolefin mullane the invention may also contain one or more neutralizing and/or stabilisasi agents, or any other agent, traditionally used in sizing compositions for the combined threads.

According to a preferential options for the implementation of the present invention when combined threads according to the invention contain polyolefin filaments (in particular, polypropylene) and are designed to reinforce polyolefin material (in particular, polypropylene), main mixture composition according to the invention covering the above thread contains at least one binding agent type silane, preferably aminirovanie ensuring the adhesion of the composition to the fiber, and at least one coagent linking polyolefin (polypropylene, respectively), graft-copolymerizing at least one acid or one acid anhydride, preferably maleic anhydride, which in addition to linking agent of the type of silane allows to improve the relationship between the fiber/polyolefin (polypropylene, respectively), and at least one neutralizing or stabilizing agent for temporarily neutralized prior to drying functions graft copolymerization agent linking polyolefin (polm the silane may be gamma aminopropyltriethoxysilane or N-beta(aminoethyl)gamma aminopropyltriethoxysilane, and neutralizing or stabilizing agent may be organic or inorganic base (sodium hydroxide, hydroxide, ammonia or primary, secondary or tertiary amine and so on).

A sizing composition according to the invention contains in addition to the basic mixture, at least one additive in the form of ester fatty acids. Preferably such an additive is an ester of alkoxysilanes fatty acids and preferably contains one or more hydroxypoly. As an example, such an additive may be an ester of ethoxylated fatty acids with gidroksilirovanii functions.

The composition usually contains an additive (s) in the form of complex (s) ether(s) fatty acids from 1 to 15 wt.%, preferably from 1 to 10 wt.% from the basic mixture. Preferably, this content is from 1 to 8 wt.% and most preferably from 1 to 6 wt.% from the basic mixture. This (these) additive (s) may be added at the time of receiving the basic mixture or directly in already received the bulk mixture.

It should be noted that the above-mentioned neutralizing (or stabilizing) agent may also neutralize the alcohol function added difficult AI as silane is used aminirovanie silane. In this case, if your main mixture contains neutralizing (or stabilizing) agent, the weight content of the neutralizing agent in the composition according to the invention is not necessarily higher than the original content of the neutralizing agent in the basic mixture, ensuring, at the same time, the desired neutralization in the basic mixture (e.g., neutralizing agent linking polyolefin in the above method implementation) and neutralization of complex fatty acid ester.

Ester of a fatty acid can also be neutralized by neutralizing (or stabilizing) agent other than used, if necessary in the basic mixture, with this additional neutralizing agent is added when obtaining the composition according to the invention.

According to preferred variants of implementation of the present invention, in which the combined threads contain polypropylene filaments (typically, polyolefin) and/or are designed to reinforce polypropylene material (polyolefin, respectively), the composition according to the invention covering these threads, contains the basic mixture containing from 0.05 to 3 weight. %, preferably from 0.1 to 1.5 wt.% tie the th, at least one acid or anhydride, and 0.1 to 5 wt.%, mainly from 0.2 to 1.5 wt.% neutralizing or stabilizing agent, and the composition contains, in addition to this basic mixture, one ester of fatty acid of from 1 to 10 wt.%, preferably from 1 to 6 wt.% from the basic mixture and optionally one additional neutralizing agent, identical or not already present in the basic mixture in a quantity sufficient to neutralize the complex ester fatty acids.

Combination thread according to the invention receives, in particular, in the following way: pull streams of molten glass in the form of paintings continuous filamentary fibers through one or more nozzles and cover the filaments of a sizing composition according to the invention (i.e., a composition comprising a primary mixture, to which is added an ester of a fatty acid) with one or more sealing devices, such as a sizing rollers, simultaneously forming thermoplastic organic material, while the trajectory filamentary optical fibers and thermoplastic filament match up to their connections in the combined thread pulled mechanically.

