RU2182135C2 - Glass thread covered with oiling compound; oiling compound; method for producing oiled glass threads and composite based on mentioned glass threads - Google Patents

Abstract

FIELD: production of oiled glass threads and composite parts from them. SUBSTANCE: oiling compound for glass threads is formed by solution of viscosity lower than or equal to 400 cP including less than 5 mass percent of solvent and incorporating at least one thermally polymerized base system; mentioned base system has at least 60 mass percent of components whose molecular mass is below 750 and at least 60 mass percent of component (components) mixed up with at least one reactive epoxy group and component (components) with at least one reactive anhydride group. Compound may include catalyst, crosslinking agent, film-forming agent, and textile agent. Oiled glass threads are produced using this compound prepared by this method. Glass threads produced in this way are well compatible with various materials used for manufacturing composite parts. EFFECT: enhanced flexibility, integrity and effective shielding of threads against abrasive wear. 13 cl, 2 tbl, 14 ex

Description

 The invention relates to a sizing composition for glass fibers, and this composition is reactive when heated. The present invention also relates to a method for producing reinforcing glass fibers using this composition, as well as glass fibers and composites based on these fibers.

 In this description, under the terms "polymerization", "polymerize", "polymerizable". .. understand, respectively, "polymerization and / or crosslinking", "polymerization and / or crosslinking", "polymerizable and / or crosslinkable" ...

 Reinforcing glass fibers are obtained from streams of molten glass flowing from the openings of the spinnerets. These trickles are drawn in the form of continuous elementary fibers, which are then joined to form the warp yarn, then combined.

 Before the fibers are combined to form a filament, the glass fibers are coated with a sizing agent by passing through a sizing device. The application of a sizing is necessary for the formation of threads, which allows you to connect the thread with other organic and / or inorganic materials to obtain composites.

 The sizing is primarily used to lubricate and protect the threads from abrasion caused by friction of the thread at high speed against various elements of the machine during the above method.

 The sizing also ensures, in particular, after polymerization, the integrity of the above filaments by bonding elementary fibers to each other inside the filaments. This integrity is especially sought when yarns are used to obtain textile materials in which they are subjected to strong mechanical stresses. So, if elementary fibers are poorly interconnected, then they are easily torn and interfere with the operation of textile machines. In addition, incoherent fibers are considered difficult to process.

 The sizing also facilitates the wetting and / or impregnation of the threads with the reinforced material, and promotes the formation of bonds between the above threads and the above material. On the quality of adhesion of the reinforced material to the threads and on the ability to wet and / or impregnate the threads with reinforced materials, in particular, the mechanical properties of the composites obtained from the above material and the above threads depend.

 The sizing compositions used must be sufficiently stable and compatible with the drawing speeds of the elementary fibers, which must pass through the sizing (several tens of meters per second). They must be particularly resistant to shear deformation, which occurs when elementary fibers pass through the machine, and should well wet the surface of the fibers at the above speeds. In the case when the compositions polymerize when heated, they must have a sufficiently high reaction temperature in order to remain stable under the die. It is also desirable that these compositions have, after polymerization, a maximum degree of conversion (this degree corresponds to the ratio between the number of functions that reacted in the sizing after heat treatment and the content of reactive functions in the sizing before heat treatment) to ensure, in particular, the production of oiled fibers of constant quality (a sizing, the degree of conversion of which is very low in relation to the theoretically expected, can change over time).

 Most of the sizing agents currently in use are easy-to-use aqueous sizing agents, however, they need to be applied in large quantities to elementary fibers in order to become effective. Water in these sizing agents, respectively, is 90 wt.% (In particular, due to viscosity), which requires drying the threads before using them as amplifiers, because water can improve adhesion between threads and reinforced materials. Such drying, long and costly, must be adapted to the conditions of manufacture of the threads, and its effectiveness is not always optimal. When drying is carried out during a fiberization operation (that is, before the filaments are formed by combining the filament filaments), or the filaments themselves (international application 92/05122) or the filaments themselves (US patent application 3853605), it is necessary to install drying devices for each spinneret, and if drying, in particular, is carried out by wound filaments, this creates the risk of uneven and / or selective migration of sizing components into the winding (despite the fact that water sizing by themselves have tende unevenly distributed on the threads), as well as the possible appearance of dyeing of the threads or deformation of the winding. Winding deformation is also observed in the absence of drying, on windings with straight edges (layer-by-layer winding) of thin threads (that is, having a "titer" or "linear mass" of 300-600 tex (g / km) or less) coated with water sizing.

 Some patents describe non-aqueous lubricants, but these lubricants usually use cautious organic solvents that can harm the health of people near them because they are toxic and / or create viscosity problems that should be addressed by heating these lubricants (patent US 4,604,325) or additions of appropriate agents (US Pat. No. 4,609,591). These lubricants also often require the installation of special devices below each die; in particular, when the yarns are grouped in the form of windings, it is necessary to process the yarn before winding in order to avoid gluing the windings of each winding together, since this gluing makes it difficult to unwind the yarns. These treatments, the effectiveness of which depends on the operating conditions, consist, for example, in the polymerization of a sizing agent, by exposing the oiled fibers to ultraviolet radiation to give them the necessary integrity and ease of handling (US Patent Application 5049407). However, the polymerized sizing prevents slipping of the filaments relative to each other, and the lack of such mobility causes, upon mechanical destruction of the sizing, cracking of the threads during their cutting and can cause problems when using threads for textile purposes, where the threads used must be both solid and flexible.

