Chemical treatments for fibers and wire-coated composite strands for molding fiber-reinforced thermo

专利摘要:
PURPOSE: Chemical treatments for fibers and wire coated composite strands for molding fiber reinforced thermoplastic composite articles are provided to size and/or preimpregnate the fibers in use of a chemical treatment to fibers (10), such as reinforcing fibers (12) suitable for making a composite article. CONSTITUTION: A chemical treatment has a relatively low viscosity and is substantially solvent free and non radiation curable. Heat energy may be employed to lower the viscosity and improve the wetting ability of the applied treatment and/or to increase the molecular weight of, or otherwise cure, the treatment with essentially no generation of solvent vapor. The treated fibers (32) are used to form a composite strand (14), which may be subsequently processed in-line or off-line into a composite article having fibers disposed in a polymeric matrix. Another general aspect relates to encased composite strands, in thread or pellet form, and to wire coating methods and apparatus for making them. The strands are moldable into fiber reinforced thermoplastic composite articles. Each strand is made from fibers, including reinforcing fibers and optionally fibers of a matrix material, that are impregnated with a chemical treatment so that the treatment is disposed between substantially all of the fibers.
公开号:KR20000029969A
申请号:KR1019997001215
申请日:1997-08-07
公开日:2000-05-25
发明作者:우드사이드앤드류비.
申请人:휴스톤 로버트 엘；오웬스 코닝；
IPC主号:

专利说明:

Chemical treatments for fibers and wire-coated composite strands for molding fiber-reinforced thermoplastic composite articles}
Fibers and fiber materials are often used as reinforcements in composite materials. The ceramic is fed to the bushings in molten form, the fibers are stretched from the bushings, and chemically treated agents such as size are used on the stretched ceramic fibers and then the sizing fibers are tow or stranded. Gathering typically produces glass and other ceramic fibers. There are essentially three known forms of chemical treatment agents: solvent based systems, melt based systems and photocurable based systems.
In a broad sense, solvent-based chemical treating agents include organic materials that are aqueous solutions (ie, dissolved, suspended or otherwise dispersed in water), as well as those dissolved in organic solvents. U.S. Patents 5,055,119, 5,034,276 and 3,473,950 describe examples of such chemical treating agents. Solvents (ie, water, organic solvents or other suitable solvents) are used to lower the viscosity of the chemical treatment to promote humidification of the glass fibers. The solvent is substantially unreactive with other components of the chemical treatment agent and is sent out of the chemical treatment agent after humidification of the glass fibers. In each method using a solvent based chemical treating agent, water or other solvents are evaporated or otherwise removed from the used chemical treating agent using an external source of heat or some other apparatus outside the fiber to leave the coating of organic material on the glass fibers. One disadvantage of the solvent based method is that the added step of solvent removal increases the manufacturing cost. In addition, some organic solvents are very flammable in vapor form and are exposed to fire hazards. Another problem with the solvent based system is that removing all solvents from the chemical treatment agent used is not impossible, but very difficult. Therefore, solvent-based chemical treating agents are limited as practical methods in systems in which any residual solvent remaining before the coating of the organic material remaining on the fiber does not have a significant adverse effect.
Conventional molten base chemical treatment agent, which melts thermoplastic organic solids and is used for glass fibers. U.S. Patent Nos. 4,567,102, 4,537,610, 3,783,001 and 3,473,950 describe examples of such chemical treating agents. One disadvantage of conventional melt substrate processes is the energy cost associated with melting the chemical treatment agent. The molten organic solid is used for glass fibers by melting the organic solid used in the conventional molten substrate system at a relatively high temperature. High temperatures are required because the organic solids used in the past have a relatively high molecular weight. The high melting temperature also exposes the operator to the risk of flames by the equipment used to melt the plastic material and the molten plastic itself. In addition, special equipment is typically required to use hot melt plastic materials and otherwise manipulate them.
Photocuring chemical treatment agents are typical acrylate based organic chemicals, with or without solvents, cured by ultraviolet radiation via a photoinitiator. U.S. Patent Nos. 5,171,634 and 5,011,523 describe examples of such chemical treating agents. The main disadvantage to the method of using such chemical treating agents is that the light used, such as ultraviolet light, and the chemical treating agents such as acrylate used are relatively dangerous, and often require special handling and safety precautions. Some of the methods, such as US Pat. No. 5,171,634, require photocuring repeated several times to obtain maximum benefit. Each additional photocuring step increases the associated risk and adds additional cost to the method. Moreover, photocurable thermoset plastics, and their essential photoinitiators, represent a very specific site of heat settling chemistry. After all, the photocuring chemical treating agents are expensive and are not usually available with various kinds of matrix resins.
To produce the composite part, the strands of glass fibers are often chemically treated with the polymer resin in further offline deposition. The resin can be one part or two parts thermosetting or thermoplastic. In one example, the preformed and sized continuous glass fibers are impregnated with a thermoset resin and then drawn through a heated draw die to cure the resin and produce a composite, such as a ladder rail. In the off-line method, continuous glass fibers must be separated in some manner to impregnate the resin between the fibers and then recombine. This essential step always leads to the use of additional hardware such as applicator plates, impregnation baths, and drying or curing ovens. This type of method has the disadvantage of adding cost and complexity to the method. In addition, the resulting further manipulation of the glass fibers results in the destruction of the individual glass filaments, thereby degrading the properties of the composite. Therefore, while the off-line method is effective, it is time-consuming and inefficient (ie, additional processing steps are required) and therefore expensive.
Thus, there is a need in the prior art for a safer, more efficient and more cost effective method of using chemical treating agents on glass fibers, where the viscosity of the chemical treating agents is sufficiently low to sufficiently humidify the glass fibers without the need for solvents and The chemical treatment does not require photocuring and the viscosity of the chemical treatment used increases the generation of water, volatile organic carbon (VOC) or solvent vapors, if any, to a very small, chemically treated product glass fiber into the composite. It is suitable for subsequent processing. There is also a need for an inline method of forming pre-impregnated glass composite strands from a plurality of continuously formed glass fibers chemically treated in this manner, wherein the resulting prepreg is suitable for subsequent inline or offline processing into a composite. Do.
The use of composites with fiber reinforced polymer matrices is broad. Fiber reinforced polymer composite products have been prepared using a variety of methods and materials. As a reference to the above, one method involves impregnating a thermoplastic material with one or more strands or bundles of reinforcing fibers (eg, glass fibers, synthetic fibers or some other reinforcing fibers), and using composite composite strands. It relates to molding the article. The composite strands have been used in the form of continuous yarns (ie, long length strands) and separation pellets (ie, short length strands). The fibers from the composite strands provide reinforcement and the thermoplastic material forms at least part of the matrix as a composite.
It is desirable to completely impregnate each fiber strand with a thermoplastic matrix material, ie distribute the thermoplastic material essentially completely uniformly between each bundle of fibers and between the fibers. Since all fibers are enclosed by the matrix material, the fully impregnated fiber strands can be molded less expensively and more efficiently and the corresponding composites can exhibit improved properties. However, it is difficult and time-consuming to impregnate fiber strands completely with typical thermoplastic matrix materials (eg, engineering thermoplastics). At high yields, it is particularly difficult to fully impregnate the strands with the output typically experienced during the production of continuously formed glass reinforced fibers.
In order to completely impregnate the continuously formed glass fiber strands, the number of fibers (ie, fiber density) used to form each strand is reduced to less than 1200 fibers / strands at a typical density of about 2000 fibers / strands, so that each fiber strand The time taken to impregnate has been reduced. However, by reducing the number of fibers in each strand processed at a given time, it can adversely affect the yield and cost efficiency of processing. In addition, complete impregnation even at fairly low density strands is still a waste of time, preventing low density strands from being fully impregnated and processed at high yields typically approaching the production of continuous glass reinforced fibers.
In order to obtain a high yield, one conventional method only partially impregnates the fiber strands and coats the strands with a homogeneous layer of thermoplastic matrix material and removes the core of the non-impregnated fibers with a thermoplastic resin. Partial impregnation of the coating and fibers is accomplished by drawing strands through a device referred to as a so-called "wired coating" device. Wireline coating devices, such as those described in US Pat. No. 5,451,355, typically include an extruder for supplying a molten thermoplastic matrix material and a die having an inlet, an outlet, and a sheathing chamber located therebetween. The extruder feeds the molten thermoplastic material into the coating chamber. When the strands pass through the coating chamber, the strands are covered with a thermoplastic matrix material and partially impregnated, and the coating is formed into a homogeneous layer when the coated strands pass through the exit of the die. The resulting coated strands are used in the form of yarns (eg compression molding) or cut into separate pellets (eg injection molding coating). Since the strand is only partially impregnated with the thermoplastic matrix material, the strand can be processed to a relatively high yield.
However, the partially impregnated mammary gland strands also present a number of problems due to the core of the non-impregnated fibers. In the form of pellets, the fibers in the non-impregnated cores tend to deviate from the thermoplastic coating. If the strands are in the form of yarns, the nuclei do not easily escape, but the nuclei of the mammary covering yarn still need to be impregnated to some degree to optimize the properties of the resulting composite. Impregnation of the core of the mammary gland during the melting operation is not practical but impossible and time consuming as a practical method. Thus, molding into the streamlined sheath can reduce the overall production rate rather than increase as desired.
Therefore, even when each strand has a relatively high fiber density, a method of producing a fully impregnated fiber strand at a high yield is required, wherein the composite strands produced in the form of yarn or pellets are suitable for molding fiber reinforced thermoplastic products. .
The present invention relates to the use of chemical treating agents in fibers suitable for processing into composites. More particularly, the present invention relates to the use of chemical treating agents on fibers having low viscosity and substantially free of unreactive solvents. Even more particularly, the present invention utilizes thermal energy to lower the viscosity and improve the humidification of chemical treatment agents after use in fibers and / or increase the molecular weight of volatile organic carbon (VOC) or produce volatile organic carbon, if any It relates to curing very little used chemical treatment agent.
FIELD OF THE INVENTION The present invention relates generally to streamlined fiber / polymer composite strands used for the production of fiber reinforced composites, in particular for the molding of fiber reinforced composites. More particularly, the present invention relates to thermoplastic encapsulated fiber / polymer composite yarns and pellets moldable into fiber reinforced thermoplastic composites.
1 is a perspective view of an embodiment of an apparatus suitable for chemically treating a fiber formed continuously from a molten material and producing a composite.
2 is a perspective view of another embodiment of a system for chemically treated fibers, wherein a heat retainer is disposed between the fiber forming apparatus and the chemical treating agent applicator.
3 is a perspective view of an additional embodiment of an apparatus for chemical treatment of fibers continuously formed from preformed fibers drawn from molten material and a package.
4 is a perspective view of one embodiment of an apparatus for manufacturing and cutting a plurality of pellets suitable for molding thermoplastically encapsulated composite strands of pre-impregnated reinforcing fibers into fiber reinforced thermoplastic composites.
5 is a plan view of a winding device for winding into a package of seals suitable for molding thermoplastically encapsulated composite strands into fiber reinforced thermoplastic composites.
6 is a perspective view of one embodiment of an apparatus for making and cutting thermoplastic encapsulated composite strands of preimpregnated fibers into a plurality of pellets suitable for forming into fiber reinforced thermoplastic composites.
Detailed description of the invention
One general feature of the present invention relates to an inherently solventless chemical treatment agent for use in fibers to process composites. One or more chemical treating agents may be used in the fibers, such as with one or more conventional applicators, to size and / or preimpregnate a sufficient number of reinforcing fibers to achieve the desired composite properties.
More particularly, the fibers or filaments are sized and / or preimpregnated with a chemical treatment agent. The chemical treating agent is low viscosity, is substantially free of unreactive solvents and is not cured by actinic radiation. Low viscosity can be obtained by selecting a relatively low molecular weight component for the chemical treatment agent.
Thermal energy can be used to lower the viscosity and improve the humidification of the chemical treatment agent after the treatment agent is used in the fibers. Additionally or instead, thermal energy can be used to increase the molecular weight of the chemical treatment agent used, or else to cure (ie, increase the molecular weight of the crosslinking or otherwise used chemical treatment agent). Instead, thermal energy may not be supplied to the chemical treatment agent used. Regardless of whether heating is used, there is little generation of water vapor, volatile organic carbon (VOC) vapor or other solvent vapors, if any.
Chemically treated resultant fibers are suitable for forming composite strands, ie pre-impregnated strands (“prepregs”). The composite strand can be a composite having reinforcing fibers that are continuously processed in-line or off-line to be placed in the polymeric matrix material.
Apparatus suitable for producing one or more composite strands in the form of yarns or pellets suitable for molding into fiber reinforced thermoplastic composites include a source of reinforcing fibers, and optionally one or more other types of fibers. One such circle is a bushing of melt reinforcing material (eg, glass) that stretches the continuous reinforcing fibers to a sufficient number, if any, to form at least a portion of the strand. It may also be desirable for the source of reinforcing fibers to be one or more spools or other packages of preformed reinforcing fibers. A circle of preformed reinforcing fibers can be used in combination with a circle of continuous forming reinforcing fibers. The circle of fibers may also comprise matrix fibers, for example, which are continuously produced from a bushing or spinner and / or preformed and provided in a suitable packaging such as a spool.
When forming glass reinforced fibers, the fiber forming apparatus forms fibers from molten glass fiber materials, such as circles of conventional glass reinforced bushings. The fiber forming operation can be run off-line from the device or inline with the device. If the fibers formed are glass reinforced fibers, the fiber forming apparatus forms the fibers from a source of molten glass reinforced fiber material. In one embodiment, the fiber forming apparatus releases thermal energy for a short time after forming and forming the fibers.
Applicators are used to use chemical treating agents on virtually all fibers. The applicator can be conventional or any other structure suitable for using the desired form and amount of chemical treatment agent. The applicator can be placed in-line with the fiber forming apparatus for use with the chemical treating agent to form a plurality of coated fibers. The applicator uses a chemical treatment agent that is substantially solvent free and is substantially photocurable.
One embodiment of the apparatus includes an applicator system using a chemical treating agent when the fiber is at a temperature higher than the temperature of the chemical treating agent used. When using a chemical treatment agent, the fiber is at a high temperature sufficient to provide sufficient thermal energy such that the chemical treatment agent used lowers its viscosity or at least partially (e.g., if the chemical treatment agent is thermoset), or both Can be generated. However, when chemical treatment agents are used, the temperature of the fibers is insufficient to cause significant degradation of the chemical treatment agents used. The temperature difference of the fibers used and the chemical treating agent used can be obtained by including a heat retainer as part of the applicator system. The temperature difference also places the applicator close enough (eg, close to) the fiber forming apparatus to be sufficiently hotter than the chemical treatment agent when using the fiber. The applicator system may include a heat retainer disposed during and / or after use of the chemical treatment agent to help maintain the temperature of the fibers or at least reduce the rate of temperature drop.
Gathering shoes or some other gathering or bundlers are used to gather the treated fibers into at least one strand. The strand can then be covered or encapsulated with a suitable polymeric material, preferably a thermoplastic, and formed into the desired composite.
The material used to coat or encapsulate the chemically treated strand can be provided from a source of molten thermoplastic material, such as an extruder. To coat the treated strands and form composite strands, the treated strands may be drawn through or otherwise passed through a suitable coating apparatus. For example, encapsulated composite strands can be formed by drawing or other strands through a corresponding number of dies, each die having one or more outlets sized to provide a desired coating (eg, about 30:70). To a thermoplastic cover) that produces a thermoplastic to glass weight ratio of from about 70:30.
Preferably, a wireline coater is used to enclose the strand. A wireline covering is a device or group of devices that can coat one or more strands with a plastic material to form a lid of relatively uniform thickness on each strand. Preferably, the streamlined sheath comprises some form of a die that molds the sheath to a desired uniform thickness and / or cross section.
The strand is fed or passed through a coating apparatus using a suitable apparatus. For example, a drawer is used to draw strands to the wireline sheath. The drawer may be separated from the wireline coater or a portion thereof. The cutter can also be employed to act as a drawer or to assist the drawer in drawing strands to the wireline sheath.
The resulting coated or encapsulated composite strands can be separated into cut or separated lengths to form a plurality of encapsulated composite pellets, wound or otherwise packaged to form encapsulated composite yarns. Chemical treatment aids in tying the fibers with each polymer encapsulated composite pellet or thread.
The composite may be made by molding into one or more enclosed composite strands, such as pellets, yarns or other forms. The covering of the encapsulated composite strand may form at least a portion or all of the matrix of the composite being molded. Exemplary molding methods used to form composites include injection molding, compression molding and other suitable molding techniques.
1-3 demonstrate a preferred embodiment of chemically treating a number of fibers 10 suitable for making composites. Typical composites include a plurality of reinforcing fibers 12 disposed in a polymeric material.
In addition to the reinforcing fibers 12, the fibers 10 may also include other types of fibers suitable for the manufacture of the composite, such as matrix fibers 13. Matrix fiber 13 is preferably made from a polymeric matrix material and forms at least part of the matrix. Reinforcing fibers 12 can be continuously stretched from a circle of molten glass reinforcing material (eg, conventional glass fiber reinforced bushings such as those shown in FIGS. 1 and 2). Particularly advantageous is the glass reinforcing fibers formed continuously, since the heat energy remaining in the glass fibers from the forming method can effectively raise the heat to the chemical treatment agent used. In addition to or instead of the use of continuously formed glass fibers, reinforcing fibers 12 may include preformed reinforcing fibers made from glass and / or synthetic reinforcing materials.
The term "preformation" refers to fibers that are formed off-line before being fed or provided with a chemical treatment agent in accordance with the present invention. The term "glass" is intended to include glassy mineral materials as well as ordinary silicate glass suitable for the production of reinforcing fibers, such as borosilicate glass, glass wool, rock wool, slag wool and mineral wool, which solidify in an amorphous state upon cooling. Means the inorganic product of the lysate. In contrast, "synthetic" reinforcing materials are non-glass materials such as Kevlar®, carbon or graphite, silicon carbide (SiC), and non-glass materials with suitable reinforcing properties. When using fibers made from different materials, it is contemplated that the same or different treating agents can be used for various types of fibers.
In one embodiment, the chemical treatment agent is used depending on the method and the device used to affect one or more of the two changes in the chemical agent used using thermal energy. Thermal energy can be used to lower the viscosity, which improves the humidification of the chemical treatment agents used in the fibers. Alternatively or additionally, thermal energy may be used to increase the molecular weight of the chemical treatment agent used or otherwise cure. 1 and 2 describe exemplary embodiments of apparatus and methods using chemical treating agents.
Chemical treatment agents used to coat fibers 10 have a relatively low molecular weight and viscosity relative to the matrix material and are also substantially non-reactive solvents. An “unreactive solvent” (eg, water and any organic solvent) is a solvent that evaporates out of the chemical treatment agent in the presence of thermal energy rather than reacting with components or matrix materials of the chemical treatment agent. Chemical treatment agents are practically “solvent free”, ie essentially free of such unreactive solvents. Thus, although there may be traces of unreacted solvent in the chemical treatment agent, the amount of solvent present is sufficient by itself to sufficiently lower the viscosity of the chemical treatment agent (ie, affect the performance of the chemical treatment agent to humidify the fibers). Not. In addition, the chemical treating agent used is not sufficiently free of any unreactive solvent and does not generate significant amounts of water vapor, VOC vapor, or other solvent vapors when the chemical treating agent is heated, including during molding of the composite. Due to the solvent-free, the present chemical treatment agent can reduce and / or thermoset its viscosity without significant drop in mass. Thus, most of the chemical treatment agents used for fiber 10 remain in the fiber.
Although the chemical treating agent is solventless, it does not exclude the use of one or more additives in chemical treating agents that are compatible with soluble or other ingredients (eg, coupling agents). For example, a commercially available viscosity modifier such as the HELOXY® product available from Shell Chemical Company, for example diglycidyl ether of 1,4-butanediol (HELOXY modulator 67). Or polyglycidyl ether of castor oil (HELOXY modulator 505) may be used in the film-forming agent to lower or lower the viscosity of the chemical treatment agent instead of interacting or reacting one or more other components to remove them in the form of steam in the presence of thermal energy. .
It does not cure the chemical treating agent by actinic radiation to any significant extent (ie, it is photocurable). That is, the chemical treating agent reacts photochemically and does not harden or significantly increase the viscosity due to the effect of actinic radiation.
Chemical treatment agents, which may be thermosetting or thermoplastic in nature, are used to size and / or pre-impregnate the number of reinforcing fibers 12 needed to obtain composites of the desired properties. Chemical treatment agents are also used to size and / or pre-impregnate other types of fiber 10, such as fiber 13 made from polymeric matrix material.
The matrix fibers can be continuously formed or preformed in-line and subsequently used to form some or all of the matrix of the composite. When using matrix fibers, the step of using the chemical treating agent may include sizing and / or preimpregnating with the same or different chemical treating agents in addition to those used for the reinforcing fibers.
In most cases, sizing as well as preimpregnation is preferred, and therefore it is desirable to use the same chemical treatment agent for sizing and preimpregnation of fibers 10. However, optionally, one chemical treating agent may be used to size the reinforcing and / or matrix fibers, and another chemical treating agent may be used to pre-impregnate the reinforcing and / or matrix fibers. If different types of matrix fibers are used, it may be desirable to use different chemical treating agents for various types of matrix fibers.
Sizing the fibers involves using at least a single layer of chemical treatment on various fibers. When using a chemical treatment agent content on the fiber 12 of about 0.1% to 1% by weight, for example about 0.5% by weight relative to the total weight of the treated fiber, the glass reinforcement fiber 12 is considered to be sized. Pre-impregnation relates to the substantial filling of the spaces between the fibers when a sufficient amount of chemical treatment agent is coated or otherwise used to bundle the fibers 10 into bundles or strands 14. Bundles or strands 14 of glass reinforcing fibers 12 are generally considered to be preimpregnated when the strands 14 have a chemical treatment content of about 2% to 25% by weight.
For example, when using small amounts of chemical treatment agents and / or having sufficiently low viscosities, the fibers can be sized without preimpregnation at the same time. The viscosity of the chemical treatment agent can be adjusted by adjusting its temperature. For example, the viscosity of the treating agent can be appropriately adjusted after using the heat present in the fiber.
Preferably at least about 2% to about 15%, more preferably about 5% to about 15%, and even more preferably about 8% of reinforcing fiber 12 of strand fiber 10 (relative to the weight of the treated fiber) Cover with% chemical treatment. Conventional loss on ignition (LOI) methods can be used to determine how much of the chemical treatment agent used should be in fiber 12, preferably glass.
Preferred LOI ranges or values are those that provide the desired composite strand properties at minimal cost. At an LOI value of 8%, it was found that sample strand 14 is well impregnated with the touch but not humidified. Too low LOI values result in fuzzing of strand 14 (ie, cutting of many individual glass fibers in the strand) in subsequent inline or offline processing and manipulation. However, the more chemical treatment is added, the more the final product will be consumed. High LOI can bleed low viscosity components out of strand 14. In any case, LOI values of about 25% to about 40% by weight are preferred for making the composite from all matrix polymers that provide composite strand 14.
Thus, the fiber 10 can be chemically treated according to the invention to form a prepreg (pre-impregnated composite strand) 14, or a composite strand 14 containing only sized fiber 10. One or more composite strands 14 can be continuously processed in-line or offline to produce a variety of composites. For example, the step of forming the composite strand can be accomplished inline in the gathering step. Exemplary composites that can form strand 14 include mats, fabrics, sheets, panels, filament wound pipes, drawn products, or spray-up products (gun roving). Strand 14 may also be cut into lengths or pellets suitable for use in injection or other molding methods to form a composite.