As a broad interpretation under "combined yarns, coated with a sizing composition described ... "threads, consisting of filamentary organic and glass fibers and coated with a sizing composition . . . in other words , not only covered the composition of the filaments obtained by tersenyum organic filament and oily filamentary optical fibers, but also yarn after drying and/or other processing to remove some of the components of the composition (in particular, water) and/or polymerization of certain components of the composition.

Composite yarn according to the invention can be obtained in the form of continuous filaments or tapes, as well as shtabelirovaniya either directly in filiere using the mechanical body of the actuator, or later after rewinding the obtained filaments, etc. Thus, the form of representation of the composite filaments varies depending on their destination.

The amount of sizing applied to the composite yarn according to the invention, is of the order of 0.2-5%, preferably 0.2 to 3% by weight of the filament. These strands are dried before connecting with a reinforcing organic material.

As it was marked the, is to obtain composite materials in combination with or without additional organic material. Composite materials can be, in particular, received at food extrusion machine combined yarns according to the invention, as described in patent application EP-A-0541441.

A sizing composition for combination of threads and a yarn according to the invention are described in the following examples, illustrated by drawings, where:

- Fig. 1A is a photograph of electron microscope slice traditional combined filament, Fig. 1B is a simplified diagram of this photograph;

Fig. 2A is a photograph of electron microscope slice of combination thread according to the invention, Fig. 2B is a simplified diagram of this pictures.

CONTROL EXAMPLE

800 filamentary optical fibers with a diameter of 17 microns, obtained by extraction in filiere molten glass E coated with a sizing roller is made of graphite of a sizing composition that is typically used for composite filaments of polypropylene filaments and filamentary optical fibers, combined with 800 polypropylene filamentary on a cylindrical bobbin.

Polypropylene filaments were formed by extrusion product having the trade name "VM 6100 K" SHELL, to which was added a binding agent having a trade name "Polybond 3002" by UNIROYAL CHEMICAL, 4% by weight of polypropylene.

A sizing composition applied to filamentary fiberglass, contained approximately 1 wt.% scanned silane, about 0.5 weight. % neutralizing agent type amine, about 13 wt.% emulsion of polypropylene grafted maleic anhydride, and this emulsion contained approximately 55% water. The total amount of water in the sizing was approximately 93%.

For filamentary optical fibers or polypropylene fibers constituting a combined thread, the contact angle caused by the sizing was measured on monofilament using weights Khan.

The results are shown in table I, which is attached below. Tests for attrition were conducted on the obtained mixed threads when they are passing through 3 steel grating with a diameter of 8 mm with a speed of 100 m/min and a tension at the input of F1about 120 cN. Measured yarn tension at the output of F2and the coefficient of friction was determined by the formula

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The results are shown in table II.

Also, using an electrostatic voltmeter Rotschild R 4021 test was performed Rothschild thread with a relative humidity of 60% and 20oC to assess the ability of the threads to the accumulation of static electricity. The thread was placed between 2 electrodes (150 V), the time values of polarized are shown in table II.

Were also measured mechanical properties of the composite materials obtained by injection-moulding of fibrogranular length of 12 mm from the previously received mixed yarn. Tear resistance tensile, bend strength, resistance to impact Charpy without potholes and lzod potholes were measured under the conditions specified by ISO R 527 ISO R 178, ISO R 179 and ISO R 180, respectively, and are shown in table III.

Received a combined thread, also, was passed through the nozzle sealing for further cutting, then sealed the thread soaked up termotehnika resin, then passed in a vacuum to remove bubbles before cutting and grinding, then the cross section of the obtained filaments were photographed under an electron microscope.

Fig. 1A is a photograph, illustrious the current example. Fig. 1b, which shows a simplified diagram of the slice (Fig. 1A) and "reference points" (Fig. 1A, they are not shown for reasons of clarity), illustrates a combined thread, consisting of filamentary optical fibers 1 and polypropylene filament 2, and the filament is surrounded by a protective (sealing) shell and has, in some places, traces termotehnika a sealing resin 4 (sealing shell and resin are used exclusively for photography). On pictures showing significant segregation (separation) of thermoplastic filaments studied the combined thread.