 The object of the present invention is a sizing composition with improved properties that does not have the above disadvantages, intended for coating glass fibers and capable of polymerizing when heated, the composition makes the oiled threads easy to handle, even before polymerization, and gives them flexibility compatible with their subsequent processing; in addition, this composition after polymerization provides good integrity to the threads and has a significant degree of conversion; this composition also effectively protects the fibers from abrasion, gives them the ability to combine well with various reinforced materials to obtain composite products with high mechanical properties; it is very stable, in particular under the die, and is compatible with the drawing speeds of elementary fibers.

 The object of the present invention is also a method for producing oily glass fibers, as well as oily glass fibers, easy to handle, and having improved characteristics, the aforementioned filaments being an effective enhancer of the organic and / or inorganic materials from which the composites are obtained.

The sizing composition according to the invention is a solution with a viscosity lower than or equal to 400 cps containing less than 5 wt.% Solvent and a thermopolymerizable base system, the above base system containing at least 60 wt.% Components with a molecular weight below 750 and at least 60 wt.% mixture:
- component (s) containing at least one reactive epoxy functional group and
- component (s) containing at least one reactive anhydride functional group.

 The invention also relates to a method for producing oily glass fibers, according to which a plurality of molten glass jets are drawn from a plurality of holes located at the base of one or more dies, in the form of one layer or several layers of continuous elementary fibers, then the elementary fibers are joined to form one or several threads that are combined on a moving carrier, and the above method consists in applying to the surface of elementary fibers during the drawing process and before connecting the elementary fibers into the thread of the above sizing composition.

 The invention relates to threads coated with a sizing of the above composition, obtained according to the above method.

 Hereinafter, the expressions "epoxy (e) component (s)" and "anhydride (e) component (s)" mean, respectively, "component (components) with at least one reactive epoxy group" and "component (components) with at least one reactive anhydride group. "

 In the compositions according to the invention, the possible solvents present are mainly the organic solvents necessary for dissolving some of the polymerizable compounds. The presence of these solvents in a limited amount does not require special measures to remove them; moreover, in most cases, the lubricants according to the invention do not contain a solvent at all, that is, a compound playing only the role of a solvent in the solution.

 Due to the low viscosity (lower than or equal to 400 centipoise and preferably lower than or equal to 200 centipoise), the sizing composition according to the invention is compatible with the conditions for the production of glass fibers directly, and the viscosity of the composition is selected depending on the speed of drawing and the diameter of the elementary fibers (filaments) subjected to oiling. The composition according to the invention also has a wetting speed of the thread, compatible with the speed of drawing threads.

 Under the "thermopolymerizable base system" according to the invention is meant one or more compounds necessary for the sizing, the main function of which is to participate in the formation of the structure of the polymerized sizing, and these compounds are capable of thermally polymerizing. Typically, the base system comprises 60-100 wt.% Of a sizing composition according to the invention, in particular 70-99.5 wt.% Of the composition, and, in most cases, 75-90 wt.% In the composition.

 The basic system consists mainly of (preferably 80 wt.% And reaches 100 wt.% In most cases) of an epoxy component (epoxy components) and an anhydride component (anhydride components), and using a mixture of these components allows, after polymerization, epoxy anhydride copolymers (polyesters), constituting the largest part of the structure of the polymerized lubricant, and the properties of the oiled fibers directly depend on this structure.

 In addition, in the base system, most (preferably at least 70-75 wt.% And reaches 100 wt.%) Of the component (s) has a molecular weight below 750, and this component (these components) are usually the majority (and in most cases, each of them) the above epoxy and anhydride components.

 Preferably, and generally, the above components with a molecular weight below 750 have a molecular weight below 500. Likewise, in most cases, and preferably, these components are monomers (mono- or polyfunctional (which will be described below), however, the basic system may also contain components with a molecular weight below 750 in the form of oligomers or polymers with partially polymerized functional groups.

 According to some embodiments, the base system according to the invention, if necessary, may contain a small fraction of the component (s) involved in the formation of the structure of the polymerized sizing, but not containing an epoxy or anhydride group and / or having a higher molecular weight.

 According to a preferred embodiment of the invention, which achieves particularly satisfactory results, the base system consists solely of one or more components having at least one epoxy functional group and one or more components having at least one anhydride functional group , and / or may consist solely of components with a molecular weight below 750.

 Epoxy or anhydride components that can be used in the base system can have one (monofunctional components) or several (multifunctional components) of identical reactive groups selected from epoxy and anhydride groups.

The epoxy component of the base system can be, in particular, one or more of the following components: a simple alkyl glycidyl ether with an aliphatic C ₄ -C ₁₆ chain, etc .; simple cresyl or phenyl or nonyl phenyl or p-tert. butylphenyl or 2-ethylhexyl, etc. -glycidyl ether; limonenepoxide; cyclohexene monoxide; glycidyl ester of versatic acid or neodecanoic acid; etc. (moreover, the above components are monofunctional components); simple 1,4-butanediol or neopentyl glycol or resorcinol or cyclohexane dimethanol or 1,6-hexanediol or dibromonone neopentiglycol, etc. diglycidyl ether; a diepoxidized bisphenol-A or -F derivative; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate; bis (3,4-epoxycyclohexyl) adipate; polyglycol diepoxide; diglycidyl ether of hexahydrophthalic anhydride; diglycidyl hydantoin; 2- (3,4-epoxycyclohexyl) -5,5-spiro (3,4-epoxycyclohexyl) m-dioxane, vinylcyclohexene dioxide; simple trimethylol ethane or trimethylol propane or trisphenylol methane, etc. Triglycidyl ether, palm triglycidyl ether; p-aminophenol triglycidyl ether; tetra (p-glycidoxyphenyl) ethane; 4.4 '- (diglycidylamino) diphenylmethane; polyglycidyl ether of aliphatic polyhydric alcohol, epoxidized polybutadiene; novolac epoxyphenol or novolac epoxycresol resin; triglycidyl isocyanurate; N, N, N ', N'-tetraglycidyl-A, A'-bis (4-aminophenyl) - or N, N, N', N'-tetraglycidyl-A, A'-bis (4-amino-3, 5-dimethylphenyl) - etc. p-diisopropylbenzene; etc. (these components are multifunctional components).