In addition, the chemical treating agent according to the present invention includes a thin film forming agent and a coupling agent. Thin film formers form a layer of polymeric material around each fiber treated with a chemical treatment agent. The coupling agent, if appropriate, may also be selected to assist the thin film forming agent or to interact with the polymer matrix material.
The chemical treating agent used acts as a thermosetting or thermoplastic resin. In addition, the treating agent may have both heat-setting and thermoplastic components, for example, the treating agent may contain substantially thermoplastic polymers having reactive end groups that may participate in the heat-setting / curing reaction. The thin film forming agent used on either side of the chemical treatment agent may be the same polymeric material as that used for the composite matrix.
Chemically treating agents in the thermoset form may be used with polymer matrices that are partially or fully thermoset, substantially non-curable, and are thermoset or thermoplastic. If the chemical treating agent acts as a thermosetting resin, the thermal energy used may be at least partially cured and increase the viscosity of at least a portion of the used chemical treating agent that is cured. Preferred chemical treating agents are thermosets at temperatures of about 350 ° C. (660 ° F.) or less.
In an exemplary heat-setting chemical treatment agent, the film-forming agent comprises one or more relative low molecular weight monofunctional monomers, one or more low molecular weight or high molecular weight multifunctional monomers or mixtures thereof. Monofunctional monomers have one reaction site per molecule, and polyfunctional monomers have two or more reaction sites per molecule. The monomer is thermoset without generating significant amounts of water vapor, volatile organic carbon vapors, or other solvent vapors. For example, the film-forming agent of the heat treatment form of the chemical treatment agent may include, for example, polyester alkyd, epoxy resin, and a mixture of glycidyl ether functional groups sufficient to form a thin film in each layer but do not constitute an epoxy resin. have. Other suitable functional monomers for use as part or all of the thin film forming agent include urethanes, vinyl esters, dark acids, Dielsalder reactive species (such as dienes or dienophiles) and cope rearrangeable molecules. The molecular weight of the functional monomer is moderately low compared to the matrix material to obtain a chemical treating agent having a low viscosity.
In an exemplary thermoplastic form of the chemical treatment agent, the film forming agent preferably comprises one or more low molecular weight thermoplastic polymer materials having a relatively low viscosity at elevated temperatures. Thermoplastic resins usually have a relatively high molecular weight and thus high viscosity as compared to typical uncured thermosetting resins. However, if pyrolyzed or otherwise processed to a sufficiently low molecular weight, the high molecular weight thermoplastics can still be used in thin film forming agents of chemical treatment agents in thermoplastic form. High molecular weight thermoplastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), other polyesters, and polyamides such as nylon may be suitably pyrolyzed for this purpose.
Even in the case of pyrolysis, some thermoplastic resins may undesirably have high viscosity. In this case, a processing aid or a viscosity modifier may be used in the thin film forming system. For example, a monomer equivalent of a thermoplastic material, or a mixture of monomer equivalents and oligomers (eg, pyrolyzed thermoplastic materials) can be used as processing aid having a high molecular weight thermoplastic. Exemplary thermoplastic monomer equivalents include di-benzoate esters of di-n-butyl terephthalate and 1,4-butanediol for PBT; Dibenzoate esters of diethyl terephthalate and ethylene glycol for PET; And adducts of caprolactone, adipolychloride and n-aminohexane, and adducts of 1,6-hexanediamine and hexanoylchloride for nylon. In this example, the monomer equivalent may act as a processing aid to cause high molecular weight thermoplastics such as PBT, PET and nylon to form at least part of the thin film former in the chemical treatment agent.
The exemplary monomer equivalent processing aids may be used with other thermoplastics, and / or may be prepared reactively and used with heat-setting resins or thermoplastics. Satisfactory results are obtained using butoxyethylstearate (BES) as the processing aid in the BES containing chemical treating agent described in the Examples below for the thermosetting matrix. Preferably, the processing aid contains functional groups of the same kind as the matrix polymer. There may be a myriad of molecules and / or combinations of molecules that may be useful as monomeric equivalent processing aids.
If the chemical treating agent acts as a thermosetting resin, the heating step is preferably used to at least partially cure the chemical treating agent used and to cure at least a portion of the used chemical treatment agent (ie the portion that is most directly exposed to heat). To increase the viscosity. The increase in viscosity may be caused by an increase in molecular weight upon curing of the chemically treating agent in a thermoset form. Thin film forming agents in the thermoset form are thermosets without the generation of significant amounts of solvent vapor upon heating. Preferably, the functional monomers used as thin film forming agents are no greater than about 350 ° C. (662 ° F.) as the risk of permanent deterioration increases to an undesirable extent for many chemical treatment agents at temperatures above about 350 ° C. (662 ° F.). It is thermoset at the temperature of.
If the chemical treatment agent used acts as a thermoplastic, heating may reduce the viscosity of at least a portion of the used chemical treatment agent (eg, adjacent to the thermal fibers) most directly exposed to heat. If the viscosity is low during the heating step, preferably the viscosity is sufficiently lowered to improve the performance of the chemical treatment agent in the thermoplastic form used as desired to humidify the fiber 10 (covering the fiber and interacting with the fiber surface). The humidification of the chemical treatment agent used on the fiber 10 is easier to further improve if the viscosity decrease occurs in at least some of the used chemical treatment agent disposed on the fiber surface. In order to reduce the chance of permanent deterioration during heating, it is also desirable for the thin film formers, especially in the thermoplastic form, and generally the chemical treatment agents in the thermoplastic form to exhibit sufficiently low viscosities at temperatures below about 350 ° C. (662 ° F.).
The viscosity of either form of the chemical treatment agent is low, if not all, but at least in part, sufficiently humidifies the fiber 10 when the chemical treatment agent is initially used. In order to use prior art (eg, single or double roll applicators 26) chemical treatment agents without breaking many fibers 10, especially glass fibers, the chemical treatment agents preferably have a viscosity of about 1000 cps or less prior to use. Has The lower the viscosity of the chemical treatment agent used, the more the fiber 10 can be processed without significant fiber breakage. Thus, more preferably, prior to use, the chemical treatment agent has a viscosity of about 300 cps or less. In a preferred embodiment for the advantageous processing of fiber 10, the chemical treatment agent, when used, has a viscosity of about 50 cps, more preferably about 10 cps, as measured by a conventional viscometer (e.g., Brookfield or ICI viscometer). Has
The following are specific examples of thin film formers divided into two main categories: liquid and meltability. In the "liquid" category, there are three examples of synthetic maleate based thin film formers. In addition, there are 12 epoxy based thin film formers made from commercial components. There is another liquid thin film forming agent (allyl propoxylate urethane) that can be used as a chemical treatment agent in a thermosetting or thermoplastic form. There are two thin film forming systems, each made from one of the commercially available polycaprolactone and liquid thin film forming agents in the "melt" category. Exemplary polycaprolactone systems are solid polymers at room temperature. The exemplary thin film forming agents are all processable according to the present invention.
It is an object of the present invention to obtain a chemical treating agent for fibers, such as glass fibers, ie substantially free of unreacted solvents. Another object is to obtain a solvent-free chemical treating agent that is substantially non-photocurable. It is an additional object of the present invention to provide a chemical treating agent having enhanced humidification. A further object is to provide a solvent-free chemical treatment agent which can reduce its viscosity by using thermal energy in a chemical treatment agent that can be cured or coated on fibers. Yet another object is to provide an advantageous method by which chemical treatments are used on the fibers to produce composite strands useful for forming the coated fibers into composites. An additional object is to provide a method of producing fibers that are completely impregnated with a chemical treatment agent.
This object is attained by a method for producing a composite product, such as a composite strand or a molded article made from the strand product, which method usually involves producing a thermoplastic encapsulated composite strand material which is placed in a matrix material. The thermoplastic encapsulation composite is prepared in the following steps: forming a preimpregnated fiber using a chemical treating agent in an amount sufficient to substantially cover all of the plurality of fibers containing the reinforcing fibers (the chemical treating agent is compatible with the matrix material). ; Gathering the pre-impregnated fibers into pre-impregnated strands having a chemical treatment agent disposed substantially between all of the plurality of fibers; And encapsulating the pre-impregnated strand in a method comprising: streamline coating the pre-impregnated strand with a thermoplastic material to form a thermoplastic coating and forming the thermoplastic coating with a thermoplastic cover to form a thermoplastic encapsulated composite strand. In a preferred embodiment, the thermoplastic encapsulated composite strand is cut to form a plurality of pellets. Instead, thermoplastic encapsulated composite strands can be packaged as yarn. In one embodiment, the reinforcing fibers comprise preformed reinforcing fibers. Many fibers may also contain matrix fibers. The method may further comprise steps such as making by a method comprising the continuous formation of reinforcing fibers from molten glass or the preforming of matrix fibers from a polymeric material. Optionally, the method may comprise making the reinforcing fibers in-line in a method comprising continuously forming the reinforcing fibers from the molten glass material. The chemical treating agent used in the process may contain water and organic materials in an amount that provides from about 2% to about 25% by weight of the organic material content to the pre-impregnated strand, and before gathering substantially all of the water in the chemical treating agent Evaporate. The organic material may be solid or liquid dispersed or emulsified in water. More preferably, the organic material content is about 2% to about 15% by weight, the evaporation step comprises heating of the chemical treatment agent after the use step, even more preferably the organic material content is about 6% to 7% by weight, Heating includes supplying thermal energy to a chemical treatment agent from an external source or multiple fibers. In one embodiment, the chemical treating agent is thermoset and the preparation of the thermoplastic encapsulated composite strand material further includes at least partially curing the chemical treating agent after the use step. The chemical treating agent is preferably substantially solventless and substantially photocurable, and the organic material comprises a thin film forming agent and a coupling agent. In one embodiment, the chemical treating agent is thermoplastic, the thin film forming agent comprises a low molecular weight thermoplastic polymer, and the coupling agent comprises a functionalized organic material. In another embodiment, the chemical treating agent is thermosetting, the film forming agent comprises at least one multifunctional monomer and a low molecular weight monofunctional monomer, and the coupling agent comprises a functionalized organic material. The method may further comprise combining the thermoplastic encapsulated composite strand with the matrix material to form a composite blend and molding the composite blend. Moreover, the method may include forming thermoplastic encapsulated composite strands into pellets and molding the pellets combined with the resinous matrix material to form fiber reinforced composites. The invention also relates to a product produced according to the above method.
Additionally, the present invention relates to a composite product comprising a plurality of thermoplastically encapsulated composite strands useful for forming fiber reinforced composites containing matrix material, wherein each thermoplasticly encapsulated composite strand is thermoplastic or thermoset compatible with the matrix material. It contains pre-impregnated strands containing a plurality of gathered fibers, including reinforcing fibers substantially coated with a chemical treatment agent. In one embodiment, the composite product comprises pellets cut from the composite strands, while the chemical treating agent retains all of the gathered fibers in the form of pellets. Instead, the composite strands can be packaged in thread form. Preferably, the number of multiple gathered fibers ranges from about 1,500 to about 10,000, more preferably from about 2,000 to about 4,000. Many gathered fibers may optionally include matrix fibers made from thermoplastic materials. In one embodiment, the chemical treating agent comprises an organic material and each preimpregnated strand is from about 2% to about 25% by weight, more preferably from about 2% to 15% by weight, and even more preferably from 6% by weight to Has an organic material content of 7% by weight. The chemical treating agent may be thermoplastic, substantially solvent-free, and substantially matt-free, and may contain (i) a thin film-forming agent containing a low molecular weight thermoplastic polymer material and (ii) a coupling agent containing a functionalized organic material. . Instead, the chemical treating agent may be heat-setting, substantially solvent-free, and substantially matt-free, and (i) a thin film-forming agent containing at least one multifunctional monomer and a low molecular weight monofunctional monomer and (ii) a functionalized organic material. It may contain a coupling agent containing. Many composite strands can be molded with the matrix material.
The invention further relates to a process for producing a composite product, the process comprising the following steps: coating a thermosetting or thermoplastic chemical treating agent with a chemical treatment agent used using a plurality of fibers, including glass or synthetic reinforcing fibers. Forming the woven fiber (chemical treatment agent is substantially solvent-free and is substantially photocurable); Heating the chemical treatment used to lower the viscosity of at least a portion of the chemical treatment used, partially curing the chemical treatment used, or using both to form the coated fiber. The chemical treating agent may be used in an amount of about 0.1% to about 1% by weight to size the plurality of fibers, or may be used in an amount of about 2% to about 25% by weight to pre-impregnate the plurality of fibers. The fibers may further comprise polymeric matrix fibers. In a preferred embodiment, the reinforcing fibers comprise glass reinforcing fibers and the heating step comprises supplying thermal energy to the used chemical treating agent exiting the glass reinforcing fibers, wherein the glass reinforcing fibers are preferably in the range of about 150 ° C. About 350 ° C, more preferably about 200 ° C to about 300 ° C. The reinforcing fibers may comprise preformed reinforcing fibers and the method may further comprise a preheating step of the preformed reinforcing fibers. In addition, the reinforcing fibers may comprise glass fibers, the method further comprising forming glass fibers from a source of molten glass reinforcing material, wherein the heating step comprises thermal energy remaining in the glass reinforcing fibers from the forming step. It includes supplying to the chemical treatment agent used. The heating step may include feeding chemical fibers thermal energy used from an external source to the plurality of fibers. In one preferred embodiment, the chemical treating agent is thermoset and the heating step cures at least part of the chemical treating agent used. Instead, the chemical treating agent is thermoplastic and the heating step lowers the viscosity of at least a portion of the chemical treating agent used. The method may further comprise gathering the coated fibers into the composite strand, wherein a heating step may occur after the gathering step. The chemical treating agent may contain an organic material and the composite strand has an organic material content of about 2% to 25% by weight. The method may also include forming the composite strand into a composite having a plurality of fibers disposed in a matrix at least partially formed by a chemical treatment agent used. Many fibers optionally include polymeric matrix fibers forming at least a portion of the matrix of the composite. The forming step can be run inline with the gathering step. In addition, reinforcing fibers and matrix fibers may be mixed to provide a plurality of fibers. The use step may simultaneously involve coating the reinforcing fibers and the matrix fibers with the chemical treatment agent.
In addition, the present invention relates to an apparatus for implementing the method.
The present invention also relates to a chemical treating agent used in fibers to form a hemp oil-reinforced composite by processing into a composite strand useful for placement in a matrix material, the chemical treating agent containing: a thin film containing at least one multifunctional monomer. Tonic; And a coupling agent containing a functionalized organic material. The chemical treating agent is heat stable, at least partially heat curable, substantially solvent free, and substantially matt. Optionally, the treatment may comprise a processing aid, such as an epoxyfunctional viscosity modifier or butoxyethylstearate. In a preferred embodiment, the chemical treating agent is thermoset at a temperature of about 150 ° C to about 350 ° C. Thin film formers may include monomers selected from polyester alkyds, epoxy resins, and compounds containing glycidyl ether functional groups. Thin film formers may also include one or more selected from urethanes, vinyl esters, dark acids, Diels Alder reactive species, and Cope rearrangement compounds. Preferably, the chemical treating agent has a viscosity of about 300 cps (centipoise) or less in the temperature range of about 93 ° C to about 110 ° C.
Moreover, the present invention is directed to chemical treating agents used in fibers to form fiber reinforced composites by processing into composite strands useful for placement in matrix materials, the chemical treating agents comprising: thin film forming agents containing one or more low molecular weight thermoplastic polymer materials; And a coupling agent containing a functionalized organic material, wherein the chemical treatment agent is thermoplastic, substantially solvent-free, and substantially photocurable. Optionally, the treatment may contain a processing aid. Low molecular weight thermoplastic polymers may include pyrolyzed polyesters or polyamides, the polyesters or polyamides being preferably selected from polyethylene terephthalate, polybutylene terephthalate and nylon. In a preferred embodiment, the treating agent is di-n-butyl terephthalate, dibenzoate ester of 1,4-butanediol, diethyl terephthalate, dibenzoate ester of ethylene glycol, caprolactone, adipolychloride and n-aminohexane A processing aid comprising an adduct of and a monomer equivalent selected from adducts of 1,6-hexanediamine and hexanoylchloride. Preferably, the chemical treating agent has a viscosity of about 300 cps or less in the temperature range of about 93 ° C to about 110 ° C.
Other objects, features and advantages in various aspects of the invention will become apparent in the preferred embodiments together with the description of the invention and the accompanying drawings thereof.
Examples 1 to 6: Liquid Thin Film Forming Agent
Example 1 Propylene Glycol-Fumarate:
A conventional 10 gallon (38 L) stainless steel reactor is charged with 17.02 kg propylene glycol (manufactured by Ashland Chemical Company, Columbus, Ohio) and 12.98 kg fumaric acid (manufactured by Huntsman Specialty Chemical, Salt Lake City, Utah). For stability, 3.62 g (120 ppm) of toluhydroquinone (THQ) (made by Aldrich Chemical Company, Milwaukee) is added to the reactor. The molar ratio of input is 2: 1 propylene glycol (PG) to fumaric acid (FA). The mixture is heated at 380 ° F. (193 ° C.) for 5 hours under a nitrogen atmosphere. The end point of the reaction is determined by the viscosity of the PG-FA product, which is 360 to 450 cps at 120 ° F. (49 ° C.) as measured by a cone-and-plate viscometer such as the ICI product of Delaway, Wilmington. . The acid value at the end of the reaction is typically measured from alkyd 10 to 36 Meq KOH / g (milliequivalents of potassium hydroxide per gram of alkyd). The material can be used directly as a thin film forming agent.
Example 2 Propylated Bisphenol-A-Maleate:
Into a 50 gallon (189 L) stainless steel reactor is charged 159.68 kg of propylated bisphenol-A (manufactured by Milliken Chemical, Mann.) And 20.33 kg of maleic anhydride (manufactured by Huntsman Specialty Chemical). For stability, 18 g (100 ppm) of hydroquinone (HQ) (from Aldrich Chemical Company) is added to the reactor. The mixture is heated under nitrogen atmosphere at 175 ° F. (79 ° C.) for 2.5 hours and then at 275 ° F. (135 ° C.) for 3.5 hours. The end point of the reaction is determined by acid value and the reaction is judged to be terminated when the acid value reaches a level of 63.6 Meq KOH / g of alkyd and no further maleic anhydride is measured by infrared spectroscopy. The viscosity of the product ranges from 100 to 130 cps at a temperature of 200 ° F. (93 ° C.) as measured by an ICI conical viscometer. The material can be used directly as a thin film forming agent.
Example 3 Propoxylated Allyl Alcohol-Maleate:
15.49 kg propoxylated allyl alcohol (manufactured by Arco Chemical Company of Newtown Square, Pennsylvania) and 9.88 kg (Huntsman Specialty Chemical) maleic anhydride are charged to a 15 gallon (57 L) stainless steel reactor. For stability, 2.53 g (100 ppm) of HQ is added into the reactor. The mixture is heated at 250-300 ° F. (121-149 ° C.) for 4 hours under a nitrogen atmosphere. The end point of the reaction is when the acid value reaches a level of 263.4 Meq KOH / g of alkyd and no more maleic anhydride is measured by infrared spectroscopy. The viscosity of the product is 200 ° F. (93 ° C.) as determined by an ICI conical viscometer. At a temperature of 100 to 130 cps. The material can be used directly as a thin film forming agent.
Examples 4A to K Low Viscosity Epoxy
Typical epoxy based thin film forming agents include one or more epoxy products from Shell Chemical Company, such as EPON resin 8121, EPON resin SU-2.5, EPON resin 160, HELOXY modifier 62 (cresyl glycidyl ether), HELOXY modifier 67 (1,4-butanediol Diglycidyl ether), and HELOXY modifier 505 (polyglycidyl ether of castor oil). All the epoxy based thin film forming systems described below have a viscosity of less than 50 cps at room temperature. The percentage stated is in weight percent (the percentages and ratios given throughout this specification are by weight unless otherwise indicated).
(A) 100% HELOXY modifier 67
(B) 98% HELOXY modifier 67, 2% HELOXY modulator 62
(C) 98% HELOXY modifier 67, 10% HELOXY modulator 62
(D) 98% HELOXY modifier 67, 2% EPON resin 160
(E) 90% HELOXY modulator 67, 10% EPON resin 160
(F) 98% HELOXY Regulator 67, 2% EPON Resin SU-2.5
(G) 90% HELOXY Regulator 67, 10% EPON Resin SU-2.5
(H) 97% HELOXY modifier 67, 3% HELOXY modifier 505
(I) 100% HELOXY modifier 62
(J) 70% HELOXY Regulator 62, 30% EPON Resin 8121
(K) 65% HELOXY Regulator 62, 30% EPON Resin 8121, 5% EPON Resin SU-2.5
Example 5 High Viscosity Epoxy
In addition to the epoxy based, an exemplary high temperature, high viscosity epoxy thin film forming system is a one-to-one mixture of DER 337 epoxy resin (manufactured by Dow Chemical) and Araldite GT7031 (manufactured by CibaGeigy Corp., Switzerland). Thin film formers have a viscosity of 350-450 cps at 200 ° F. (93 ° C.) as measured using a Brookfield viscometer.
Example 6 Allyl Propoxylate Urethane:
3.63 kg (21.6 moles) of Desmodur H (21.6 moles) in a 12 liter 3-neck, round bottom glass reactor with heated mantle, Friedrich chiller, 1 liter addition funnel, electric overhead stirrer, and thermocouple temperature probe Methylene diisocyanate, Pennsylvania, Pittsburgh Bayer Chemical) is administered. To this is added 0.5 g (50 ppm) of dibutyl tin dilaurate (manufactured by Aldrich Chemical Company). 6.37 kg (43.6 mol) of ARCAL Allyl Proproxylate 1375 (propoxylated allyl alcohol, manufactured by Arco Chemical Company) is then added via addition funnel. Allyl propoxylate is added dropwise and the addition rate and temperature of the heating mantle are changed while maintaining the temperature at 80 ° C. Upon completion of the addition, the temperature of the reactor contents is maintained at 80 ° C. for 3 hours or until the 2200 wavenumber peak disappears in the infrared spectrum of the reaction mixture corresponding to the isocyanate group of Desmodur H. The thin film former can be used directly without any purification or further manipulation.
Examples 7 and 8: Meltable Thin Film Formant
Example 7 Propoxylated Bisphenol-A Maleate / TONE 0260
Propoxylated bisphenol-A maleate from Example 2 is mixed with TONE 0260 (polycaprolactone polymer from Union Cabide) in a weight ratio of 1: 1. The mixture is solid at room temperature but has a viscosity of 50-250 cps at a temperature of 200-230 ° F. (93-110 ° C.).
Example 8 Propoxylated Allyl Alcohol Maleate / TONE 0260
From Example 3 propoxylated allyl alcohol maleate is mixed with TONE 0260 in a weight ratio of 1: 1. The mixture is solid at room temperature but has a viscosity of 50-250 cps at a temperature of 200-230 ° F. (93-110 ° C.).
Ingredient
Other viscosity modifiers such as, in addition to or in place of the above, n-butyl amic acid can also be used as modifiers to suitably react with thermoplastic or thermosetting materials to lower the viscosity of the thin film former and the overall chemical treatment agent. Preferred dark acid reactivity modifiers are prepared as follows:
150 g (1.53 mol) of maleic anhydride (manufactured by Huntsman Specialty Chemical) in a 2-liter 3-neck, round bottom glass reactor with heating mantle, Friedrich chiller, 1 liter addition funnel, electric overhead stirrer, and thermocouple temperature probe; and 0.02 kg of hydroquinone (manufactured by Aldrich Chemical Co.) is administered. The solid is dissolved by the addition of 350 ml of acetone (high purity grade from Aldrich Chemical). The solution of maleic anhydride and hydroquinone is stirred in the reactor. A solution of 111 g (1.51 mol) (from Aldrich Chemical) of n-butyl amine in 150 ml of acetone is added to the reactor. The n-butyl amine solution is added dropwise and the addition rate and the temperature of the heating mantle are varied while maintaining the temperature at 55 ° C. Once the addition is complete, the temperature of the reactor and the contents are maintained at 60 ° C. for 3 hours. Acetone is then removed by reduced pressure and rotary evaporation at 60 ° C. The solid n-butyl dark acid product can be removed from the reactor as a liquid at 90 ° C. and used directly without further purification or manipulation. A small amount of n-butyl amic acid produced is recrystallized from acetone. The melting point of the recrystallized material is 74.9 ° C. by differential scannig calorimetry (DSC).
Coupling agent