EXAMPLE 1

Acted as well as in the control example, adding to a sizing composition 3 wt.% of ester ethoxylated fatty acids with hydroxy groups, this product is commercially available under the trade name "Ensital PRF 416" firm SIDOBRE SINOVA.

The results of the various tests are shown respectively in tables I, II, III.

Fig. 2A is a photograph of a cross section of the obtained filaments made, as in the control example. There is a fairly homogeneous mixture (deep mix) filamentary optical fibers 11 (corresponding to white spaces in Fig. 2A and 2b) and thermoplastic is Ino for photography as in the control example.

EXAMPLE 2

Act the same way as in example 1, adding to a sizing composition of 6 wt.% "Ensital PRF 416".

The results of the various tests are shown respectively in tables I, II, III.

Noted (table I) that the traditional sizing composition used in the control example, very good wets the fiberglass and very bad polypropylene. Thus, it tends to settle on filamentary the optical fibers. A sizing composition according to the invention used in examples 1 and 2, moisten very well as fiberglass and polypropylene. Thus, part of the composition, covering filamentary fiberglass, migrates on polypropylene filaments. This migration occurs as a result of contact filamentary optical fibers and polypropylene filament.

It was also noted (table II) that the use of a sizing composition according to the invention leads to a reduction of the friction coefficient, depending on the concentration of ester ethoxylated fatty acids in the composition. In addition, when using a string according to the control example as the basis for the loom EOW laid threads. Conversely, the filaments of examples 1 and 2 do not give Ugarov and tens of thousands of meters so the main thread vrabatyvaetsja without stopping the loom.

There is also a very significant reduction in the capacity of threads according to examples 1 and 2 to the accumulation of static electricity, in comparison with the threads on the control.

Finally it is noted that the mechanical properties of the composite materials obtained from the yarns according to examples 1 and 2, as well as the mechanical properties of the composite materials of the yarns according to the control example. Such a conclusion is done regardless of the method of manufacturing a composite material of the composite filaments. So, as for composite materials woven plates of the composite fibers, the mechanical properties of the composite materials of the yarns according to the invention, at least the same as the mechanical properties of composite materials from traditional mixed threads.

A sizing composition according to the invention is suitable for all types of combined yarn: fibre/polyamide, fiberglass/polyair ... and combined yarn, coated with lubricant according to the invention, can material by molding, injection (injection molding), etc.

1. Combined thread containing filamentary glass and thermoplastic fibers and a coating of a sizing composition comprising the General mixture containing water and at least one binder, wherein the thread is coated with a sizing composition comprising a basic compound containing at least 85 wt.% water and optionally at least one additive in the form of ester fatty acids.

2. Combined thread under item 1, characterized in that the sizing composition comprises at least one additive in the form of ester fatty acids in quantities of 1 to 15% by weight of the basic mixture.

3. Combined thread under item 1 or 2, characterized in that the sizing composition comprises at least one polyolefin.

4. Combined thread on p. 4, characterized in that the sizing composition comprises at least one polypropylene, cross stitched, at least one acid or anhydride.

5. Combination thread according to any one of paragraphs.1 to 4, characterized in that the sizing composition comprises at least one neutralizing or stabilizing agent.

7. Combination thread according to any one of paragraphs.1 - 6, characterized in that the losses during combustion of 0.2 - 5 wt.%.

8. A sizing composition for composite yarns containing the primary mixture of at least 85 wt.% water and at least one binding agent and at least one additive in the form of ester fatty acids.

9. Composite material based on at least one organic material and an optical fiber, characterized in that it contains, at least partially, the composite yarn according to any one of paragraphs.1 - 7.

 

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