 In general, as a rule, according to the invention, the amount of one or more epoxy components in the base system is 15-85 wt.%, Based on the weight of the sizing composition, in particular about 25-70 wt.%, Based on the weight of the sizing composition. In most cases, this amount is 35-60 wt.%, Calculated on the total weight of the sizing composition.

 The anhydride component (s) of the base system can be, in particular, one or more of the following components: methyl bicyclo (2,2,1) heptene-2,3-dicarboxylic acid anhydride; hexahydrophthalic anhydride; dodecyl succinic anhydride; phthalic anhydride; 1,4,5,6,7,7-hexachlorobicyclo- (2.2.1) -5-heptene-2,3-dicarboxylic acid anhydride; endo-cis-bicyclo- (2,2,1) -heptene-2,3-dicarboxylic acid anhydride; tetrachlorophthalic anhydride; pyromellitic dianhydride; 1,2,3,4-cyclopentantetracarboxylic acid dianhydride; polyazelaic acid polyanhydride; polisebacinic anhydride; glutaric anhydride; or polyester anhydride; bromo or dibromophthalic anhydride; cyclic sulfopivalin anhydride; bicyclic dicarboxylic anhydride; diphenoxyphosphinyl succinic anhydride; alkylene-2-glutaric anhydride; cycloaliphatic polyanhydride; styrene maleic anhydride; cyclooctadiene maleic anhydride; perchlorocumalin maleic anhydride; myrcene-monoepoxide maleic anhydride; cyclohexadiene dicarboxy maleic anhydride; poly (cyclopentadienyl) maleic anhydride; a derivative of trimellitic anhydride (neopentyl glycol bis (trimellitic) anhydride, an acidolysis product of tricarboxylic acid anhydride and an ester or amine, an oxyalkylated derivative of trimellitic anhydride); phenylene bis anhydride (3-butanedicarboxylic acid); benzophenone tetracarboxylic acid dianhydride; phenylalkylpentantetracarboxylic acid dianhydride; alkyl substituted tricyclodecodanecarboxylic acid dianhydride; dicarboxytetrahydronaphthalene succinic acid dianhydride; etc.

 As a rule, according to the invention, the amount of anhydride component (the proportion of anhydride components) in the base system is 5-65 wt.% Based on the total weight of the sizing composition, in particular about 10-55 wt. % of the total weight of the composition. In most cases, it is 15-45 wt.% Based on the total weight of the sizing composition.

 Preferably, according to the invention, the components of the base system and their amounts in the base system are selected so that the ratio "r" between the number of reactive anhydride centers and the number of reactive epoxy centers is 0.2-6 (moreover, one epoxy function is considered as one epoxy reactive center , and one anhydride function is considered as two reactive anhydride centers), so that the polymerization of the sizing composition can undergo a sufficient degree, in particular, due to formation epoksiangidridnyh copolymers (polyesters), and carrying out the polymerization by heat treatment. In most cases, according to the invention, this “r” ratio is 0.3-4 and, preferably, it is higher than 0.4 and lower or equal to about 2.0, in order to favor the formation of epoxy anhydride copolymers such as diesters, which are more stable (however , the formation of copolymers of the type of monoesters is not excluded when the ratio "r" is higher than 1, and this may provide advantages for enhancing some matrices).

According to an embodiment of the invention, the sizing composition, in addition to the base system, includes at least one specific catalyst that promotes the polymerization of the sizing agent by heating, facilitating the disclosure of the anhydride and / or epoxy functions, especially when the anhydride component or anhydride components of the base system are not very reactive, and / or possibly in the case where the base system does not contain cycloaliphatic epoxy components. This catalyst is preferably selected from amine derivatives, such as, for example, trialkylamines, hexamethylenetetramine, condensation products of aniline with formaldehyde, condensates of substituted aniline with aliphatic aldehyde (anhydrobutyraldehyde / toluidine), epoxy amines (N-2,3-diepoxypropylaniline) amines, N, N-dialkylalkanolamines, aminated polyacid salts, quaternary ammonium salts, quaternary imide-azoline salts, dicyanodiamide, etc .; or among derivatives of boron and phosphorus, such as, for example, organoboron ammonium salts, trialkanolaminoborates, fluoroborates substituted with organic substituents phosphines, etc .; or among metal derivatives, such as, for example, tin tetrachloride (SnCl ₄ ), salts of divalent tin, metal chelates containing epoxy groups; oxides of magnesium, barium, zinc, cadmium, etc .; or among alcohols.

 The polymerization of the epoxy and anhydride components can also be initiated by the presence of water (even in trace amounts), hydroxyl or carboxyl groups of the components of the sizing composition (presence, for example, hydrolyzed silanes), using moisture from the surrounding air, etc. In the absence of a catalyst, such as the one mentioned above, the ratio of "r", in addition, usually below 3, preferably below 2.

 The content of the above specific components, which play only the role of catalysts in the sizing composition, is below 3 wt.%, Based on the weight of the sizing composition, in most cases below 1 wt.% And preferably below or equal to 0.5 wt.%, Based on the sizing composition. The presence of a catalyst conducive to the disclosure of anhydride functions allows the use of less reactive anhydrides and a reduction in the polymerization temperature of the sizing agent, as will be explained later. In the case of highly reactive anhydride components, such as phthalic anhydride, maleic anhydride or succinic anhydride, the presence of a catalyst is usually avoided.