As a thermosetting or thermoplastic chemical treating agent, the coupling agent comprises a functionalized organic material (ie one or more organic functional groups bonded to the organic material). Exemplary forms of functionalized organic materials include alcohols, amines, esters, ethers, hydrocarbons, siloxanes, silazanes, silanes, lactams, lactones, anhydrides, carbenes, nitrenes, orthoesters, imides, enamines, imines, amides Imides and olefins. The functionalized organic material creates fibers at elevated temperatures (preferably between about 100 ° C. (212 ° F.) and about 350 ° C. (662 ° F.)) to create sufficient coupling or bonding between the reinforcing fibers and the matrix material to achieve the desired properties. Interact with and / or react with the surface of Interactions involve affinity, such as bonds resulting from hydrogen bonds or van der Waals bonds. The reaction involves chemical bonds, typically covalent bonds. The functionalized organic material may also interact or react with the matrix material. Exemplary coupling agents include silanes such as gammaaminopropyltriethoxysilane (A-1100), gammamethacryloxypropyltrimethoxysilane (A-174) and gamma glycidoxypropyltrimethoxysilane (A-187) ( All of which are manufactured by the Witco Chemical Company of Chicago, Illinois. Nonsilane coupling agents may also be used. One or more suitable functionalized organic materials for the coupling agent system may be selected to obtain the desired mechanical properties between the reinforcing fibers and the matrix material in the composite.
It is not intended to be limited to any theory with respect to chemical treatments, so a possible explanation of how the treatments work is provided below. Silane-type coupling agents are typically found in hand-based chemical treatment agents. From the present point of view, the alkoxysilane portion of the molecule is hydrolyzed with a conventional silane coupling agent to hydroxysilane or silanol to accommodate the coupling agent. One end of the molecule reacts or interacts with the glass surface and the other end of the molecule reacts or interacts with the matrix material. More particularly, coupling agents that have typically been used in the glass industry are organosilanes, where the organic moieties react or interact with the matrix polymer and silane moieties, or more specifically the silanol moieties react or interact with the glass surface. Also, in some cases, the organic portion of the organosilane may react (eg, covalent or ionic bond) or interact with (eg, hydrogen or van der Waals bond) with the glass surface. Typically, hydrogen bonds and other bonds are considered to be thermodynamic (reversible under mild reaction conditions). In some cases, when bonding to silanol glass surfaces, chemical bonding is considered a thermodynamic method. Thus, in conjunction with previous coupling agent technology, the binding of a water based chemical treatment agent to glass occurs as a thermodynamic method. This is because conventional methods are usually carried out under relatively mild conditions and are usually quite reversible. In conventional methods, the glass fibers are coated with a water based chemical treatment agent, and then the coated fibers are packaged and dried in an oven. There is a potential that some of the organic functionalities of the organic binder in the oven react reversibly with some of the organic functionalities in the thin film forming agent. This typically does not occur in any wide range because the oven temperatures typically used, about 150-190 ° F. (66-88 ° C.), are not high enough.
In contrast, with the solventless chemical treatment agents according to the invention, the bonding or coupling method is more active in nature. That is, the bond may occur in relatively rough conditions (eg, at high temperatures) and may be substantially related to the irreversible reaction. Moreover, in addition to the coupling agent that binds to the fiber surface, interfacial zones can be formed between the reinforcing fibers and the matrix material of the composite. The interfacial zone is at least partially formed with the chemical treatment agent used. The interfacial zone may also comprise a zone around the fiber in which the chemical treatment agent and the matrix material interact and / or react with each other, in whole or in part. Chemical treating agents may also be fully dispersed or decomposed in the surrounding matrix material.
Although conventional silane coupling agents can be used in the present chemical treatment agents, the mechanism of interaction or reaction with the glass surface differs from that occurring in conventional methods. Since there is essentially no water present during the process, the alkoxysilane reacts directly with the glass surface to provide siloxane bonds and liberate the alcohol. Indeed, there is experimental evidence (proton NMR data) suggesting that alkoxysilanes do not hydrolyze in the present chemical treatment under the conditions exposed when processed according to the present invention. The alkoxysilane groups of the coupling agents used in the present chemical treatment agents are active to react or interact with the glass surface to form siloxane bonds and liberate the alcohol. Thus, when the alkoxysilane coupling agent is present in the chemical treatment agent according to the present invention, good composite properties are obtained in both the thermosetting and thermoplastic composites, whereas less desirable composite properties are obtained when the alkoxysilane coupling agent is not present in the chemical treatment agent. As evidenced by the observation that they are obtained in both thermoset and thermoplastic composites, the method is mechanical rather than thermodynamic.
If the alkoxysilane coupling agent in the present chemical treatment agent reacts or interacts with the newly formed glass or other reinforcing fiber surface via some mechanical methods, other forms of molecules containing sufficiently reactive functional groups, such as those noted above, may also Via will react or interact with the glass or other reinforcing fiber surface. In addition, the same functional group that reacts or interacts with the glass or other reinforcing fiber surface via a mechanical method may also react or interact with the remainder of the organic material and / or the matrix material in the chemical process agent. It can then act to create interfacial zones on or near the glass or other fiber surface, and also to increase the average molecular weight of the chemical treatment agent, thereby imparting the desired physical properties to the resulting glass strand product. Thus, the advantages of the present invention include the flexibility of using in a wide range of coupling agents and creating an interfacial zone between the fiber and the matrix.
As a composite that exhibits the desired mechanical properties between the reinforcing fibers and the matrix material, the chemical treating agent is preferably compatible with the matrix material of the composite. If the chemical treating agent can interact with and / or react with the matrix material, it is generally considered that the chemical treating agent is compatible with the matrix material. Thin film formers of either type of chemical treatment agent used may comprise the same polymeric material as the matrix material and provide in sufficient quantity to form part or all of the matrix of the composite.
The chemical treating agent may be miscible in whole or in part with the matrix material and / or form a separate phase from the matrix material. If it is a separate phase, the chemical treatment agent located around each fiber may form a single, separate phase zone surrounding a plurality of separate phase zones and / or their corresponding fibers dispersed in the matrix material.
If it is desired to prepare the composite from one type of chemical treating agent and a different type of matrix material, then the thermosetting chemical treatment agent is preferably used with the thermoplastic matrix. Chemical treatment agents in low molecular weight thermosetting forms may cure during the thermoplastic process and / or may react with the chain ends of the thermoplastic matrix material. Eventually, molecules of this type will not plasticize the preliminary thermoplastic matrix material. In selecting a suitable chemical treatment agent, it should be noted that some low molecular weight thermoplastic materials may plasticize the thermoplastic matrix resin if the chemical structure of the thermoplastic matrix resin and the low molecular weight thermoplastic material are very different. Examples of such different thermoplastic materials are dibutyl terephthalate as part of the chemical treatment agent and polypropylene as the matrix material.
Optionally, the chemical treating agent may further comprise a compatibilizer to improve the interaction and / or reaction between the chemical treating agent and the matrix material, thereby further making it more compatible in incompatible or small compatible polymeric components or matrix materials. A component of a treating agent that is sexual (eg, more miscible) is prepared. When a thermosetting or thermoplastic chemical treating agent is used with the thermoplastic matrix material, exemplary compatibilizers include PET monomer equivalents di-n-butyl terephthalate and dibenzoate esters of 1,4-butanediol; Dibenzoate of PET monomer equivalent diethyl terephthalate and ethylene glycol; And adducts of nylon monomer equivalents caprolactone, adiflochloride and n-aminohexane and adducts of 1,6-hexanediamine and hexanoylchloride.
When using any form of chemical treatment agent with a thermophilic matrix, it is preferred to use more reactive compatibilizers. For example, as polyester or vinyl ester thermosetting resins, suitable compatibilizers are esters of glycidyl methacrylate terminated diacids and trimellitic anhydride systems. Specific examples of suitable compatibilizers for polyester and vinyl ester thermoset resins include diallylphthalate (DAP, commercially available), glycidyl methacrylate encapsulated isophthalic acid, trimellitic anhydride-dodecinate, bisallyl of terephthalic acid Alcohol adduct and CH ₃ CH ₂ (OCH ₂ CH ₂ ) _n (CH ₂ ) _m CO ₂ H (wherein n is an integer from 3 to 7 and m is 16 (eg CBA-60, Illinois, Chicago) Witco Chemical))). As epoxy-based thermosetting resins, the esters described in glycidol are suitable compatibilizers such as glycidyl methacrylate by itself, diglycidyl esters of adipic acid and triglycidyl isocyanurate (TGIC). Can be.
Chemical treatment agents may also include one or more processing aids to promote the use of chemical treatment agents to some extent during the manufacturing process and / or optimize the properties of the resulting composite. As the heat treatment chemical treatment agent, the processing aid may include, for example, a viscosity lowering agent to lower the viscosity of the heat treatment chemical treatment agent before use in the fiber. Viscosity lowering agents are substantially solvent free and preferably assist in curing the thermosetting thin film formers. Processing aids used in thermosetting forms of chemical treatment agents may include, for example, styrene and peroxides. Styrene is preferably used to thin the film-forming agent and participate in the heat setting reaction. Peroxides preferably act as catalysts or curing agents.
Optionally, other forms of non-aqueous forms of additives typically used to size glass fibers may also be used as processing aids in the present chemical treatment agents. For example, processing aids or additives may be used to help control the lubricity of the glass tow or strand, to control the relative amount of static generated, or to control the operability of the glass strand or tow product. Processing aids or lubricants, for example polyethylene glycol ester emulsions in mineral oils (eg, Emerlube 7440, manufactured by Henkel Textile Technologies, Charlotte, Charlotte); Polyethylene glycols such as PEG-400-MO (polyethylene glycol monooleate) and PEG-400-monoisostearate (manufactured by Henkel Corporation); And butoxyethylstearate (BES) can be added to adjust lubricity. The lubricant acts as a lubricant to enhance the flow of glass and, if used wisely, should have little adverse effect on the properties of the final composite, if any. The generation of electrostatics can be controlled by adding processing aids such as polyethyleneimine, such as Emery 6760-O and Emery 6760-U (manufactured by Henkel). Process aids such as polyvinyl pyrrolidone (eg, PVP K90, manufactured by GAF Corporation of Wayne), which can provide good strand integration and cohesiveness, and the performance of matrix materials that wet fibers. Can be fortified with a humidifier or surfactant such as Pluronic L101 and Pluronic P105 (both manufactured by BASF Corporation). However, any component present has a blend and is added in an amount in which the chemical treatment agent remains solventless.
Preferred embodiments of the apparatus of the method for using the present chemical treatment agent will be described in further detail with reference to the drawings. 1 demonstrates one embodiment of an apparatus 20 for the use of a chemical treatment agent on fibers 10 used in the manufacture of composites, and continuously a plurality of glass reinforced fibers 12 from a source of molten glass material in a melter over bushing 24. Thin-film forming mechanisms 22, such as conventional glass fiber reinforced bushings 24, employed in accordance with known techniques for forming. In the exemplary method, glass reinforcement fiber 12 discharges thermal energy for a while after it is formed. One or more applicators 26 such as standard single or double roll applicators 28 and fans 30 may be used to form a plurality of coated fibers 32 using one of the exemplary chemical treating agents in the reinforcing fibers 12. The method of continuing the process after using the chemical treating agent, i.e. without cutting a significant number of fibers 10, lowers the viscosity of the chemical treating agent sufficiently low before use or a sufficient amount after use as described above.
Two alternative methods of using chemical treating agents on newly formed glass fibers 12 are described below. Exemplary Method 1 is used when the viscosity of the chemical treatment agent is relatively low at relatively low temperatures (eg, viscosity up to 150 cps at temperatures up to 150 ° F. (66 ° C.)). Exemplary Method 2 is used with high viscosity chemical treating agents. Chemical treatments comprising one of the thin film formers from Examples 1-4 (K) and 6 can be used in Method 1. Chemical treatments comprising one of the thin film formers from Examples 5, 7 and 8 can be used in Method 2. Any chemical treatment agent used in Method 1 may also be used in Method 2. Any chemical treatment agent that can be used in Method 1 or Method 2 can also be used in Method 3, which is another exemplary system.
Method 1:
The method using a chemical treatment agent uses a conventional glass reinforcing fiber forming apparatus adjusted in the zone around applicator 26 to position the applicator 26 in a plane perpendicular to the air stream of glass fiber 12 (ie, fiber 10 Flow)) as well as in the plane containing the fiber 10. Secure applicator 26 to wheeled cart using cantilever. The cart is placed on the rail for easy positioning along an axis perpendicular to the flow direction of the fiber. The upper part of the cart is connected to the body by a scissors jack and the gear arrangement comes out. This raises or lowers applicator 26 against bushing 24. While the processing is in progress, the position of the applicator 26 can be adjusted along both axes. Chemical treatments are stored in metal pails, such as 5 gallon (19 L) buckets.
Heating of the chemical treatment agent is optional. To heat the chemical treating agent, the bucket may be placed on a hot plate and / or surrounded by a bucket heater, such as Model 5 from OHMTEMP Corporation of Garden City, MI. The temperature of the chemical treatment is maintained to the desired degree by various AC thermoelectric pair heat regulators, such as those that are major experimental feed house agents such as Fisher Scientific or VWR Scientific. Chemical treatment agent peristaltic pump 30 to reciprocating peristaltic pumps, such as all (division of Coal Farmer in Barrington, Illinois) Barnant Company Jane, Masterflex Pump Regulator Model # 7549-50 and Masterplex Pipe # 6402 Pump using Masterplex Model # 7529-8 with -73. The applicator 26 is a standard design for the glass fiber forming method and supports a single graphite roller 28 driven by an electric motor at a diameter of 3.0 inches (7.6 cm) and in the range of 3 to 20 feet (0.9 to 6.1 m) per minute. It consists of a metal fan 30. Alternative pumps may be used to deploy peristaltic pumps such as the Zenith pump model # 60-20000-0939-4, manufactured by Parker Hannifin Corporation, NC, Sanford, Zenith Pump Division. The alternative pump is a geared pump equipped with a heating inlet and return hose combination and typically has the following characteristics: Teflon wire, high pressure, internal diameter 0.222 ″ (0.564 cm) × length 72 ″ (183 cm), 12,000 psi ( 83 MPa) Combustion, 3000 psi (21 MPa) Working Pressure, Stainless Steel, 7 / 16-20 Seal JIC Internal Switching Unit, 120 Volt, 300 Watts, 100 Ohm Platinum RTD, Ohio, The Conrad Company, Inc. of Columbus. 72 ″ long string with Amphenol # 3106A-14S-06P plug (heat hose combination is the difference between two alternative (linked to geared) pump systems).
Method 2:
In another exemplary method, a double roll applicator is used to apply a high viscosity, elevated temperature chemical treating agent in a non-aqueous form. The double roll applicator is fixed at a position proportional to the glass forming apparatus. The position of the double roll applicator is the same as originally found in the standard glass fiber forming method, which is approximately 50 inches (127 cm) from the bushing. The heating system and pump system used as the chemical treatment agent in the above method are the same as those for the method 1 above.
The double roll applicator includes a secondary applicator roll larger than two rolls for transferring and measuring the chemical treatment agent to the small primary applicator roll. Direct primary rolls are used to apply chemical treatments to the fibers. The relative small diameter of the primary rolls provides a reduced area of tangency between the rolls and the fibers, reducing the traction force. The tension in the fiber is also reduced due to the reduction in traction. The thickness of the chemical treatment agent used can be measured by adjusting the gap between the primary and secondary rolls and providing a doctor blade on a small roll. The double roll applicator is described in US Pat. No. 3,817,728 to Petersen and US Pat. No. 3,506,419 to Smith et al, incorporated herein by reference.
Method 3:
In this preferred embodiment, the double roll applicator of method 2 and the positioning performance of method 1 are used in conjunction with the heating and pumping system for a chemical treatment agent. The coated fiber 32 is gathered on the strand 14 using a gathering mechanism 34 such as a conventional gathering shoe. A drawing device 36, such as a conventional pair of counter drawing wheels, is used to continuously draw fibers 12 from bushing 24 in a manner well known in the art. Strand 14 is wound on a package (not shown) or cut into pieces of the desired length and stored in composite for subsequent processing offline. Instead, composite strand 14 can be processed directly into the composite inline in a gathering step.
In addition to the continuously formed reinforcing fibers 12, the fibers 10 may further comprise a plurality of matrix fibers 13 made from suitable matrix materials. If matrix fiber 13 is used, the step of using the chemical treating agent includes sizing and / or preimpregnating the matrix fiber 13 with the same or different chemical treating agent used for the reinforcing fiber 12. If different types of fibers 13 are used, it may also be desirable to use different chemical treating agents for each type of matrix fibers 13. Similarly, if different types of reinforcing fibers 12 are used, it may be desirable to use different chemical treating agents for each type of reinforcing fibers 12. If formed or preformed continuously, the same techniques and equipment can be used to chemically treat each type of reinforcing fiber and matrix fiber.
Chemical Treatment Example
Provided below are examples of chemical treatment agents suitable for use in glass reinforced fibers and various matrix fibers and for use with PBT, nylon and polypropylene matrix resins. Various matrix fibers are made of the same material as the corresponding matrix resins. The names "HEAT" and "NO HEAT" mean that the chemical treatments listed are heated to or without heating, respectively, after use on their corresponding fibers. The following chemical treating agents for reinforcing fibers with "NO HEAT" can also be used on matrix fibers made from the corresponding matrix resins. If the previously formed glass fibers reach the applicator at a conventional location (eg, when the applicator is a significant distance from the circle of molten glass), the glass fibers still dissipate some residual heat. However, at this distance from the bushing, the amount of heat dissipated from the fiber may not be sufficient to have any significant effect on some of the chemical treatment agents used. The name "NO HEAT" therefore encompasses the above conditions.
Example A
Composite matrix resin: PET.
Formulation for Reinforcing Fibers:
(1) for HEAT: 83% HELOXY modifier 67, 10% EPON SU-2,5, 5% maleic anhydride and 2% A-1100;
(2) for NO HEAT: 95% HELOXY modulator 67, 3% HELOXY modifier 505 and 2% A-1100.
Formulation for Matrix Fibers:
(1) for HEAT: 83% HELOXY modulator 67, 10% EPON 160 and 7% DICY;
(2) for NO HEAT: 83% HELOXY modulator 67, 10% HELOXY modulator 62 and 7% TGIC.
Example B
Composite Matrix Resin: Nylon.
Formulation for Reinforcing Fibers:
(1) for HEAT: fumarate with 44.5% PG-hydroxy end groups, 44.5% TONE 0260, 5% DESMODUR N-100, 5% BES and 1% A-1100;
(2) for NO HEAT: (a) 47% propoxylated bis-A maleate, 47% TONE 0260, 5% BES and 1% A-1100; (b) 99% allylpropoxylate urethane and 1% A-1100.
Formulation for Matrix Fibers:
(1) for HEAT: (a) 90% allylpropoxylate urethane and 10% dark acid; Or (b) 90% allylpropoxylate urethane, 5% PG-fumarate (hydroxy terminus) and 5% DESMODUR N-100;
(2) For NO HEAT: 47.5% propoxylated bis-A maleate, 47.5% TONE 0260 and 5% BES.
Example C
Composite Matrix Resin: Polypropylene.
Formulation for Reinforcing Fibers:
(1) For HEAT: (a) 68% PG-fumarate, 20% propoxylated allyl alcohol, 5% maleic anhydride, 5% TBPB and 2% A-1100 or A-®; Or (b) 83% PG-fumarate (hydroxy terminated), 5% DESMODUR N-100, 5% maleic anhydride, 5% TBPB and 2% A-1100 and A-®;
(2) for NO HEAT: (a) 88% allylpropoxylate urethane, 10% EPON 8121 and 2% A-1100; Or (b) 90% allylpropoxylate urethane, 5% diallylphthalate, 2% maleic anhydride, 2% BPO and 1% A-1100.
Formulation for Matrix Fibers:
(1) for HEAT: 91% allylpropoxylate urethane, 5% diallylphthalate, 2% maleic anhydride and 2% TBPB;
(2) for NO HEAT: (a) 90% allylpropoxylate urethane and 10% EPON 8121; Or (b) 91% allylpropoxylate urethane, 5% diallylphthalate, 2% maleic anhydride and 2% BPO.
The abbreviation DICY stands for dicyanodiiimide, which is a high temperature amine based curing agent for epoxy resins. Both DICY curing agents and reactive modifier diallylphthalates (for decreasing viscosity) are from Aldrich Chemical Company. DESMODUR N-100 is from Witco Chemical Company. PG-fumarate, propoxylated bis-A maleate (propoxylated bisphenol-A maleate), allylpropoxylate urethane, propoxylated allyl alcohol and acid (i.e. n-butyl amic acid) are all It can manufacture. BES stands for butoxyethylstearate, which in whole or in part, in the chemical treatment agent, is an adduct of compounds such as adipolychloride and n-aminohexane or an adduct of 1,6-diaminohexane and hexanoylchloride, Caprolactone (manufactured by Aldrich Chemical Co.), and amic acid, such as n-butyl amic acid, which can carry out other functions in addition to those provided by BES. TPBP and BPO are peroxide t-butylperoxybenzoate and benzoyl peroxide, respectively, and are manufactured by Akzo-Nobel Chemical Company of Chicago, Illinois. EPON 8121 is a bisphenol-A type epoxy resin from Shell Chemical Company.
99% allylpropoxylate urethane and 1% A 1100 chemical treating agent are used for the glass fibers, the coated fibers are formed in the composite strands, the composite strands are covered or encapsulated with the nylon thermoplastic matrix material, and the encapsulated composite The strands are cut into pellets and the pellets are injection molded into composite test pieces. Encapsulated composite pellets are formed using the wireline coating method of the present invention as described later. In the composite test piece glass fibers are not completely dispersed in the matrix material. This lack of complete dispersion of the glass fibers from the individual strands in the finished composite prevents at least some of the chemical treatment agents from reacting to some extent during the manufacturing process to prevent the fibers from separating and dispersing into the molten matrix material during molding of the composite ( That is, to maintain strand aggregation). Dilute allylpropoxylate urethane with another thin film forming agent to reduce its reactivity (ie, reduce fiber agglomeration in each composite strand during the composite molding process) and thereby obtain more dispersion of reinforcing fibers in the matrix material. For example, TONE 0260 (polycaprolactone, manufactured by Union Carbide Corp.) for nylon can be used.
The following are further examples of chemical treating agents in the thermosetting and thermoplastic forms according to the invention.
Nylon-Based Chemical Processing Agents:
About 9 kg of polycaprolactone, specifically TONE 0260 (manufactured by Union Carbide Corporation), and about 9 kg of polyester alkyd, specifically propoxylated bisphenol-A maleate, are accumulated in a fractional 5 gelon (19 L) metal can To produce particularly preferred nylon-based thermoplastic forms of chemical treatment agents. Upon complete melting or liquefaction of the two materials, they are mixed in a heated 5 gallon (19 L) can and stirred until the mixture is homogenized. The temperature is maintained above 200 ° F. (93 ° C.) with continued stirring until complete mixing is achieved (about 30 minutes). Then stop heating and cool the mixture to 190 ° F (88 ° C). While maintaining the temperature at 190 ° F. (88 ° C.), about 360 g of the amine silane coupling agent A-1100 (gammaaminopropoxytriethoxysilane) is added to the mixture with continued stirring. The resulting chemical treating agent contains 49-49.5 wt% TONE 0260, 49-49.5 wt% propoxylated bisphenol-A maleate and 1-2 wt% A-1100. The chemical treating agent is a solid at about 25 ° C. and 660 cps at 75 ° C., 260 cps at 100 ° C., 120 cps at 125 ° C. and 60 cps at 150 ° C.
The chemical treating agent, along with its container, is then transferred to the bucket heater described in Method 2 above and pumped to a suitable applicator. Glass fiber 12 is diluted and the applicator roll 28 is contacted. The chemical treatment is then transferred onto glass fiber 12 at about 115 ° C. Fiber 12 is gathered in a conventional shoe 34 and wound onto a collet to make and cool a square edge package.
The resulting package is stable and transportable, and the rovings flow out well. The resulting composite strand 14 can be streamlined and cut into pellets for ultimate use in injection molded coatings.
PBT based chemical treatment agents:
17.28 kg of diglycidyl ether of 1,4-butanediol (HELOXY 67) are accumulated in a 5 gallon (19 L) metal can to prepare a chemical treatment agent in the form of a particularly preferred PET based thermoplastic. 540 g (HELOXY 505) of polyglycidyl ether of castor oil is added to the above. 180 g of A-1100 (gammaaminopropyltriethoxysilane) is added to the mixture as a coupling agent. The resulting chemical treating agent contains 96 weight percent HELOXY 67, 3 weight percent HELOXY 505 and 1 weight percent A-1100. The mixture is stirred until uniform. It is then transferred along with its container to a bucket heater, such as that of method 1 (although it is not necessary to heat the chemical treatment agent for processing). In order to use the chemical treatment agent, applicator 26 is raised from bushing 24 to 8-10 inches (20.32-25.4 cm).
Polyester or vinyl ester based chemical treatment agents:
6.75 kg of DER 337 epoxy (bisphenol-A epoxy resin, manufactured by Dow Chemical Compnay) is accumulated in a 5 gallon (19 L) metal can to prepare a chemical treatment agent in the form of particularly preferred polyester or vinyl ester based thermosets. The material is heated to 220 ° F. (104 ° C.) until all solids are completely liquid. 6.75 kg of Araldite GT7013 epoxy (bisphenol A epoxy resin, manufactured by Ciba Geigy Corporation) is added to the liquid. Araldite is added slowly with considerable stirring for 2 hours. Upon complete dissolution of the araldite epoxy, the mixture was cooled to 200 ° F. (93 ° C.) in air, 0.76 kg of Pluronic L101 (ethylene oxide / propylene oxide copolymer surfactant, made by BASF) and 2.21 kg of Pluronic P105 (Ethylene oxide / propylene oxide copolymer surfactant, also made by BASF) is added. At the same time, 1 kg of PEG 400 MO (polyethylene glycol monooleate, manufactured by Henkel) and 0.5 kg of butoxyethylstearate (BES) (Illinois, manufactured by Stepan Company, Northfield) are added. The mixture is further cooled with further stirring at a temperature of 160-170 ° F. (71-77 ° C.), at which point 2 kg of A-174 (gammamethacryloxypropyltrimethoxysilane, Witco Chemical Corporation) is added. do. Finally, 20 g of Uvitex OB (Fluorescent Light Emitter from Hawthorne, Ciba-Geigy, NY) is added to the mixture with stirring to promote good dispersion. The resulting chemical treatment agent was 33.78 wt% DER 337 epoxy, 33.78 wt% Araldite GT7013 epoxy, 3.79 wt% Pluronic L101, 11.05 wt% Pluronic P105, 5 wt% PEG 400 MO, 2,5 wt% BES, 0.10 wt% Uvitex OB and 10% by weight A-174 are added. The chemical treating agent is then transferred along with its container into a bucket heater as described in method 2.
Epoxy-Based Chemical Processing Agents:
Except for using A-187 (gammaglycidoxypropyltrimethoxysilane, manufactured by Witco Chemical Company) instead of A-174, the formulation of the heat treatment of the thermosetting form of the above examples is carried out in the polyester and vinyl ester based Same as above for the chemical treatment agent.
In the preferred embodiment shown in FIG. 3, matrix fiber 13 is preformed and then mixed with reinforcing fiber 12 before gathering into composite strand 14. The matrix fiber 13 finally forms part or all of the resulting composite. Fiber 10 may include only reinforcement fibers 12 or preformed reinforcement fibers formed continuously and preformed. If preformed reinforcing fibers 12 are used, they can be processed directly into strand 14 containing only preformed reinforcing fibers 12. The preformed reinforcing fibers 12 may also be mixed with any other type of fibers in the same or similar manner as in the preformed matrix fibers 13 shown in FIG. 3. While only representing a spool or package of two preformed fibers, A suitable number of packages of preformed fibers can be supplied in a proven or another suitable manner.
Prior to gathering the fibers into strand 14, the same applicator 26 was both preformed fibers (e.g., preformed matrix fibers indicated by phantom 13 ') and continuously formed fibers (e.g., continuous formed reinforcing fibers 12). Can be used for chemical treatment. Instead, separate applicator 26 'can be used to chemically treat preformed fibers (eg, preformed matrix fibers 13). If using a separate applicator 26 ', the gathering mechanism 34 assists in mixing the fibers 12 and 13 before gathering into strand 14, including a bar or roller 39. Preformed and continuously formed fibers can be chemically treated using the same applicator together or separately using different applicators, as described in US Patent Application Serial No. 08 / 527,601, filed Sep. 13, 1995, Its description is inserted by reference. Instead, a portion of the fiber 10, for example matrix fiber 13, can be gathered together with the coated fiber 32 without first using a chemical treatment agent.
The chemical treatment agent used may be heated before, during and / or after the gathering step of the fibers. If this acts as a thermosetting resin, the chemical treatment agent used can be partially or fully thermally cured to some degree of compound strand 14 formulation. The method and time of thermosetting the thermosetting chemical treatment agent used depends on the type of composite produced from strand 14. For example, composite strand 14, complete, partially or thermoset free of the chemical treatment agent used, can be cut into a number of short separation lengths, mixed into molding compounds and injection molded into the composite.
To cut the length of strand 14, the chemical treatment agent used is sufficiently cured, if any, to ensure that the short length of composite strand 14 is agglomerated (ie, fibers 10 are together) during subsequent processing. If it acts as a thermosetting resin or otherwise heat curable, the used chemical treating agent on the coated fibers is preferably only partially cured during formation of the composite strand 14. The curing of the chemical treatment agent used is preferably completed by the subsequent inline or off-line method of the composite strand 14 (eg pultrusion, filament winding, transition injection molding, compression molding, etc.). If the molecular weight of the chemical treatment agent becomes infinity (ie, maximized) during the formation of the composite strand 14, the thermally stable form of the chemical treatment agent is preferably of the composite part since the strand 14 cannot be processed further in the downstream composite forming coating. Only partially cures until formation. The partial cure can also be achieved by selecting components that react completely with each other under the conditions present during the complex stranding process. It may also be achieved by selecting a relative amount of each component of the chemical treatment agent (eg, by adjusting the stoichiometry of the chemical treatment agent) so that at least one heat-setting component in the chemical treatment agent is only partially reacted or cured until the formation of the composite. Can be. Exemplary chemical treating agents having one or more respective components that can only be partially reacted or cured during the stranding process are about 85% by weight PG-fumarate, about 10% by weight styrene and about 5% by weight t-butylperoxybenzoate It contains.
In the chemical treatment agents listed in Examples A-C, several reactive species appear. In most cases it is desirable for some unreacted species to remain on strand 14 in the strand forming process, while in some cases the species is fully reacted when in strand form, for example in the chemical treatments listed above containing isocyanates or acid acids. It may be desirable. As isocyanates, if a diol is present in a sufficient amount (eg, about 20 times the isocyanate group) and if a chemical treating agent is used at a sufficiently high fiber surface temperature, the isocyanate groups will be sufficiently reacted in the composite strand 14. Similarly, if the reaction conditions are correct (eg, high temperature and relative low concentrations), it will completely convert the acid to the imide in the chemical treatment agent.
Chemical treatments containing about 45 wt% PG-fumarate, about 50 wt% styrene and about 5 wt% t-butylperoxybenzoate can be prepared. This represents a polyester resin blend that can be used on glass fibers using an applicator device as described in Methods 1 to 3 above and that can be cured to a hard material on glass fiber strand 14 upon addition of heat emanating from the newly formed glass fiber. . By removing about 90% by weight of styrene, the polyester resin chemical treating agent can only be partially cured when used in fibers. An additive chemical treating agent containing about 35% by weight of epoxy resin Epon 828, manufactured by Shell Chemical Company, about 35% by weight of reactive epoxy modifier HELOXY 505, about 28% by weight maleic anhydride and about 2% by weight A 1100 can be prepared. have. The epoxy resin blend can be used for glass fibers using the optional applicator device and can be cured to a hard material on glass fiber strands 14 upon addition of heat emanating from the newly formed glass fibers. About 90% of all maleic anhydride is removed, so that the epoxy resin chemical treating agent can only be partially cured when used in fibers.
Raise applicator 26 to a position closer to heat emanating from the molten glass (eg, bushing 24), above applicator roll 28 (ie where roll 28 is in contact with glass fiber 10), as well as glass fiber 12. It was observed that the viscosity of the chemical treatment agent of the thermoplastic form was lowered on the surface of. Chemical treatment agents in thermosetting form, which act as thermoplastics at the stage of the process, will also experience a significant drop in its viscosity. A component in viscosity of the chemical treatment agent was observed along the surface of the applicator roll 28. The viscosity was found to be the lowest behind glass fiber 10 and appears to increase toward either end of roller 28.
For the FIG. 1 embodiment of device 20, when fiber 12 is at a sufficiently high temperature (i.e., fiber 12 releases sufficient thermal energy) a desired lowering in viscosity and / or crosslinking or otherwise used chemical treatment agent is used with chemical treatment agent. Place applicator 26 in close proximity or otherwise sufficiently close to bushing 24 which generates the desired degree of thermosetting by increasing the molecular weight of. At the same time, applicator 26 is positioned far enough from bushing 24 such that fiber 12 is at a temperature that does not cause significant loss (eg, degradation of any organic chemicals or compounds) to chemical treatment agent while using chemical treatment agent. In this way, the resulting strands 14 are provided with the desired properties for subsequent processing into composites.
Exemplary fiber temperatures for using chemical treatment agents are about 350 ° C. (662 ° F.) or less, and the use of some treatments at high temperatures is possible without significant deterioration or other damage. Fiber temperatures as low as about 150 ° C. (302 ° F.), or even lower, may be used. In order to protect the chemical treatment agent used and to generate one or more of these two changes in the chemical treatment agent used, the fiber 12 is preferably at a temperature of about 200 ° C. (392 ° F.) to about 300 ° C. (572 ° F.). Satisfactory results are obtained when the viscosity of either type of chemical treatment agent drops from about 200 cps to about 400 cps at a temperature of about 200 ° C. to about 300 ° C. For conventional bushings 24 having conventional throughput, or glass-reinforced fibers 12 drawn from bushings 24 (i.e., from where fiber 12 leaves the bushings), applicator 28 is preferably placed so that the chemical treatment agent is at least about 3 inches (7.62) cm), and typically at glass fibers 12 at a minimum of about 6 inches (15.24 cm). Chemical treatment agents can be used for the glass reinforcement fibers 12 at a distance of about 8 inches to about 10 inches (20.32 cm to 25.4 cm) from the bushing 24. The exact position of the applicator 26 relative to the bushing 24 is, for example, The shape of the bushing 24 (eg, the number of fibers drawn from the bushing), the temperature of the molten glass material, the type of chemical treatment agent used, the desired properties of the interfacial zone around the reinforcing fibers 12 and the resulting strand 14 and ultimately the composite Depends on the desired characteristics.
With reference to the alternative embodiment depicted in FIG. 2, device 38 comprises the components of preliminary described device 20 and heat retainer 40. Accordingly, components of the same or similar device 38 as those of the device 20 are denoted by the same reference numerals. The heat retainer 40 is partially or completely disposed at least around the fiber 12 and modulated using conventional techniques to maintain heat energy emanating from the surface of the fiber 12 and further from the fiber forming apparatus 22 for a long time. Low throughput glass using an exemplary heat retainer 40 made from sheet metal formed into an open rectangular box shape of about 15 inches (38.1 cm) long, about 3 inches (7.62 cm) wide and about 16 inches (40.64 cm) high. Satisfactory results are obtained with fiber bushing 24. Low throughput glass fiber bushings 24 typically form glass reinforcement fibers 12 at rates of up to about 30-40 lbs./hr (13.62-18.16 kg / hr). A box-shaped heat retainer 40 is placed between the thin film forming apparatus 22 and the applicator 26 to draw at least fiber 12 through openings 42 and 44. Preferably, the heat retainer 40 is sufficiently insulated so that the surface of each fiber 12 at a temperature of about 150 ° C. (302 ° F.) to about 350 ° C. (662 ° F.) by the time the applicator 26 uses the chemical treatment agent on the fiber 12. Keep it.
The use of the heat retainer 40 is particularly advantageous when using a low throughput continuous fiber forming bushing 24. The amount of thermal energy stored by the fibers 12 formed using the low throughput bushings 24 is less than that stored by the fibers 12 formed using conventional or high throughput bushings. Thus, heat retainer 40 allows fibers 12 formed using low throughput bushings to be maintained at a temperature necessary to produce the desired reaction (low viscosity and / or at least partial thermal curing) with the chemical treatment agent used. Adjusting heat retainer 40 to place it below or below the applicator 26 is to keep the fiber 12 at the desired elevated surface temperature at or below the applicator 26. For example, the heat retainer 40 and another heat retainer of the same structure can be disposed between the periphery of the partially or fully coated fiber 32 and the applicator 26 and the gathering mechanism 34. The use of the additive heat retainer may be desirable if additional curing of the chemical treatment agent is necessary prior to collecting strand 14, for example on a spool, or else before processing. Examples of means that may be useful, such as heat retainers, after use of the present invention, in particular chemical treating agents, are described in US Pat. No. 5,055,119, the disclosure of which is incorporated herein by reference.
The energy used to heat the chemical treatment agent used may be supplied, if not entirely, with thermal energy emanating from the coated fiber 32, at least in part. For example, residual heat flowing out or remaining from continuously formed glass fibers can provide a significant amount of thermal energy. Residual heat emanating from the continuously formed polymeric matrix fiber 13 can be similarly used to effect the desired change in the chemical treatment agent used.
If residual heat is not available or insufficient from the fiber forming method, for example, if fiber 10 is preformed, cooled or otherwise not at the desired temperature, fiber 10 may be preheated to give the desired thermal energy to the chemical treatment agent used. Can be. The preheating can be achieved using a conventional heating system. For example, referring to FIG. 2, a conventional open / close furnace (not shown) may be used in place of heat retainer 40 to preheat at least fiber 12 to a desired temperature prior to using a chemical treatment agent.
With the heat energy emanating from the fiber 32 supplying at least a portion of the required heat energy, the chemical treatment agent used decreases its viscosity and / or is at least partially from the surface of the fiber 32 coated externally through at least a portion of the chemical treatment agent used. Thermally cured. Heating from outside the fiber surface is a particularly preferred and effective way to heat the chemical treatment agent used and to help optimize the bonding between the chemical treatment agent and the surface of the coated fiber 32. In addition, heating from the surface of the coated fiber 32 allows for a large variation in the planning of the interfacial zones formed by the chemical treatment agent used between each of the coated fiber 32 and the matrix material of the composite. For example, the heating of the chemical treatment agent in the thermoplastic form used from the inside helps to confirm that its viscosity at the surface of the fiber is sufficiently low to obtain adequate humidification of the fiber surface. In addition, the heating of the thermoset chemical treatment agent used in this manner causes the chemical treatment agent used to fully cure only at its interface to the fiber surface, thereby only partially curing or retaining the outer zone of the uncured chemical treatment agent, which is then It can be cured completely at the desired time and place during processing. For example, it may be desirable for the outer zone to be partially cured or uncured to facilitate bonding between the chemical treating agent and the subsequently used matrix material or the contact layer of the chemical treating agent used on adjacent fibers.
Preferably, the heat emanating from the fiber 12 is used to heat the chemical treatment used. Optionally, the energy used to heat the chemical treatment agent used may be partially, substantially or completely provided by thermal energy exiting from a source outside the coated fiber. For example, after using a chemical treatment agent, the coated fiber 32 may be passed through a conventional open / close furnace (not shown) before, during or after gathering the coated fiber 32 with strand 14. The treating agent used can also be heated externally during the formation of the strand 14 into the composite. By externally heating it, the treating agent used decreases its viscosity and / or is at least partially thermally cured from its outer surface with the chemical treating agent used towards the surface of the coated fiber 32. Thus, the energy used to heat the used chemical treating agent is also provided by a combination of the coated fibers 32 and heat exiting from the dispersed one or more external heat sources to heat at least the reinforcing fibers 12 before and / or after using the chemical treating agent. Can be.
The chemical treating agent can be kept cold before use on the fibers 12 to allow the use of highly reactive components and to help reduce the risk of exacerbation due to heat of the chemical treating agent. Prior to use, the temperature of the chemical treatment agent may be kept below about room temperature for the same reason. The chemical treating agent may be maintained at the desired temperature by any suitable means. For example, cooling coils (not shown) may be deposited in the chemical treatment agent. In the case of forming continuously forming glass fibers, the apparatus can also be fixed to surround the glass fibers 12 with an inert atmosphere before using the chemical treatment agent. An inert atmosphere should help prevent moisture from accumulating on the surface of the fiber 12 and thereby initiating moisture induced pyrolysis and passivation, which is a source of moisture for potential reactive species on the glass fiber surface. Inert atmospheres may be undesirable if high temperature bushings are used or if the temperature of the glass fibers is sufficiently high at any other time. A heat retainer 40 (see FIG. 2) or a similar structure surrounding the glass fibers can be used to surround glass fiber 12 with an inert atmosphere, and when the fiber 12 passes through it, pipes the inert atmosphere to the heat retainer 40. do. Suitable inert atmospheres include, for example, one or a mixture of nitrogen and argon gas.
An advantage of the chemical treating agents of the present invention is that they can be processed using known fibers, strands and composite forming devices. In a preferred embodiment, solvent-free chemical treating agents can be advantageously used in the following streamline coating systems.
Enclosed Strand Manufacturing
Another general aspect of the present invention is to encapsulate one or more plastics into a composite having a polymer or resin material reinforced with a fiber made from a suitable reinforcing material, such as a glass material, a synthetic or polymeric material, or another suitable non-glass material. A method and apparatus for producing a composite article. The enclosed composite strands may be in thread form (ie, long length) or pellet form (ie, short length).
More particularly each encased composite strand has a plurality of fibers, including at least reinforcing fibers and optionally fibers made of thermoplastic matrix material used in the composite. While processing the fibers into strands or bundles, each strand preferably contains about 1,500 to about 10,000 fibers, more preferably about 2,000 to about 4,000 fibers. It is preimpregnated with a chemical treatment agent before forming the strands.
The preimpregnated composite strand is sealed with a cover of thermoplastic material. When encapsulated composite strands are formed into pellets, a chemical treatment agent is used between the fibers in a sufficient amount and a sufficient number to prevent the fibers from falling out of the pellets. When encapsulated composite strands are formed into yarns, a chemical treatment agent is disposed between substantially all of the fibers.
In a preferred embodiment, the chemical treating agent is a polymeric material in thermoplastic form. Instead, the chemical treating agent that impregnates the composite strand may be a polymeric material in a thermoset form that is fully cured, partially cured or uncured. Fiber strands may optionally be fully impregnated with those used to enclose or coat engineering thermoplastic matrix materials such as composite strands. Although some engineering thermoplastics have relatively high melting points and high viscosities that can be very difficult or impractical to use in engineering fibers using conventional applicators, those skilled in the art will appreciate that engineering thermoplastics used as chemical treatment agents in the present invention. Resin can be adjusted suitably.
Preferably, the lid encapsulating the composite strand is made of the same thermoplastic material used to form the matrix of the composite. The thermoplastic sheath material may form part or all of the matrix of the composite, depending on the thickness of the sheath. At least until the molding of the composite, the chemical treatment agent preferably helps to bind the fibers in strands which are sufficiently bonded or otherwise pre-impregnated. In addition, the chemical treating agent is at least compatible with the thermoplastic matrix material of the composite.
In the preferred method for producing at least one thermoplastically encapsulated composite strand, a streamlined or extrusion coating method is used. The method includes the steps of: providing a plurality of fibers comprising at least reinforcing fibers; Coating substantially all of the fibers with the chemical treatment agent thereby forming the preimpregnated fibers; Gathering or otherwise mixing the coated fibers into one or more preimpregnated strands having a chemical treatment agent disposed between substantially all of the fibers forming the preimpregnated strands; Coating at least the exterior of the preimpregnated strands with a thermoplastic material to form one or more coated strands; And forming the coated strand into one or more streamlined or otherwise enclosed composite strands.
The fibers can be provided using an inline method that includes continuously forming reinforcing fibers from a source of melt reinforcing material, such as glass. In addition to the continuous forming reinforcing fibers, provided fibers may comprise preforming reinforcing fibers, preforming matrix fibers, continuous forming matrix fibers or mixtures thereof. If it is an aqueous system, a significant amount of moisture is evaporated here before gathering the coated fiber into the preimpregnated strand by heating the chemical treatment agent used on the fiber. If it is in a thermoset form, chemical treatment agents are used for the fibers in the uncured or partially cured state. Uncured or partially cured chemical treating agents that stop impregnating the encapsulated composite strands can be processed (eg by heating) to induce addition partial or complete curing, depending on the desired conditions of the encapsulated composite strands during molding of the composite. In a preferred embodiment, such solvent-free chemical treating agents are used. Instead, a two part nonaqueous chemical treating agent may be used as described in US Patent Application Serial No. 08 / 487,948, filed June 7, 1995, the content of which is incorporated herein by reference.
Exemplary systems for the formation of polymer encapsulated strands are shown in the figures, in particular FIGS. 4 to 6. 4 shows one embodiment of an apparatus 110 for directing a circle 112 of fiber 113, consisting of reinforcing fibers 114 in the above embodiment. One exemplary embodiment 112 is a conventional bushing 115 of a melt reinforcing material (eg, glass) that draws a continuous reinforcing fiber 114.
Applicator 116 uses a chemical treatment on substantially all fibers 114. In a preferred embodiment, the chemical treating agent used is aqueous, and applicator 116 is a conventional form suitable for using an aqueous based chemical treating agent. Exemplary applicator 116 includes a back applicator roller 118 that uses a chemical treating agent on reinforcing fibers 114, thereby forming preimpregnated or coated fibers 120. The chemical treating agent is used in contact with the roller 118 when the fiber 114 passes. A trough 122 containing a chemical treatment agent is placed under roller 118. The roller 118 extends to the trough 122 and transfers the chemical treatment from the trough 122 to the fiber 114 when the roller 118 is rotated with a conventional drive such as a motor (not shown). Other suitable devices or techniques used to use size or other chemical treatment agents may be used to use chemical treatment agents on the reinforcing fibers 114 in place of the applicator roll assembly 116.
The aqueous based chemical treatment agent used on the preimpregnated or coated fiber 120 is heated to evaporate a significant amount of moisture therein, and the coated fiber 120 is then gathered into the preimpregnated composite strand 124. Moisture can be used to drain the aqueous based chemical treatment agent using any suitable heating device 125. For example, one of the hot plates described in U.S. Patent Application Serial Nos. 08 / 291,801, filed August 17, 1994, and 08 / 311,817, filed September 26, 1994; A substantially similar heating device 125 may be contacted, the description of which is incorporated herein by reference.
Conventional gathering shoes or some other type of gathering machine 127 may be used to gather the dry fibers 120 at least one pre-impregnated strand 124. The preimpregnated strand 124 is covered or encapsulated with a layer of polymeric material and thereby formed into an encapsulated composite strand 126 by drawing or otherwise passing the preimpregnated strand 124 through a wire coater 128. Mammary coating is a device or apparatuses, or means, which can coat one or more preimpregnated fiber strands with a polymeric material to form a polymer covering on each preimpregnated strand 124. Preferably, each strand contains about 1,500 to about 10,000 fibers, more preferably about 2,000 to about 4,000 fibers.
The fibers 113 used to form the encapsulated composite strand 126 can be produced using an inline method as shown in FIG. 4, wherein the reinforcing fibers 114 are continuously tensioned from a bushing 115 of a melt reinforcing material such as glass. In addition to or instead of the continuously formed reinforcing fibers 114, the fibers 113 may contain preformed reinforcing fibers. Further, fiber 113 may comprise preformed matrix fibers and even continuously formed matrix fibers, or mixtures thereof. Exemplary systems for forming pre-impregnated strands using aqueous chemical treating agents in continuous and preformed hemp oils are described in the above incorporated US patent application Ser. No. 08 / 311,817.
The matrix fibers ultimately form part or all of the resulting composite or product, such as pellet 132. Examples of suitable polymeric materials for matrix fibers include polyesters, polyamides, polypropylenes and polyphenylene sulfides. Continuous and preformed reinforcing fibers may be glass fibers, synthetic fibers, and / or any other suitable reinforcing fibers, such as fibers of conventional silicate glass, rock wool, slag cotton, carbon, and the like. When using various fibers made from different materials, the same or different chemical treating agents can be used for each type of fiber.