 In addition to the base system and the specific catalyst, the composition according to the invention may contain in a small amount additives that impart special properties of the sizing composition, however, do not significantly participate in the structure of the sizing, in contrast to the base system. Although these additives are different from the base system, they can be thermally polymerized as compounds of the base system.

 The composition according to the invention may contain, as an additive, at least one crosslinking agent, allowing the sizing agent to be attached to the glass, the amount of the crosslinking agent being 0-25 wt.%, Calculated on the sizing, and preferably below or equal to 20 wt.%, based on the sizing. These agents may be one or more of the following components: silanes, such as gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, polyethoxylated-propoxylated trimethoxysilane, gamma-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, phenylaminophenyl; titanates, zirconates, siloxanes, etc.

 The composition according to the invention may also contain, as an additive, at least one film-forming agent that has only one function - it facilitates gliding and facilitates fiber production, the amount of this agent is 0-10 wt.% And preferably less than or equal to 5 wt.% . The presence of this agent prevents significant friction of the filaments on the oiling device when the filaments are pulled at a high speed (more than 40 m / s) and / or when they are very thin, but these agents are expensive and can cause deterioration of the mechanical properties of the composites. Such agents may be one or more of the following components: silicones, siloxanes or polysiloxanes, such as glycidyl (n) polydimethylsiloxane, alpha-omega-acryloxypolydimethylsiloxane, etc. derivatives of silicones, such as silicone oils, etc.

 The composition according to the invention can also include, as an additive, at least one agent used for textile purposes, which plays mainly the role of a lubricant, in amounts of 0-15 wt. % and preferably 0-8 wt.%. These agents may include the following components: fatty esters (possibly ethoxylated or propoxylated), glycol derivatives (in particular ethylene or propylene glycol), such as isopropyl palmitate or cetyl palmitate, isobutyl stearates, decylaurates, ethylene glycol adipates, polyethylene glycols and polyethylene glycols 2000, isopropyl stearates, etc.

 The sizing may also contain, as an additive, at least one agent for adapting the yarn to the reinforced materials, in particular cement materials.

The sizing composition according to the invention effectively protects the fibers from abrasion, it is stable under the die (the composition according to the invention does not polymerize until it reaches 100 ^° C and is exposed to temperatures not exceeding 70 ^° C under the die), is compatible with drawing speeds of elementary fibers and does not require drying operations before polymerization or special processing between applying a sizing agent on the fiber and the operation of combining oily fibers.

 In addition, when the composition according to the invention is applied to elementary fibers during the drawing process, it is very quickly distributed over their entire surface with the formation of an almost protective film on each fiber. The yarn obtained by combining elementary fibers and coated with a thermally untreated composition (i.e., not yet polymerized) is thus a bundle of elementary fibers in a sheath that can slide against each other, while such a thread has considerable flexibility, which is especially important when the thread must be cut, and the presence of a sheath for elementary fibers creates additional protection against abrasive wear. Such a thread does not yet have integrity in the usual sense of the word, that is, it does not consist of elementary fibers interconnected by type, for example, gluing, which is provided by one or more sizing components, such as film-forming gluing agents, present in significant quantities in sizing. Despite this, it is easy to work with such a thread coated with a non-polymerized composition, and if the thread is wound in the form of packages, then such a thread can be easily removed from the packages without pre-processing by polymerization of the sizing. The filaments coated with an unpolymerized sizing composition also have a very good ability to wet and impregnate with reinforced materials, so the impregnation can be carried out much faster (which creates a gain in productivity), and the resulting composites have a more uniform appearance, and some of their mechanical properties improve .

 The integrity of the thread by gluing the elementary fibers that make up the thread is achieved by polymerization of a sizing composition under the influence of heat. This integrity is imparted to yarns, which are subsequently subjected to strong mechanical stresses if they are used, for example, for textile processing (the ratio “r” of the composition is preferably about 0.5-2, if the yarn is used to make fabrics), or, in some cases cut threads, i.e. staple fibers designed to reinforce organic and / or inorganic materials. In the described cases, the polymerization of the sizing is preferably carried out respectively before using yarns for textile purposes or before introducing the cut yarns into the reinforced materials.

 The integrity achieved after the polymerization of the sizing agent is particularly high, while the content of the sizing agent on the threads is relatively low (the loss on ignition of the threads coated with a sizing composition and / or obtained by the method of the invention does not exceed 3 wt.%). The amount of sizing composition that needs to be applied to the yarns to obtain the desired effect is preferably small, however, it allows yarns to have very good characteristics, including high integrity (this integrity is high even when the sizing on the fibers is of the order of 0 , 6 wt.%).

 The sizing composition according to the invention after polymerization has a maximum degree of conversion, and the degree of conversion of the anhydride components, for example, is close to 100% when the ratio "r" is approximately lower than 1.

 In addition, it was unexpectedly found that properties such as tensile strength of the yarn according to the invention are improved after short aging in a humid environment, compared with the properties achieved by the yarn before aging.

 The filaments according to the invention can be introduced into various reinforced materials to obtain composite elements having good mechanical properties. The composition according to the invention gives the yarns excellent compatibility with reinforced materials, in particular with organic materials, for example epoxy materials, as well as with inorganic materials such as cement materials. It also provides impregnation of oily threads with reinforced materials. This composition is particularly suitable for producing continuous filaments, combined in the form of packages with layered winding, Easter cakes, cops or assembled into mats, etc., or to obtain cut filaments, and these various filaments consist of elementary fibers with a diameter in the range of about 5-20 microns . The sizing composition according to the invention is particularly suitable for producing continuous thin filaments (with a titer below 600 tex), which are in the form of packages with layered winding, in contrast to traditional aqueous sizing.

 The sizing composition according to the invention is preferably applied in the process of the method according to the invention to elementary fibers intended to form a filament, then it is polymerized by heat treatment, and the above treatment is carried out independently of the fiber formation operation (i.e. there is no need to install devices under each die) and it can be carried out at various stages of the method after fiberization operations.

Heat treatment can, in particular, be carried out on the combined threads or during the preparation of the composite by introducing oily fibers into the organic material. In the case when the obtained yarns are combined in the form of windings, then heat treatment of the wound yarns is carried out before their use, in particular, before textile processing. If the heat treatment of the wound yarns is carried out before unwinding the yarn, it is desirable that the turns of wound yarns forming a package have an intersection angle of at least 1.5 ^° so that the windings do not stick together with a polymerized sizing, since this bonding makes it difficult to unwind.

 The filaments obtained after connecting the elementary fibers can also be combined on moving receiving receiving devices. So, they can be applied using a device that also serves to draw the fibers onto the receiving surface, which is moved in the transverse direction to the applied threads to obtain a layer of continuously randomly arranged threads forming a "mat", in this case, the heat treatment of the threads can be carried out on the receiving surface , where they are. If necessary, a binder (and this binder may optionally contain the above catalyst added to the sizing) can be added to the mat before heat treatment of all the combined threads, and heat treatment can lead to the polymerization of both the binder and sizing.

 The threads, before combining them, can be cut using a device that also serves to draw them, and the cut fibers are collected on moving receiving carriers, in this case, heat treatment of preferably cut threads located on the receiving carriers is carried out.

Heat treatment of filaments in the form of packages with layered wrapping, weighing several kilograms, is carried out for at least 1 hour at a temperature above about 140 ^o C, preferably about 160 ^o C, if the fibers are coated with a composition according to the invention that does not contain a specific catalyst ( high temperature favors the formation of more stable compounds), and the processing time varies depending on the shape and weight of the layer-by-layer packaging, with the majority of this time spent on increasing e the temperature of the mass of glass contained in the winding. When the yarns coated with the composition according to the invention, which does not contain a specific catalyst, are combined on one or more moving supporting devices and when they are heat treated, the processing time is about 15-20 minutes at temperatures usually above about 140 ^o C. Processing temperature, regardless of the method combining the filaments may be reduced by several tens of degrees (it can be reduced, e.g., at 10-30 ^o C and between about 120-140 ^o C) and the treatment time reduced when the coating n ti composition comprises at least one specific catalyst such as defined above.

 Glass fibers can also be combined without heat treatment, in which case heat treatment is carried out later. In particular, the filaments can be combined in the form of windings, then they are extracted from the above windings in order to undergo additional processing (for example, cutting using a device that also serves to draw them, mechanically), and the heat treatment of the fibers can be carried out before time or after additional processing (in particular, when cutting, heat treatment can be carried out on the device on which the cut fibers are collected).

Oiled threads can also be combined without heat treatment, then they are subjected to heat treatment after joining the threads with organic material during the preparation of the composite, and the above material may include at least one catalyst mentioned above. Depending on the organic material used, heat treatment may be accompanied by UV treatment, electron beam processing, etc. The heat treatment time during preparation of the composite is usually at least 2 hours, at temperatures above about 130 ^{° C.} and preferably about 180-200 ^° C.

 Glass fibers coated with a sizing according to the invention and / or obtained according to the method of the invention are coated with an unpolymerized sizing or sizing polymerized after heat treatment. These threads have a loss on ignition, preferably below 3% by weight, and preferably below 1.5%. A small amount of sizing applied on the threads can significantly reduce the problems of bonding between the threads, especially when they are in the form of windings, which allows better access to the fibers during the impregnation of the reinforced material and is an economic advantage.

 The yarns obtained according to the invention are yarns that are easy to work with, and after combining them, they can be in various forms, requiring or not requiring additional processing steps, these steps being carried out before or after heat treatment and / or combining of the yarns. Glass fibers in this way can be in the form of continuous threads, cut threads, can be assembled into strands, tapes, mats or nets, woven or non-woven. The filaments according to the invention have particularly good tensile strength properties.

 Composites, preferably obtained using at least one glass fiber according to the invention and in at least one organic and / or inorganic material (the glass content in these composites is usually 30-70 wt.%), Have good mechanical properties, as illustrated below in examples.

 Other advantages and characteristics of the invention are given in light of illustrative examples, but not limiting the scope of the invention, in which sizing compositions according to the invention and characteristics of fibers coated with these compositions and characteristics of composites containing the above fibers are presented.

EXAMPLE 1
Elementary fibers with a diameter of 14 microns, obtained by drawing streams of molten glass according to the method of the invention, are coated with a sizing of the following composition, expressed in mass percent:
Components of a base system with a molecular weight below 750:
Trimethylolpropantriglycidyl ether (1) - 34.0%
Simple 1,4-butanediol-diglycidyl ether (2) - 18.4%
1,2-Epoxyhexadecane (3) - 29.1%
Methyltetrahydrophthalic anhydride (4) - 10.0%
Catalyst:
1-Methylimidazole (5) - 0.5%
Additives:
Polyethoxylated alkylsilane (6) as a crosslinking agent - 8.0%
The ratio of "r" in this composition is 0.24.

Elementary fibers are combined to form filaments, which are wound in the form of packages with layered winding having an approximate weight of 13.5 kg, then the package is heated at 140 ^o C for 6 hours.