Preferably, the streamlined coater 128 comprises a source of molten polymer material, such as a conventional extruder, to provide the material used to enclose the preimpregnated strand 124. Streamlined cloth 128 also preferably includes a die or other suitable means having one or more outlets or switches for shaping the cover to a desired thickness and / or cross section, preferably a thickness and cross section that remain relatively uniform along its length. do. Exemplary wireline machine 128 is manufactured by Killion of Cedar Grove, NJ, which includes a KN200 2 inch (5 cm) extruder equipped with a cross-head coated die. do. One or more encapsulated composite strands 126 may be formed by drawing or otherwise passing through one or more cladding strands 124. The covering material is preferably thermoplastic and can form part or all of the matrix of the composite, for example depending on the thickness of the covering. In a preferred embodiment, the lid encapsulating composite strand 124 is made from the same thermoplastic material used to form the matrix of the composite.
If the encapsulated composite strand 126 is desired to be short in length, the apparatus 110 may include means such as a cutter 130 to cut or otherwise separate the encapsulated composite strand 126 into a plurality of encapsulated composite pellets 132. Exemplary cutter 130 is a Model 204T cutter manufactured by Conair-Jettro of Bay City, Michigan. When forming pellets 132, the chemical treatment agent helps to collect the fibers 114 in each encapsulated composite pellet 132 (helps prevent a significant number of fibers 114 from falling out of the pellets 132).
Although the encapsulated composite pellets are larger or smaller than suitable, the encapsulated composite pellets are preferably about 3/16 inches (0.467 cm) to about 11/2 inches (3.8 cm). In an exemplary embodiment, the pellets have a length of about 0.5 inches (1.27 cm). Of course, the length of the pellets can vary from one application to another. Moreover, the shape of the encapsulated composite strands can vary and can be tailored to a particular coating.
For example, a fiber 114 may be drawn through the device 110 using a drawer 134 which serves to draw the reinforcing fiber 114 from the bushing 115 and draw the preimpregnated strand 124 through the streamlined coater 128. An exemplary drawer 134 successfully used inline with the Killion Streamliner 128 is a 4/24 High Speed Puller (also manufactured by Killion). Instead, the wireliner 128 and / or cutter 130 can be modified to perform the operation of the drawer or to help drawer the preimpregnated strand 124 through the wireliner 128.
In order to seal the encapsulated composite strand product in the form of a yarn, the cutter 130 draws the strand 124 stretched and pre-impregnated the reinforcing fiber 114 from the bushing 115 through the wire wrapper 128, and the encapsulated composite strand 126 into the encapsulated composite yarn 140 It can be replaced by a winding device 136 which is wound into a spool or other package 138. When in yarn form, strand 124 is at least substantially impregnated, unless fully impregnated with the chemical treatment agent used. In other words, the strand 124 is sufficiently impregnated to impart sufficient properties to the composite formed by impregnation.
Optionally, the winding device 136 may include a tensioner that assists in stretching the fiber 114 and / or tensioning the strand 124. The example winding device 136 shown in FIG. 5 includes a rotatable member or collet 142 equipped with a removable large diameter spool 144. The winding device 136 also includes a transversal mechanism for distributing the continuous compound strand 126 along the length of the spool 144 to form the package 138. The air supply (not shown) can provide a to collide with the strand 126 to supply an air stream that cools the strand 126 before winding it.
An example winding device 136, which may be used in combination with an offline wired cladding operation, may combine Hall Capstan Machine # 634 (tensioner) and Hall Winder Machine # 633 (both of which are Hall Industries of Branford, Connecticut products). In this off-line streamlined operation, the pre-impregnated strand 124 is faceted and packaged, then the packaged strand 124 is then released offline and tensioned through the streamlined coater 128, and the resulting encapsulated composite strand 126 is returned to the package. It is wound. If appropriate, the above-mentioned Hall wire wound device can be used using known techniques in wired operation and cable operation processes, which are operated at high process speeds in connection with the in-line wireline coating process. For example, the spool 144 on which the encapsulating composite thread 140 is wound can be wound to a large diameter.
As an example, the setup procedure of instrument 110, generally wireliner 128, passes or threaded the free end of pre-impregnated strand 124 through wireliner 128 and sufficiently tensions through strand 124. Thereby allowing the process to proceed on its own (ie, the strands to be automatically tensioned). This set-up process involves a conventional tension wheel 137 located at the free end of the pre-impregnated strand 124 (denoted by imaginary line 124 '), for example, away from the wire wrapper 128, whereby the pre-impregnated strand 124 is routed through the wire wrapper 128. Tensioning to a length sufficient to pass. This length of pre-impregnated strand 124 is passed through streamlined coater 128, through which it is tensioned by tensioner 134, cutter 130, winding 136, or a combination thereof. For the streamlined coater 128, a feed line is preferably used for threading the free end of the pre-impregnated strand 124 through the streamlined die. This feed line has an end that can protect the free end of strand 124. For example, a streamlined length with a hook at one end can be used. The feed line may be preliminarily located through the wireline die and the glass end of strand 124 is doubled, hooked by the feedline, and then drawn through the wireliner 128. This setup process is preferably performed during the process and at breakout (ie when the fiber strands are broken).
Preferably, the die used for the wire wrapper 128 has an openable arrangement or “clamshell” arrangement such that the pre-impregnated strand 124 is threaded longitudinally through the die from one end to the other. Place it into the die. This openable die can eliminate the need for the supply line. An example clamshell die includes two die halves that can be paired using a guide post or pin arranged through a matching hole formed opposite the die halves. do. Alternatively, the two half dies can be hinged along adjacent edges and locked together along the opposite edge when the halves are hinged and closed. The front of each die half defines half of the die cavity through which the impregnated strands are tensioned. When the die halves mate with each other, the die cavity opens and opens. The inlet is preferably larger in size than the encapsulated composite strand 126 to minimize fiber wear, and the outlet is preferably of a size that defines the desired final diameter and outer thickness of the encapsulated composite strand 126.
When the die halves are separated, strand 124 is quickly placed between the die halves, and strand 124 is trapped therebetween in the die cavity by closing the die halves. A hot gasket may be arranged between the opposite sides of the two die halves along the length of the die cavity. Each die half has one or more holes (ie through holes) through which one or more streams of molten thermoplastic coating material, for example from the extruder, are moved into the die cavity, with pre-impregnated strands 124 in between. When stretched through, it is covered. Each die half can be used to accommodate a variety of inserts trimmed through different die cavities to vary the cross-sectional profile (eg, round, rectangular, oval, rugged, etc.) of cladding strand 126. As such, the inserts are replaceable, so that different fiber diameters can be manipulated with the same die, reducing the time it takes to replace the entire die.
Preferably, the chemical treatment agent is selected to assist or bind the outer circumference to maintain the fibers 113 in the encapsulated composite strand 126 until at least the composite is molded. In order to assist the composite to exhibit optimal mechanical properties between the reinforcing fibers and the matrix, the chemical treating agent must be compatible with the thermoplastic matrix material of the composite. Chemical treating agents are considered to be compatible with the matrix material, provided they do not inadequate important properties of the resulting composite, such as tensile strength, tensile modulus, flexural strength or flexural modulus. Such compatibility can be achieved by formulating the chemical treating agent to interact and / or react with the thermoplastic matrix material. Interactions and / or reactions between chemical treating agents (eg, thermoplastic or thermoset forms) and matrix materials can occur when making encapsulated composite strands, molding composites, or during these two processes.
The chemical treating agent may form a layer that is miscible in whole or in part with the matrix material and / or is separated from the matrix material. If a separation layer is formed, the chemical treatment agent arranged around each fiber may form a plurality of separation layer sites arranged within the matrix material and / or a single separation layer site surrounding the fibers. Chemical treatment agents, such as those described below, may be selected to enhance the properties of the composite.
Aqueous chemical treatment agents
For example, the aqueous chemical treating agent used with the apparatus 110 may contain one or more polymer thin film forming agents in solid powder form or other particles dispersed in the water medium. The particle thinner may be a thermoplastic polymer, a thermoset polymer, or a mixture of both. Low molecular weight and / or high molecular weight solid thermoplastic and heat-setting polymers can be used to form the particle thinner. The aqueous chemical treating agent may also contain one or more binders dispersed in the water medium with the particles of the film forming agent. The binder may contain thermoplastic and / or thermosetting liquids, low melting thermoplastic particles, or mixtures thereof.
Preferably, the binder not only prevents the falling of solid particles of the thin film-forming agent from the encapsulated composite strands, but also prevents the fibers from falling out of the composite strands even when the strands are in pellet form. To accomplish this, the thermoplastic binder particles can be at least partially melted or melted by the thermal energy used to evaporate water from the chemical treatment agent. In addition, the liquid binder has the necessary degree of tackiness or adhesion, so as to sufficiently maintain the bonding strength of the thin film former particles and fibers. Preferably, the high melting point thermoplastic thin film powder is mixed or modified with low melting point thermoplastic binder particles such as polyvinyl acetate (PVA) particles, aqueous urethane and the like.
Aqueous chemical treating agents may also contain liquid thin film formers (eg, emulsions) dispersed in a water medium. Liquid thin film forming agents may contain one or more low molecular weight thermoplastic polymers, one or more thermosetting polymers, or mixtures thereof. Preferably, in conjunction with an aqueous chemical treating agent emulsion, the liquid thin film former can also act as a binder. The aqueous chemical treating agent may also contain a mixture of liquid-solid dispersions and liquid-liquid emulsions.
Binders and thermosetting thin film formers used in aqueous chemical treating agents may be used in the partially cured state, but are preferably used in the fibers in the uncured state. The fixed amount or curing amount of the thermosetting chemical treatment agent can be controlled by selecting an appropriate amount of the thermosetting material to be cured to the desired degree at the temperatures present during the process according to the invention. The uncured, or partially cured, thermoset type chemical treating agent to be impregnated into the encapsulated composite strand may be further or fully cured, depending on the desired conditions of the encapsulated composite strand, during the cutting operation, the winding operation, or the molding of the composite. Can be processed (e.g., by heating). The degree to which the thermosetting chemical treatment agent used is cured can be controlled by using a heating device (eg, heater 125), whether or not it is aqueous.
Therefore, the thermosetting chemical treatment agents are treated, if necessary, to impart sufficient curing to maintain the bond strength and / or degree of impregnation of the encapsulated composite strand until the composite is molded. Each fiber forming strand need not be separated in the thermoplastic matrix material to form the desired composite. The thermoset chemical treatment is then fully cured to allow the fibers to be permanently bonded even during the molding of the composite.
The aqueous solution treatment contains one or more chemical treatment polymers or other organic compounds or materials (eg thin film forming agents, binders) in an amount sufficient to allow sufficient preimpregnation of the fibers. For example, the aqueous chemical treating agent, if necessary, contains a sufficient amount of thin film forming agent and binder polymer to impregnate the fibers to the desired degree. Aqueous chemical treating agents may include one or more thin film forming agents, binder polymers, and / or other organic materials, after the organic material content of the pre-impregnated strands removes the desired amount of moisture from the chemical treatment agents used, It is preferably contained at a concentration sufficient to be about 25% by weight or less, preferably about 15% by weight or less, and more preferably about 6-7% by weight. The degree of organic material content will also be useful for non-aqueous chemical treatment agents to be described below. The LOI method can be used to determine the amount of chemical treatment agent loaded onto a fiber. Satisfactory results are obtained with a chemical treatment solution having an organic material content of about 30% by weight. This organic material concentration yields strands impregnated with 5-15% by weight of organic compounds present in the chemical treatment agent.
Suitable organic material concentrations of the aqueous chemical treating agent may generally be selected irrespective of the form of the chemical treating agent (ie, dispersion, emulsion, etc.). In addition, the concentration of organic material in the pre-impregnated strands is dependent upon a number of factors, such as how fast the fibers move, the temperature of the heating device, the temperature at which the chemical treatment agent is used, and the degree to which the chemical treatment agent remains in the impregnated strands, at a given concentration. (Ie, viscosity), speed of the applicator roller (rpm), and whether prepad water spray was used.
The following is an embodiment of an aqueous chemical treating agent that can be used, for example, for preimpregnated fibers using apparatus 110.
Example I
6000 g of chemical treatment agent are prepared by the following procedure. 15 g (0.25 wt.%) Of amine silane coupling agent A-1100 is added to 2345 g of deionized water. It is stirred for a few minutes. Then, 1875 g (31.25%) of the thin film forming agent Covinax 201 and 1500 g (25.0%) of the thin film forming agent Covinax 225 are combined in a 2 gallon bucket. Next, the silane solution is mixed with the mixture of the thin film-forming agent with gentle stirring. 480 g (8.0%) of Maldene 286 are then added to the mixture of silane and thin film former. Finally, 200 g (3.3%) of BES homogenate (fatty acid ester KESSCO BES emulsified into homogenates) is added under continuous stirring. The organic compound concentration of the resulting chemical treatment solution is 30% by weight. The resulting chemical treating agent is suitable for use in polyamide fibers as well as glass fibers.
Example II
6000 g of chemical treatment agent are prepared by the following procedure. 15 g (0.25 wt.%) Of A-1100 silane is added to 1870 g of deionized water. It is stirred for a few minutes. 3450 g (57.5%) of the thin film forming agent Synthemul 97903-00 is then poured into a 2 gallon (7.6 L) bucket. The silane solution is then mixed with the thin film former with gentle stirring. 480 g (8.0%) of Maldene 286 are then added to the mixture of silane and thin film former. Finally, 200 g (3.3%) of BES homogenate is added under continuous stirring. The organic compound concentration of the resulting chemical treatment solution is 30%. The resulting chemical treating agent is suitable for use in polyamide fibers as well as glass fibers.
Example III
6000 g of chemical treatment agent are prepared by the following procedure. 15 g (0.25 wt.%) Of A-1100 silane is added to 2325 g of deionized water. It is stirred for a few minutes. Then 1875 g (31.25%) of Covinax 201 and 1500 g (25.0%) of Covinax 225 are combined in a 2 gallon (7.6 L) bucket. The silane solution is then mixed with the mixture of Covinax thin film forming agent with gentle stirring. 30 g (0.5%) of terephthalic acid is dissolved in 30 ml of concentrated ammonium hydroxide to prepare a terephthalic acid solution. The terephthalic acid solution is added to the mixture of silane and thin film forming agent. Next, 300 g (5.0%) of Polyemulsion 43N40 is added to the mixture. Finally, 200 g (3.3%) of BES homogenate is added under continuous stirring. The organic compound concentration of the resulting chemical treatment solution is 30%. The resulting chemical treating agent is suitable for use on polypropylene fibers as well as glass fibers.
Example IV
6000 g of chemical treatment agent are prepared by the following procedure. 15 g (0.25% by weight) of A-1100 (silane) is added to 2020 g of deionized water. It is stirred for a few minutes. Next, 3450 g (57.5%) of Synthemul 97903-00 (film forming agent) is poured into a 2 gallon (7.6 L) bucket. The silane solution is then mixed with the thin film former with gentle stirring. 30 g (0.5%) of terephthalic acid is dissolved in 30 ml of concentrated ammonium hydroxide to prepare a terephthalic acid solution. The terephthalic acid solution is added to the mixture of silane and thin film forming agent. Next, 300 g (5.0%) of Polyemulsion 43N40 is added to the mixture. Finally, 200 g (3.3%) of BES homogenate is added under continuous stirring. The organic compound concentration of the resulting chemical treatment solution is 30%. The resulting chemical treating agent is suitable for use on polypropylene fibers as well as glass fibers.
Example Ⅴ
6000 g of chemical treatment agent are prepared by the following procedure. 15 g (0.25 wt.%) Of A-1100 is added to 1870 g of deionized water. It is stirred for a few minutes. 3450 g (57.5%) of Synthemul 97903-00 are then poured into a 2 gallon (7.6 L) bucket. The silane solution is then mixed with the thin film former with gentle stirring. Finally, 200 g (3.3%) of BES homogenate is added under continuous stirring. The organic compound concentration of the resulting chemical treatment solution is 30%. The resulting chemical treating agents are suitable for use in fibers made from various materials, including polyphenylene sulfides and inorganic fibers.
Example VI
6000 g of chemical treatment agent are prepared by the following procedure. 15 g (0.25 wt.%) Of A-1100 is added to 2345 g of deionized water. It is stirred for a few minutes. Then 1875 g (31.25%) of Covinax 201 and 1500 g (25.0%) of Covinax 225 are combined in a 2 gallon (7.6 L) bucket. The silane solution is then mixed with the mixture of Covinax thin film forming agent with gentle stirring. Finally, 200 g (3.3%) of BES homogenate is added under continuous stirring. The organic compound concentration of the resulting chemical treatment solution is 30%. The resulting chemical treating agents are suitable for use in fibers made from a variety of materials, including polyphenylene sulfides and inorganic fibers.
In Examples I-VI, Covinax 201 and Covinax 225 are thermoplastic vinyl acrylics that act as thin film formers and can be purchased from Franklin International, Columbus, Ohio. Synthemul 97903-00 is a thermoplastic urethane thinner and can be purchased from Reichold Chemicals Inc. of Research Triangle Park, North Carolina. Epoxy, polyvinyl acetate and polyester can also be used as thin film formers. A-1100 is a silane-based coupling agent and can be purchased from Witco Chemical Company, Chicago, Illinois. KESSCO BES is a fatty acid ester that acts as a lubricant and can be purchased from Step Co., Northfield, Illinois. Another lubricant that may be used is a mixture of stearic acid and acetic acid and is commercially available from Owens Corning under the trade name K12. Polyemulsion 43N40 is a polypropylene wax modified with maleic anhydride, dispersed in water and available from Chemical Corporation of America of East Rutherford, NJ. Polyemulsion 43N40 acts as an interfacial modifier to chemically react with the coupling agent to improve the interface site (adhesion) between the glass fiber and the polypropylene matrix material. Terephthalic acid can be purchased from Aldrich Chemical Company, Milwaukee, WI, and also acts as an interfacial modifier to improve adhesion between glass and polypropylene matrix material by reducing polypropylene to crystallize close to the glass surface. do. Maldene 286 is a partial ammonium salt of maleic acid copolymer, available from Lindau Chemical Inc., Columbia, Columbia. Maldene 286 acts as an interfacial modifier to improve adhesion between glass fibers and nylon matrix materials.
Solvent free chemical treatment
Solvent strands can be prepared using solvent-free chemical treating agents, such as those described above. The use of such chemical treating agents substantially generates water vapor, volatile organic carbon or other solvent gases in processes (e.g., heating) according to the above-described streamline coating methods, for example when molding composites. There is an advantage that does not. Substantially free of solvents, the chemical treating agent can be thermally cured and / or reduced in viscosity without substantial mass loss, thereby allowing the majority of the chemical treating agent used in the fiber to remain on the fiber. Such chemical treating agents are also preferably substantially photocurable.
Table 6 shows an embodiment of apparatus 150 that can produce one or more polymer encapsulated composite strands 126 using a solvent free chemical treating agent. The resulting encapsulated composite strand 126, which may be formed into pellets or yarns, is also suitable for forming into fiber reinforced composites. Structural elements and components of device 150 that are the same or similar to those of device 110 described above are denoted by the same reference numerals as used above. Preferred apparatus 150 includes an applicator 116 with a front applicator roller 118 that uses a chemical treating agent on the reinforcing fiber 114 to form the coated fiber 120. Conventional double roller applicators may be used in place of the single roller 118.
When a chemical treating agent is to be used on the fiber to be heated, prior to gathering the fiber 113, the preferred apparatus 150 has an applicator 116 located adjacent the lower side of the bushing 115. The applicator 116 is at a sufficiently high temperature (fiber 114 is sufficient to bring about a desired decrease in viscosity and / or a desired thermoset (increase in crosslinking or other molecular weight) in the chemical treatment agent used (fiber 114 is sufficient Dissipate thermal energy), so that chemical treatment agents can be used. At the same time, the applicator 116 is located far enough from the bushing 115 so that the chemical treating agent can be used when the fiber 114 is at a temperature that does not cause significant damage to the chemical treating agent (eg, decomposition of the organic chemical or compound). In this way, the resulting strands 126 may be endowed with properties for production into the composite in subsequent processes.
For glass-reinforced fiber 114 drawn from a conventional bushing 115 having a typical yield, the applicator 116 preferably has a chemical treatment agent (from the bushing's fiber outlet) at least about 3 inches (7.62 cm) from the bushing 115, Preferably about 6 inches (15.24 cm). Sufficient results can be obtained when using a chemical treating agent on glass reinforcing fibers 114 from about 8 inches to about 10 inches (20.32 cm to 25.4 cm) from bushing 115. The optimal position of the applicator 116 from the bushing 115 is, for example, the type of bushing used (eg, the number of fibers drawn from the bushing 115), the temperature of the molten glass material, the type of chemical treatment agent used, at least the glass reinforcement fibers 14 The desired properties of the interfacial site of and the resulting properties of the strand 124 and the final composite.
It may be desirable to store the chemical treating agent in a cryogenic form prior to use on the fiber 14 so that highly reactive components are used in the chemical treating agent and to reduce the possibility of degradation due to heat of the chemical treating agent. It may also be desirable to maintain the temperature of the chemical treatment agent at or below about room temperature for the same reason as before, before use. The chemical treatment agent can be maintained at the desired temperature by any suitable method. For example, the cooling coil may be submerged in a chemical treatment agent. In addition, when forming continuously formed glass fibers, it may be desirable to surround the glass fibers 114 with an inert atmosphere before using the chemical treatment agent with the apparatus. An inert atmosphere should prevent the buildup of moisture on the surface of the fiber 114, thereby preventing the passivation of potentially reactive materials on the fiber surface due to moisture and thermal degradation due to moisture, as described above. However, it is preferable not to use an inert atmosphere when a high power bushing is used or when the temperature of the glass fiber is sufficiently high.
In FIG. 4 illustrating an aqueous substrate system, fiber 113 coated with a solvent-free chemical treating agent comprises fibers other than continuously stretched reinforcing fiber 114. Fiber 113 may include preformed reinforcing fibers and / or matrix fibers 152. As shown in FIG. 6, the preformed fiber 152 may be drawn from a spool or other package and then mixed with the continuously formed reinforcing fiber 114 before gathering all of the fibers 113 into the composite strand 124. Fiber 113 may comprise matrix fibers, for example, made continuously from a bushing or spinner, each time mixed with reinforcing fibers 114. The preformed fiber 152 may be coated with the same or different chemical treatment agent as used for the reinforcing fiber 114 before mixing. Depending on the type of fiber 152, the chemical treating agent may not be used on the fiber 152 prior to mixing the fiber 113. Whether forming fibers continuously or performing, the same techniques and devices can be used to chemically treat each type of reinforcing fiber and matrix fiber.
Prior to gathering fiber 113 into strand 124, the same applicator 116 can be used to chemically treat both the preformed fiber 152 and the continuously formed fiber 114. Alternatively, the separated applicator 116 'may be used to chemically treat the preformed fiber 152 (indicated by the virtual line 152'). If a separate applicator 116 ′ is used, the gathering mechanism 127 can assist mixing the fibers 114 and 152 together before gathering them into strand 124, including bars or rollers 154. U.S. Patent Application Serial No. 08 / 527,601 describes another method and apparatus for chemically treating preformed and continuously formed fibers together, using the same applicator or using different applicators. Alternatively, some of the fibers 113, such as matrix fibers 152, may be gathered together with the coated fibers 120 without first using the chemical treatment agent.
The composite can then be prepared by conventional techniques, for example by molding one or more encapsulated composite strands 126, which are in the form of pellets 132, yarn 140, or both. The resulting composite can be formed using injection molding, extrusion molding, transfer molding or any other suitable molding technique. The encapsulated composite yarn 140 may be formed into a fabric, for example, by an intermediate weaving or knitting process, and then extruded or transfer molded into the desired composite. Examples of such fabric forming methods and apparatus are described in US Patent Series 08 / 527,601, filed September 13, 1995, which is incorporated herein by reference.
While the foregoing specification and embodiments of the invention are contemplated, suitable variations of the invention will be apparent to those skilled in the art. Thus, the scope of the present invention is not intended to be limited to the above description or the preferred embodiment, but also to the following claims and their equivalents.

权利要求:
Claims (100)
[1" claim-type="Currently amended] A method of making a composite product comprising preparing a thermoplastic encapsulated composite strand material for placement in a matrix material in a step comprising:
Substantially covering all of the plurality of fibers including the reinforcing fibers using a chemical treating agent in sufficient amount to form a preimpregnated fiber (the chemical treating agent is compatible with the matrix material);
Gathering the preimpregnated fibers into preimpregnated strands having a chemical treatment agent substantially disposed between all of the plurality of fibers; And
Pre-impregnating the strands with a thermoplastic material to form a thermoplastic coating and forming the thermoplastic coating into a thermoplastic sheath to form a thermoplastic encapsulated composite strand.
[2" claim-type="Currently amended] The method of claim 1 further comprising cutting the thermoplastic encapsulated composite strand to form a plurality of pellets.
[3" claim-type="Currently amended] The method of claim 1, further comprising packaging the thermoplastic encapsulated composite strand as a yarn.
[4" claim-type="Currently amended] The method of claim 1 wherein said reinforcing fibers comprise preformed reinforcing fibers.
[5" claim-type="Currently amended] The method of claim 1 wherein the plurality of fibers further comprises matrix fibers.
[6" claim-type="Currently amended] The method of claim 1 further comprising preparing the reinforcing fibers in a method that consists in continuously forming the reinforcing fibers from molten glass or preforming matrix fibers from the polymeric material.
[7" claim-type="Currently amended] 2. The method of claim 1, wherein the reinforcing fibers are made inline by a method further comprising continuously forming the reinforcing fibers from the molten glass material.
[8" claim-type="Currently amended] The method of claim 1 wherein the chemical treating agent contains water and organic materials in an amount that provides an organic material content of about 2% to about 25% by weight to the preimpregnated strand, wherein the preparation of the thermoplastically encapsulated composite strand is further described above. And evaporating substantially all of the water in the chemical treatment agent prior to the gathering step.
[9" claim-type="Currently amended] The method of claim 8, wherein the organic material is solid or liquid dispersed or emulsified in water.
[10" claim-type="Currently amended] 10. The method of claim 9, wherein the organic material content is from about 2% to about 15% by weight and the evaporating step comprises heating the chemical treating agent after the using step.
[11" claim-type="Currently amended] The method of claim 10, wherein the organic material content is from about 6% to about 7% by weight, and wherein the heating comprises supplying thermal energy to a chemical treating agent from an external source or the plurality of fibers.
[12" claim-type="Currently amended] The method of claim 1, wherein the chemical treating agent is thermoset and the preparation of the thermoplastic encapsulated composite strand material further comprises at least partially curing the chemical treating agent after the use step.
[13" claim-type="Currently amended] 2. The method of claim 1 wherein said chemical treating agent is substantially solvent free and substantially photocurable and said organic material contains a thin film forming agent and a coupling agent.
[14" claim-type="Currently amended] The method of claim 13, wherein the chemical treating agent is thermoplastic, the thin film forming agent contains a low molecular weight thermoplastic polymer, and the coupling agent contains a functionalized organic material.
[15" claim-type="Currently amended] The method of claim 13, wherein the chemical treating agent is thermoset, the thin film forming agent contains at least one multifunctional monomer and a low molecular weight monofunctional monomer, and the coupling agent contains a functionalized organic material.
[16" claim-type="Currently amended] The method of claim 1 further comprising mixing the thermoplastic encapsulated composite strand with a matrix material to form a composite blend and molding the composite blend.
[17" claim-type="Currently amended] The method of claim 1 further comprising forming thermoplastic encapsulated composite strands into pellets and molding the pellets mixed with the resinous matrix material to form a fiber reinforced composite.
[18" claim-type="Currently amended] A composite product made according to the method according to claim 16, which is a fiber reinforced composite.
[19" claim-type="Currently amended] A composite product prepared according to the method according to claim 1, wherein the thermoplastic encapsulated composite strand material is in the form of pellets or strands.
[20" claim-type="Currently amended] In a composite product comprising a plurality of thermoplastically encapsulated composite strands useful for forming fiber-reinforced composites containing matrix materials, each of the thermoplastic encapsulated composite strands is substantially coated with a thermoplastic or thermoset chemical treatment agent compatible with the matrix material. A composite product comprising a preimpregnated strand consisting of a plurality of gathered fibers comprising reinforcing fibers.
[21" claim-type="Currently amended] 21. The composite product of claim 20, wherein the chemical treating agent holds all of the plurality of gathered fibers in pellets.
[22" claim-type="Currently amended] The composite product of claim 20, wherein the composite strands are packaged in yarn form.
[23" claim-type="Currently amended] The composite product of claim 20, wherein the number of the plurality of gathered fibers ranges from about 1,500 to about 10,000.
[24" claim-type="Currently amended] The composite product of claim 20, wherein the number of the plurality of gathered fibers ranges from about 2,000 to about 4,000.
[25" claim-type="Currently amended] 21. The composite product of Claim 20, wherein said plurality of gathered fibers further comprise matrix fibers made from a thermoplastic material.
[26" claim-type="Currently amended] 21. The composite product of Claim 20, wherein said chemical treating agent contains an organic material and wherein each said preimpregnated strand has an organic material content of about 2% to about 25% by weight.
[27" claim-type="Currently amended] 27. The composite product of claim 26, wherein said organic material content is from about 2 wt% to about 15 wt%.
[28" claim-type="Currently amended] The composite product of claim 27, wherein said organic material content is from about 6% to about 7% by weight.
[29" claim-type="Currently amended] 21. The couple of Claim 20, wherein said chemical treating agent is thermoplastic, substantially solvent free, substantially photocurable, and (i) a thin film forming agent containing a low molecular weight thermoplastic polymer material and (ii) a functionalized organic material. Composite product comprising a ring agent.
[30" claim-type="Currently amended] The composite product of claim 29, wherein the plurality of composite strands are molded with a matrix material.
[31" claim-type="Currently amended] 21. The film forming agent of claim 20 wherein said chemical treating agent is thermoset, substantially solvent free, substantially photocurable, and (i) a thin film-forming agent containing at least one multifunctional monomer and a low molecular weight monofunctional monomer, and (ii) A composite product comprising a coupling agent containing a purified organic material.
[32" claim-type="Currently amended] The composite product of claim 31, wherein the plurality of composite strands are molded with a matrix material.
[33" claim-type="Currently amended] A process for preparing a composite product, which consists of the following steps:
Using a heat-setting or thermoplastic chemical treating agent on a number of fibers, including glass or synthetic reinforcing fibers, to form fibers coated with the chemical treating agent used (the chemical treating agent is substantially solvent-free and substantially matt-curable); And
Lowering the viscosity of at least a portion of the chemical treatment used or curing the chemical treatment used at least in part, or heating the chemical treatment used for all to form coated fibers.
[34" claim-type="Currently amended] 34. The method of claim 33, wherein the chemical treating agent is used in an amount from about 0.1% to about 1% by weight.
[35" claim-type="Currently amended] 35. The method of claim 34, wherein the chemical treating agent is used in an amount of about 2% by weight to about 25% by weight.
[36" claim-type="Currently amended] 34. The method of claim 33, wherein the plurality of fibers further comprises polymeric matrix fibers.
[37" claim-type="Currently amended] 34. The method of claim 33, wherein the reinforcing fibers comprise glass reinforcing fibers and the heating step supplies the used chemical treating agent to exit thermal energy from the glass reinforcing fibers.
[38" claim-type="Currently amended] 38. The method of claim 37, wherein the glass reinforcing fiber is at a temperature of about 150 ° C to about 350 ° C during the use step.
[39" claim-type="Currently amended] 39. The method of claim 38, wherein said temperature is about 200 ° C to about 300 ° C.
[40" claim-type="Currently amended] 34. The method of claim 33, wherein the reinforcing fibers comprise preformed reinforcing fibers, further comprising preheating the preformed reinforcing fibers.
[41" claim-type="Currently amended] 34. The reinforcing fiber of claim 33, wherein the heating step comprises supplying thermal energy remaining in the glass reinforcing fiber from the forming step to a used chemical treating agent, wherein the reinforcing fiber comprises glass fiber, and further glass fiber reinforcing molten glass Forming glass fibers from a source of material.
[42" claim-type="Currently amended] 34. The method of claim 33, wherein said heating step comprises supplying thermal energy from the sources outside the plurality of fibers to the used chemical treating agent.
[43" claim-type="Currently amended] 34. The method of claim 33, wherein the chemical treating agent is thermoset and the heating step cures a portion of the chemical treating agent used at least in part.
[44" claim-type="Currently amended] 34. The method of claim 33, wherein the chemical treating agent is thermoplastic and the heating step reduces the viscosity of at least a portion of the chemical treating agent used.
[45" claim-type="Currently amended] 34. The method of claim 33, further comprising gathering all the coated fibers into composite strands.
[46" claim-type="Currently amended] 46. The method of claim 45, wherein said heating step occurs after said gathering step.
[47" claim-type="Currently amended] 46. The method of claim 45, wherein the chemical treating agent contains an organic material and the composite strand has an organic material content of about 2% to about 25% by weight.
[48" claim-type="Currently amended] 46. The method of claim 45 further comprising forming the composite strand into a composite having a plurality of fibers disposed in a matrix at least partially formed by a chemical treatment agent used.
[49" claim-type="Currently amended] 49. The method of claim 48, wherein the plurality of fibers further comprises polymeric matrix fibers forming at least a portion of the matrix of the composite.
[50" claim-type="Currently amended] 49. The method of claim 48 wherein said forming step is performed inline with said gathering step.
[51" claim-type="Currently amended] 34. The method of claim 33, further comprising mixing reinforcing fibers and matrix fibers to provide a plurality of fibers.
[52" claim-type="Currently amended] 52. The method of claim 51, wherein said using step comprises simultaneously coating the reinforcing fibers and the matrix fibers with a chemical treating agent.
[53" claim-type="Currently amended] It is used in fibers to form fiber reinforced composites for processing into composite strands useful for placement in matrix materials, and in chemical treatment agents comprising: thermosetting, at least partially thermally curable, substantially solvent free and substantially Chemical treatments that are non-curable as:
One or more multifunctional monomers and low molecular weight monofunctional monomers; And
Coupling agents containing functionalized organic materials.
[54" claim-type="Currently amended] 55. The chemical treating agent of claim 53 further comprising a processing aid.
[55" claim-type="Currently amended] 55. The chemical treating agent of claim 54 wherein said processing aid contains an epoxy functional viscosity modifier.
[56" claim-type="Currently amended] 55. The chemical treating agent of claim 54, wherein said processing aid contains butoxyethylstearate.
[57" claim-type="Currently amended] 54. The chemical treating agent of claim 53 which is thermoset at a temperature of about 150 ° C to about 350 ° C.
[58" claim-type="Currently amended] 54. The chemical treating agent of claim 53, wherein the thin film forming agent contains a monomer selected from the group consisting of polyester alkyds, epoxy resins, and compounds containing glycidyl ether functional groups.
[59" claim-type="Currently amended] 54. The chemical treating agent of claim 53, wherein the thin film forming agent contains at least one selected from the group consisting of urethanes, vinyl esters, dark acids, Diels Alder reactive species and Cope rearrangement compounds.
[60" claim-type="Currently amended] The chemical treating agent of claim 53, wherein the chemical treating agent has a viscosity of about 300 cps or less in the range of about 93 ° C to about 110 ° C.
[61" claim-type="Currently amended] A chemically treating agent that is thermoplastic, substantially solvent-free, and substantially matting, for use in fibers to form fiber-reinforced composites for processing into composite strands useful for placement in matrix materials and comprising:
One or more low molecular weight thermoplastic polymer materials; And
Coupling agents containing functionalized organic materials.
[62" claim-type="Currently amended] 62. The chemical treating agent of claim 61 further comprising a processing aid.
[63" claim-type="Currently amended] 62. The chemical treating agent of claim 61 wherein the low molecular weight thermoplastic polymer comprises pyrolyzed polyester or polyamide.
[64" claim-type="Currently amended] 64. The chemical treating agent of claim 63 wherein the polyester or polyamide is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and nylon.
[65" claim-type="Currently amended] 65. The process of claim 64 further comprising di-n-butyl terephthalate, dibenzoate ester of 1,4-butanediol, diethyl terephthalate, dibenzoate ester of ethylene glycol, caprolactone, adipolychloride and n-amino A chemical treatment agent comprising a processing aid comprising an adduct of hexane and a monomer equivalent selected from the group consisting of adducts of 1,6-hexanediamine and hexanoyl chloride.
[66" claim-type="Currently amended] 62. The chemical treating agent of claim 61, wherein the chemical treating agent has a viscosity of about 300 cps or less in the range of about 93 ° C to about 110 ° C.
[67" claim-type="Currently amended] A process for preparing a composite product, which consists of the following steps:
Using a heat-setting or thermoplastic chemical treating agent on a number of fibers, including glass or synthetic reinforcing fibers, to form fibers coated with the chemical treating agent used (the chemical treating agent is substantially solvent-free and substantially matt-curable); And
Lowering the viscosity of at least a portion of the chemical treatment used or curing the chemical treatment used at least in part, or heating the chemical treatment used for all to form coated fibers.
[68" claim-type="Currently amended] 68. The method of claim 67, wherein the chemical treating agent is used in an amount from about 0.1% to about 1% by weight.
[69" claim-type="Currently amended] 69. The method of claim 68, wherein the chemical treating agent is used in an amount of about 2% by weight to about 25% by weight.
[70" claim-type="Currently amended] 68. The method of claim 67, wherein the plurality of fibers further comprises polymeric matrix fibers.
[71" claim-type="Currently amended] 68. The method of claim 67, wherein the reinforcing fibers comprise glass reinforcing fibers and the heating step supplies the used chemical treating agent to exit thermal energy from the glass reinforcing fibers.
[72" claim-type="Currently amended] 72. The method of claim 71, wherein the glass reinforcing fiber is at a temperature of about 150 ° C to about 350 ° C during the use step.
[73" claim-type="Currently amended] 73. The method of claim 72, wherein said temperature is about 200 ° C to about 300 ° C.
[74" claim-type="Currently amended] 68. The method of claim 67, wherein the reinforcing fibers comprise preformed reinforcing fibers, further comprising preheating the preformed reinforcing fibers.
[75" claim-type="Currently amended] 68. The reinforcing fiber of claim 67, wherein the heating step comprises supplying thermal energy remaining in the glass reinforcing fiber from the forming step to the used chemical treating agent, wherein the reinforcing fiber comprises glass fiber, and further comprising melting the glass fiber Forming glass fibers from a source of material.
[76" claim-type="Currently amended] 68. The method of claim 67, wherein said heating step comprises supplying thermal energy from the sources outside the plurality of fibers to the used chemical treatment agent.
[77" claim-type="Currently amended] 68. The method of claim 67, wherein the chemical treating agent is thermoset and the heating step cures a portion of the chemical treating agent used at least in part.
[78" claim-type="Currently amended] 68. The method of claim 67, wherein the chemical treating agent is thermoplastic and the heating step reduces the viscosity of at least a portion of the chemical treating agent used.
[79" claim-type="Currently amended] 68. The method of claim 67 further comprising gathering all the coated fibers into a composite strand.
[80" claim-type="Currently amended] 80. The method of claim 79, wherein said heating step occurs after said gathering step.
[81" claim-type="Currently amended] 80. The method of claim 79, wherein the chemical treating agent contains an organic material and the composite strand has an organic material content of about 2% to about 25% by weight.
[82" claim-type="Currently amended] 80. The method of claim 79, further comprising forming the composite strand into a composite having a plurality of fibers disposed in a matrix at least partially formed by a chemical treatment agent used.
[83" claim-type="Currently amended] 83. The method of claim 82, wherein the plurality of fibers further comprises polymeric matrix fibers forming at least a portion of the matrix of the composite.
[84" claim-type="Currently amended] 83. The method of claim 82, wherein said forming step is performed inline with said gathering step.
[85" claim-type="Currently amended] 68. The method of claim 67 further comprising mixing the reinforcing fibers and the matrix fibers to provide a plurality of fibers.
[86" claim-type="Currently amended] 86. The method of claim 85, wherein said using step comprises simultaneously coating the reinforcing fibers and the matrix fibers with a chemical treating agent.
[87" claim-type="Currently amended] It is used in fibers to form fiber reinforced composites for processing into composite strands useful for placement in matrix materials, and in chemical treatment agents comprising: thermosetting, at least partially thermally curable, substantially solvent free and substantially Chemical treatments that are non-curable as:
One or more multifunctional monomers and low molecular weight monofunctional monomers; And
Coupling agents containing functionalized organic materials.
[88" claim-type="Currently amended] 88. The chemical treating agent of claim 87 further comprising a processing aid.
[89" claim-type="Currently amended] 89. The chemical treating agent of claim 88, wherein said processing aid contains an epoxy functional viscosity modifier.
[90" claim-type="Currently amended] 89. The chemical treating agent of claim 88, wherein said processing aid contains butoxyethylstearate.
[91" claim-type="Currently amended] 89. The chemical treating agent of claim 87 being thermoset at a temperature of about 150 ° C to about 350 ° C.
[92" claim-type="Currently amended] 88. The chemical treating agent of claim 87, wherein the thin film forming agent contains a monomer selected from the group consisting of polyester alkyds, epoxy resins, and compounds containing glycidyl ether functional groups.
[93" claim-type="Currently amended] 88. The chemical treating agent of claim 87, wherein the thin film forming agent contains at least one selected from the group consisting of urethanes, vinyl esters, dark acids, DielsAlder reactive species and cope rearrangement compounds.
[94" claim-type="Currently amended] 88. The chemical treating agent of claim 87, wherein the chemical treating agent has a viscosity of about 300 cps or less in the range of about 93 ° C to about 110 ° C.
[95" claim-type="Currently amended] A chemically treating agent that is thermoplastic, substantially solvent-free, and substantially matting, for use in fibers to form fiber-reinforced composites for processing into composite strands useful for placement in matrix materials and comprising:
One or more low molecular weight thermoplastic polymer materials; And
Coupling agents containing functionalized organic materials.
[96" claim-type="Currently amended] 95. The chemical treating agent of claim 95 further comprising a processing aid.
[97" claim-type="Currently amended] 95. The chemical treating agent of claim 95, wherein the low molecular weight thermoplastic polymer comprises pyrolyzed polyester or polyamide.
[98" claim-type="Currently amended] 95. The chemical treating agent of claim 95, wherein the polyester or polyamide is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and nylon.
[99" claim-type="Currently amended] 99. The method of claim 98, further comprising di-n-butyl terephthalate, dibenzoate ester of 1,4-butanediol, diethyl terephthalate, dibenzoate ester of ethylene glycol, caprolactone, adipolychloride and n-amino A chemical treatment agent comprising a processing aid comprising an adduct of hexane and a monomer equivalent selected from the group consisting of adducts of 1,6-hexanediamine and hexanoyl chloride.
[100" claim-type="Currently amended] 96. The chemical treating agent of claim 95, wherein the chemical treating agent has a viscosity of about 300 cps or less in the range of about 93 ° C to about 110 ° C.