 After that, the threads are removed from the windings to measure their strength and their tensile strength under tension under conditions determined according to ISO 3341. The results obtained on 8-10 samples (indicating the type of error in brackets) are presented in the attached comparative table I, in which also indicates the titer and loss on ignition of the obtained filaments.

EXAMPLE 2
The elementary fibers with a diameter of 14 microns obtained according to the invention are coated with a sizing of the following composition (in mass percent):
Components of a base system with a molecular weight below 750:
3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (7) - 28%
A mixture based on vinylcyclohexene monoxide (8) - 28%
A mixture of phthalic anhydride with hexahydrophthalic anhydride and tetrahydrophthalic anhydride (9) - 28%
Additives:
Gamma-methacryloxypropyltrimethoxysilane as a crosslinking agent (10) - 10%
Isopropyl palmitate as an agent for textile processing - 6%
The ratio of "r" in this composition is 0.7, and this composition has a viscosity of 64 centipoise at 20 ^o C.

 Elementary fibers are combined to form filaments that are wound in the form of layered wrap packages having an approximate weight of 13.5 kg. Thus, the combined fibers are not subjected to heat treatment.

 From the obtained yarns having a titer of 320 tex, according to the standard NF 57152, composite plates with a parallel arrangement of yarns are obtained. The reinforcing resin is the resin "Epoxy LY 556", sold under the name CIBA GEYGI, to which 100 wt. parts of epoxy resin; 90 parts of hardener sold under the name "HY 917" by CIBA GAGI and 0.5 parts of an accelerator sold under the name "DY 070" by CIBA GEYGI.

The resulting plates are then subjected to heat treatment and, in accordance with ISO 178 and ISO 4585, the mechanical properties inherent in these plates, such as bending and shear deformation, are determined before aging and after immersion of these plates in water at 98 ^° C for 24 hours. The results obtained for 8-10 samples are presented in comparative table II, which is given as an appendix, in which the type of resin used for the plates, the tensile strength in bending at a glass content adjusted to 100%, before and after aging, and the tensile stress at deformation are given shear before and after aging. Error types are indicated in parentheses.

EXAMPLE 3
They act in the same way as in example 2, however, by heat treatment of the wound fibers, and not composite plates. Obtained in example 2, the package with a layered winding is heated, according to the present example, at 160 ^o C for 8 hours. No deformation of these layered wound threads was found. The results obtained for composite plates according to this example are presented in table II.

 The force and tensile strength under tension of the heat-treated yarns extracted from the windings are also measured, as in Example 1. The results are presented in Table I.

EXAMPLE 4
The elementary fibers with a diameter of 14 microns obtained according to the invention are coated with a sizing of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (7) - 25%
1,4-Butanediol-diglycidyl ether (2) - 10.0%
2-Ethylhexylglycidyl ether (11) - 20.0%
5-methyl-norbornene-2,3-dicarboxylic acid anhydride (12) - 36.5%
Catalyst:
1-Methylimidazole (5) - 0.5%
Additives:
Polyethoxylated alkylsilane (6) as a crosslinking agent - 8.0%
The ratio of "r" in this composition is 1.3, and this composition has a viscosity of 72 centipoise at 20 ^o C.

Elementary fibers are combined to form filaments, which are wound in the form of packages with layered winding weighing about 13.5 kg, then heated at 160 ^o C for 6 hours. The tensile strength and tensile strength of the strands are then determined as in example 1 (table I). The abrasion resistance of the threads is measured by weighing the mass of torn fiber obtained after passing the fibers through a series of rods. For various threads coated with the polymerized sizing described in this example, the mass of the torn fiber at the end of the test is about 1 mg per 1 kg of the test thread.

 By comparison, yarns coated with an aqueous emulsifier based on an epoxy resin, silane and surface active agent emulsion and dried by conventional methods can produce 200, even 500 mg of torn fiber per kg of yarn.

EXAMPLE 5
The elementary fibers with a diameter of 10 microns obtained according to the invention are coated with a sizing of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
Diglycidyl ether based on phenol-novolac resin (13) - 25.0%
1,4-Butanediol-diglycidyl ether (2) - 10.0%
2-Ethylhexylglycidyl ether (11) - 16.5%
Methyltetrahydrophthalic anhydride (4) - 40.0%
Catalyst:
1-Methylimidazole (5) - 0.5%
Additives:
Polyethoxylated alkylsilane as a crosslinking agent - 8.0%
The ratio of "r" in this composition is 1.57, and this composition has a viscosity of 104 centipoise at 20 ^o C.

Elementary fibers are combined to form filaments, which are wound in the form of Easter cakes weighing about 7 kg, then heated at 140 ^o C for 6 hours. The tensile strength and tensile strength of the strands are then determined as described in Example 1 (Table I).

EXAMPLE 6
The elementary fibers obtained according to the invention are coated with a sizing of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
Trimethylolpropantriglycidyl ether (1) - 24%
2-Ethylhexylglycidyl ether (11) - 24%
5-methyl-norbornene-2,3-dicarboxylic acid anhydride (12) - 40%
Additives:
Gamma-methacryloxypropyltrimethoxysilane (10) as a crosslinking agent - 12%
The ratio of "r" in this composition is 1.9.

 Elementary fibers are combined to form filaments, which are wound in the form of packages with layered winding. The resulting package is not subjected to heat treatment.

 Of these yarns, which are easily removed from the resulting packages, composite plates are obtained in the same manner as in Example 2, then they are thermally processed. The mechanical properties of these plates, measured under the same conditions as in example 2, are presented in table II.