类似技术:

---

公开号 | 公开日 | 专利标题

---

CA2832823C|2020-06-02|Composite core for electrical transmission cables

---

JP5687212B2|2015-03-18|Glass fiber material leached with carbon nanotubes and its manufacturing process

---

DE69935412T2|2007-11-08|Connection with a mineral fiber binding application and method of manufacturing thereof

---

CA2218907C|2001-09-11|Flexible low bulk pre-impregnated tow

---

FI101314B|1998-05-29|Manufacturing method of continuous wire by mechanical drawing

---

US7060326B2|2006-06-13|Aluminum conductor composite core reinforced cable and method of manufacture

---

US5593758A|1997-01-14|Method for preparing preforms for molding processes

---

US4680224A|1987-07-14|Reinforced plastic

---

US6228474B1|2001-05-08|Epoxy resin composition for a fiber-reinforced composite material, yarn prepreg, and process and apparatus for preparing the same

---

FI102467B|1998-12-15|Composite yarn, its manufacturing method and composite products obtained from it

---

CN1891423B|2010-12-22|Pre-impregnated filament bundle and / or pre-impregnated article manufacturing method

---

US5094883A|1992-03-10|Flexible multiply towpreg and method of production therefor

---

CN103987762B|2018-03-13|Asymmetrical fibre strengthens polymeric tapes

---

JP2894638B2|1999-05-24|Manufacturing method of mineral fiber products

---

EP0291023B1|1992-12-16|Method of manufacturing a cable-like plastic composite body

---

US3530212A|1970-09-22|Method of making glass resin laminates

---

JP6320380B2|2018-05-09|Improved glass fiber reinforced composite

---

JP5662156B2|2015-01-28|Method for producing long glass fiber reinforced thermoplastic composition

---

US6609674B2|2003-08-26|High-speed manufacturing method for composite flywheels

---

US5024978A|1991-06-18|Compositions and methods for making ceramic matrix composites

---

US5171630A|1992-12-15|Flexible multiply towpreg

---

US4341877A|1982-07-27|Sizing composition and sized glass fibers and process

---

KR20160042091A|2016-04-18|Nanocomposites containing spherical pyrogenic silica nanoparticles and composites, articles, and methods of making same

---

US4110094A|1978-08-29|Method of forming glass fiber

---

FI86736C|1992-10-12|Process for producing a long fiber reinforced polyamide based composite

同族专利:

---

公开号 | 公开日

---

EP1223016A2|2002-07-17|

---

NO990608L|1999-04-12|

---

JP4585631B2|2010-11-24|

---

CA2262935C|2005-10-25|

---

ES2244003T3|2005-12-01|

---

NO319981B1|2005-10-10|

---

WO1998006551A2|1998-02-19|

---

KR100491389B1|2005-05-24|

---

AT299427T|2005-07-15|

---

NO990608D0|1999-02-09|

---

EP1223016A3|2003-04-02|

---

EP0921919A2|1999-06-16|

---

NZ334085A|2000-07-28|

---

DE69733713D1|2005-08-18|

---

DE69738458T2|2008-07-31|

---

BR9711128A|1999-09-08|

---

EP1223015B1|2008-01-09|

---

EP1223015A3|2004-05-19|

---

KR20050008825A|2005-01-21|

---

CN1228050A|1999-09-08|

---

AU3911497A|1998-03-06|

---

WO1998006551A3|1998-07-23|

---

EP1223015A2|2002-07-17|

---

CA2262935A1|1998-02-19|

---

CN1341782A|2002-03-27|

---

AU733283B2|2001-05-10|

---

EP1223016B1|2015-01-07|

---

DE69738458D1|2008-02-21|

---

ES2298326T3|2008-05-16|

---

DE69733713T2|2006-04-20|

---

JP2000516162A|2000-12-05|

---

TW467873B|2001-12-11|

---

EP0921919B1|2005-07-13|

---

KR100545526B1|2006-01-24|

---

AT383233T|2008-01-15|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

法律状态:
1996-08-12|Priority to US8/695,909

---

1996-08-12|Priority to US08/695,504

---

1996-08-12|Priority to US08/695,909

---

1996-08-12|Priority to US08/695,909

---

1996-08-12|Priority to US08/695,504

---

1996-08-12|Priority to US8/695,504

---

1997-08-07|Application filed by 휴스톤 로버트 엘, 오웬스 코닝

---

2000-05-25|Publication of KR20000029969A

---

2005-05-24|Application granted

---

2005-05-24|Publication of KR100491389B1

优先权:

---

申请号 | 申请日 | 专利标题

---

US08/695,909|1996-08-12|

---

US08/695,909|US6533882B1|1996-08-12|1996-08-12|Chemical treatments for fibers and wire-coated composite strands for molding fiber-reinforced thermoplastic composite articles|

---

US08/695,504|1996-08-12|

---

US8/695,504|1996-08-12|

---

US8/695,909|1996-08-12|

---

US08/695,504|US6099910A|1996-08-12|1996-08-12|Chemical treatments for fibers|