EXAMPLE 7
Follow the same method of operation as in example 6, using an identical sizing composition, but with a lower crosslinking agent content (11.6% instead of 12%) and, in addition, containing a catalyst in the form of 2,4,6-tridimethylaminomethylphenol produced on sale under the name "Protex NX3" by PROTEX, in an amount of 0.4% based on the weight of the composition.

 The results are presented in table II.

EXAMPLE 8
The elementary fibers obtained according to the invention are coated with a sizing of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
4,4'-Diaminodiphenylmethanetetraglycidyl ether (14) - 20.0%
Cresylglycidyl ether (15) - 15.0%
Cyclohexanedimethanol-diglycidyl ether (16) - 8.0%
Methylhexahydrophthalic anhydride (17) - 42.0%
Catalyst:
2-Propylimidazole (18) - 0.3%
Additives:
Gamma-methacryloxypropyltrimethoxysilane (10) as a crosslinking agent - 8.7%
Gamma-glycidoxypropyltrimethoxysilane (19) as a crosslinking agent - 6.0%
The ratio of "r" in this composition is 1.68.

 Then they work as in example 6, using instead of epoxy resin in the obtained composite plates, the resin based on the complex polyester "M 402", sold under the same name by the company CIBA GEYGI, to which is added, per 100 wt. parts of a polyester resin, 20 parts of a flexibility agent sold under the name "F 8010 C" by CIBA GAGI, 16.5 parts of styrene and 1.5 parts of an accelerator sold under the name "TNM 60" by CIBA GAYGI.

 The results are presented in table II.

 EXAMPLE 9

They work in the same way as in example 6, replacing the sizing composition used there with a composition of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
Diglycidyl ether of bisphenol A (20) - 21.0%
Cresylglycidyl ether (15) - 25.0%
Methylhexahydrophthalic anhydride (17) - 42.0%
Catalyst:
Organometallic amine in polyglycols (21) - 0.4%
Additives:
Gamma-methacryloxypropyltrimethoxysilane (10) as a coupling agent - 11.6%
The ratio of "r" in this composition is 1.98.

 Then follow the procedure of example 6. The results are presented in table II.

EXAMPLE 10
The elementary fibers obtained according to the invention are coated with a sizing of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
Cyclohexanedimethanol-diglycidyl ether (16) - 10.0%
2-Ethylhexylglycidyl ether (11) - 14.0%
Methylhexahydrophthalic anhydride (17) - 40.0%
Components of a base system with a molecular weight below 750:
Triglycidyl ether based on an aliphatic polyhydric alcohol with an average molecular weight of 1950 (22) - 20.0%
Catalyst:
2-Propylimidazole (18) - 0.4%
Additives:
Gamma-methacryloxypropyltrimethoxysilane as a crosslinking agent - 11.6%
Isopropyl palmitate as an agent for textile processing - 4.0%
The ratio "r" in this composition is 2.96%.

Elementary fibers are combined to form filaments, which are wound into packages with a layered structure, then heated at 145 ^o C for 8 hours. The tensile strength and tensile strength of the fibers are then determined as in Example 1 (Table I).

 Composite plates are obtained from the obtained filaments, which easily come off the packages, in the same manner as in Example 3, however using, instead of the LY 556 epoxy resin, the CY 205 epoxy resin sold under the name CIBA under this name GAGEY, to which is added, per 100 wt. parts of epoxy resin, 32 wt. parts of a hardener sold under the name "NT 972" by CIBA GAGI.

The mechanical properties of the obtained plates are determined as in example 2, before aging and after immersion of the plates in water at 98 ^o C this time for 72 hours (table II).

EXAMPLE 11
Act as in Example 2, using an identical sizing composition, but containing a smaller amount of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (9.3% instead of 28%), a smaller amount of a mixture based on vinylcyclohexene monoxide (18.7% instead of 28 %) and a larger amount of a mixture of phthalic anhydride with hexahydrophthalic anhydride and tetrahydrophthalic anhydride (58% instead of 28%). The ratio of "r" in this composition is 2.84, and this composition has a viscosity of 76 centipoise at 20 ^o C.

 The results are presented in table II.

EXAMPLE 12
Work, as in example 3, using a sizing composition according to example 11. The results are presented in tables I and II. The abrasion resistance of the fibers is measured in the same manner as in Example 4. The weighted mass of the torn fiber at the end of the test is 99 mg per 1 kg of thread.

EXAMPLE 13
The elementary fibers with a diameter of 14 microns obtained according to the invention are coated with a sizing of the following composition (mass percent):
Components of a base system with a molecular weight below 750:
3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (7) - 9.25%
A mixture based on vinylcyclohexene monoxide (8) - 9.25%
A mixture of phthalic anhydride with hexahydrophthalic anhydride and tetrahydrophthalic anhydride (9) - 55.5%
Additives:
Gamma-methacryloxypropyltrimethoxysilane as a crosslinking agent (10) - 20
Isopropyl palmitate as an agent for textile processing - 6%
The ratio "r" in this composition is 4.19, and this composition has a viscosity of 62 centipoise at 20 ^o C.

Elementary fibers are combined to form filaments, which are wound in the form of a package with layered winding weighing about 13.5 kg, then heated at 160 ^o C for 8 hours. The tensile strength and tensile strength when stretching the threads is determined as in example 1 (table I).

 The abrasion resistance of the threads is determined in the same way as in example 4. The weighted mass of the torn fiber at the end of the test is 57 mg per 1 kg of thread.

COMPARATIVE EXAMPLE
The mechanical characteristics of the composites obtained using the yarns described in examples 2, 3, 6-12 are compared with the mechanical characteristics of the composites obtained using control yarns coated with an aqueous sizing based on an epoxy resin emulsion, silanes and surface-active agents, these the latter composites are obtained in the same manner as in examples 8 (carrying out, however, the heat treatment of wound threads, not composite plates) and 10 (performing heat treatment of the threads at a higher temperature), corresponding to but, and mechanical properties of the latter composites, defined as in Examples 2 and 10, respectively, are presented in Comparative Table II.

 The previous examples show that the yarns coated with the sizing according to the invention are yarns that are easy to work with, whether they are heat treated or not, and they have good tensile strength properties. It also turned out that the tensile strength of the yarns coated with the sizing according to the invention is higher after aging in a humid environment than oiled yarns studied before aging.

 The yarns obtained according to the invention, in addition, have insignificant losses during calcination, good abrasion resistance and can effectively strengthen organic and / or inorganic materials.

 The insignificant amounts of fibers obtained during the abrasion resistance tests of the yarns and the high properties with respect to tensile strength also allow us to say that the yarns obtained according to the invention have good integrity. The resulting yarns also have good texture properties.

 The filaments coated with the sizing according to the invention, in addition, allow to obtain composites having also high mechanical properties than those of composites obtained from threads coated with traditional aqueous sizing.

 The glass fibers according to the invention can serve for various purposes, for example, for textile use, in particular for the manufacture of warp warp bases, or directly as amplifiers, for example, for strengthening organic materials (e.g. plastics) or inorganic materials (e.g. cement materials ) to obtain composite products.

The values of indices (1) - (22) are as follows:
(1) marketed under the name "Heloxy 5048" by SHELL
(2) marketed under the name "Heloxy 67" by SHELL
(3) marketed under the name "UVR 6216" by UNION CARBIDE
(4) marketed under the name "HY 917" by CIBA GAGEY
(5) marketed under the name "DY 070" by CIBA GAGEY
(6) marketed under the name "Silquest A 1230" by OSI
(7) marketed under the name "UVR 6110" by UNION CARBIDE
(8) marketed under the name "UVR 6200" by UNION CARBIDE
(9) marketed under the name "HY 905" by CIBA GAGEY
(10) marketed under the name "Silquest A 174" by OSI
(11) marketed under the name "Heloxy 116" by Shell
(12) marketed under the name "NU 906" by CIBA GAGEY
(13) marketed under the name "Araldite PY 307" by CIBA GAGEY
(14) marketed under the name "Araldite MY 722" by CIBA GAGEY
(15) marketed under the name "Heloxy 62" by Shell
(16) marketed under the name "Heloxy 107" by Shell
(17) marketed under the name "NU 1102 BD" by CIBA GEYGI
(18) marketed under the name "Actiron NXJ 60" by PROTEX
(19) marketed under the name "Silquest A 187" by OSI
(20) marketed under the name "Araldite GY 250" by CIBA GAGEY
(21) marketed under the name "DY 071" by CIBA GAGEY
(22) marketed under the name "Heloxy 84" by SHELL

Claims (13)

 1. Glass fiber coated with a sizing composition consisting of a solution with a viscosity lower than or equal to 400 cps containing less than 5 wt. % solvent and at least one thermally polymerizable and / or crosslinkable base system, said base system comprising at least 60 wt. % of components with a molecular weight below 750 and it contains at least 60 wt. % mixture: at least one component containing at least one reactive epoxy functional group, and at least one component containing at least one reactive anhydride functional group.  2. Glass according to claim 1, characterized in that the basic system is 60-100 wt. % of sizing composition.  3. Glass according to claim 1 or 2, characterized in that the base system consists exclusively of one or more components having at least one functional epoxy group and one or more components having at least one functional anhydride a group.  4. Glass according to any one of paragraphs. 1-3, characterized in that the composition includes, at the same time, at least one catalyst that facilitates the opening of anhydride or epoxy groups under the influence of heating.  5. Glass according to any one of paragraphs. 1-4, characterized in that the composition includes, in addition, at least one crosslinking agent in an amount of from 0 to 25 wt.%.  6. Glass according to any one of paragraphs. 1-5, characterized in that the composition includes, in addition, at least one film-forming agent in an amount of from 0 to 10 wt. %  7. Glass according to any one of paragraphs. 1-6, characterized in that the composition includes, in addition, at least one textile agent in an amount of from 0 to 15 wt. %  8. A sizing composition for glass fibers formed by a solution with a viscosity lower than or equal to 400 cps, comprising less than 5 wt. % solvent and containing at least one thermally polymerizable and / or crosslinkable base system, the above base system comprising at least 60 wt. % of components with a molecular weight below 750 and at least 60 wt. % mixture: component (s) containing at least one reactive epoxy functional group and component (s) containing at least one reactive anhydride functional group.  9. A method of producing oily glass strands, according to which a plurality of streams of molten glass are drawn, flowing through a plurality of holes located at the base of one or more dies, in the form of one or more layers of continuous elementary fibers, then the elementary fibers are connected to form one or more filaments, which combine on a moving basis, and the above method consists in applying to the surface of elementary fibers, in the drawing process and before connecting the elementary fibers with the formation of filaments, sizing composition according to p. 8. 10. The method according to p. 9, characterized in that the threads are combined in the form of windings on a rotating basis, and the intersection angle of the windings is at least 1.5 ^o .  11. The method according to any one of p. 9 or 10, characterized in that the sizing composition is subjected to heat treatment during or after combining the threads coated with the above composition.  12. The method according to any one of paragraphs. 9-11, characterized in that the combined oily filaments are brought into contact with the reinforced organic material before the filaments are subjected to heat treatment to obtain a composite.  13. A composite containing at least one organic and / or inorganic material and oily glass fibers, characterized in that it includes at least partially oiled glass fibers according to any one of paragraphs. 1-7.

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