JPH08187728A - Manufacture of fiber-reinforced thermoplastic resin material - Google Patents

Abstract

PURPOSE: To obtain a fiber-reinforced thermoplastic resin coating material having a filament mixing ratio and a sectional shape of a target by previously heat treating a reinforcing fiber bundle at a predetermined temperature or higher, then covering it with the reinforcing fiber, cooling it and forming an uneven part on the surface of the covering resin. CONSTITUTION: A reinforcing fiber bundle 1 from a bobbin 2 is wound necessary times by a front side tension controller 4, guided to a preheater 5, heat treated at 100 deg.C or higher to evaporate and vaporize detrimental components at the time of molding, and then guided to a polymer reservoir 8 from an introducing side die 7. The bundle 1 is covered with a melted thermoplastic resin melted, pressurized and extruded by a screw 11, fed via a discharging side die 9, then throttled at the excess resin by a remolding nozzle 13 heated to the melting temperature or higher of the resin, and cooled by a cooling bath 15. Then, a tension is controlled by a rear side tension controller 17 while forming an uneven part on the surface by a resin surface uneven part forming unit 16, drawn by a drawing roll 18, and wound on a winder 19.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention uses an injection molding machine or the like to
When molding a fiber-reinforced thermoplastic resin material, the generation of gas, which greatly affects the quality of the material, is suppressed, and the reinforcing fibers are highly impregnated with resin to fully exhibit their characteristics, and the entire molding material is reinforced. The present invention relates to a method for producing a fiber-reinforced thermoplastic resin material for obtaining a high-quality molding material in which fibers are uniformly dispersed and mixed, and further, the surface of the fiber-reinforced thermoplastic resin has uniform and fine irregularities.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a fiber-reinforced thermoplastic resin material, there is generally known a method in which a chopped strand obtained by cutting a fiber bundle into about 5 mm and a resin are kneaded and extruded by an extruder. However, according to this method,
For example, in the case of aromatic polyamide fiber which is an organic fiber, when cut into a short length, the fiber becomes cotton-like and becomes extremely bulky, so that it is difficult to bite into an extruder or a kneader, and carbon fiber or glass fiber which is an inorganic fiber In the kneading process of the extruder, it was crushed by high decoupling force to 0.5 mm or less,
There is a problem that the mechanical properties of the obtained fiber reinforced thermoplastic resin material are deteriorated. Furthermore, in recent years PPS, PEE
It is said that as reinforcement with a heat-resistant thermoplastic resin such as K and PES becomes necessary, the dispersability of the fibers deteriorates due to heat deterioration of the sizing agent for the reinforcing fibers during pellet formation by the extruder and during injection molding. There were also problems. Further, when the molded product is used at high temperature, water and heat-deteriorated sizing agent of the reinforcing fiber are gasified, so that heat resistance and mechanical properties of the obtained fiber-reinforced thermoplastic resin are deteriorated. . In order to solve these drawbacks, JP-A-62-1
Japanese Patent No. 4035, Japanese Patent Application Laid-Open No. 57-90020, and the like are proposed. However, although it has an effect on the biting property and the crushing of the reinforcing fiber, it has not yet solved the problem that the water of the reinforcing fiber and the heat-degraded sizing agent are gasified. Further, regarding the raw material used for the fiber-reinforced thermoplastic resin material reinforced with continuous fibers, one of the important factors is that the filament (single fiber) mixing ratio in the length direction is one of the important factors. It is extremely difficult to make a uniform material. In addition, as disclosed in Japanese Patent Laid-Open No. 01-01591, it was also found in our analysis that the resin impregnating property between the fibers varies.

Further, in the fiber reinforced thermoplastic resin material which is reinforced with continuous long fibers prepared in the above-mentioned prior materials, the breaking elongation of the material is generally regulated by the reinforcing fiber. For example, the breaking elongation of a material reinforced with organic and inorganic fibers having a higher elongation than that of a steel reinforcing material is high. Therefore, there is also a problem that the dimensional stability and creep characteristics of the organic fiber reinforced material and the like are inferior to those of the steel reinforcing material.

Further, in the case of the fiber reinforced thermoplastic resin material prepared from the above-mentioned preceding sample, etc., when various agents are coated thereafter, the resin does not uniformly adhere to the resin surface, and it adheres as spots on the resin surface. Also, there is a problem that the adhesiveness with the post-processing agent is poor.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the problems of the prior art as described above, and has good biteability and dispersibility when used as a short fiber reinforced thermoplastic resin material. Less gas is generated due to heat deterioration at the stage,
The reinforcing fibers are highly impregnated with a resin to sufficiently exhibit their properties, and the reinforcing fibers are uniformly dispersed and mixed in the entire molding material, and further, by applying a special treatment to the fiber bundle coating resin surface, The purpose of the present invention is to provide a material excellent in adhesion with various surface-treating agents, and also when used as a continuous fiber reinforced fiber-reinforced thermoplastic resin material.
Generation of gas due to heat deterioration at the molding stage is small, reinforcing fibers are impregnated with resin to sufficiently exhibit its characteristics, there are no bubbles, and reinforcing fibers are uniformly dispersed and mixed in the entire molding material. It is an object of the present invention to propose a manufacturing method for providing a material which is provided with uniform and fine irregularities on the surface of a coating resin and which is excellent in adhesiveness, heat resistance, dimensional stability, mechanical properties and the like. The present inventors, in a manufacturing method for coating a reinforcing fiber bundle with a thermoplastic resin, heat-treat the reinforcing fiber bundle in advance to remove evaporants such as water and oil adsorbed and attached to the reinforcing fiber. By vaporizing, gasification and its generation at the time of molding are prevented, and when the reinforcing fiber bundle is coated with a molten thermoplastic resin, a high-viscosity thermoplastic resin is obtained by applying pressure to the resin. It is poured into a reinforcing fiber bundle, and the coated fiber bundle is reshaped at a temperature not lower than the melting temperature of the thermoplastic resin by using a molding nozzle to make the mixing ratio of single fibers uniform in the longitudinal direction, By passing the coated fiber bundle through a special surface treatment device, fine irregularities are formed on the resin surface, the adhesiveness with the subsequent processing agent is improved, and molding when using this as a material The adhesiveness of the material, or cut it The heat resistance of the injection molded article and press-molded products used as the raw material, which has led to dimensional stability, and found the present invention that the mechanical properties are excellent.

[0006]

That is, the present invention provides "(Claim 1) a method of coating a reinforcing fiber bundle with a thermoplastic resin, wherein the reinforcing fiber bundle is preliminarily heat-treated at a temperature of 100 ° C or higher, A step of coating the reinforcing fiber continuously with this step,
A method for producing a fiber-reinforced thermoplastic resin material, which comprises a step of subsequently cooling and a step of forming irregularities on a surface of the coated thermoplastic resin. (2) The fiber according to (1), wherein the fiber bundle coated with the thermoplastic resin is reshaped at a temperature above the melting temperature of the thermoplastic resin by a remolding nozzle and then cooled. A method for producing a reinforced thermoplastic resin material. (Claim 3) In covering with the molten thermoplastic resin, 2
The method for producing a fiber-reinforced thermoplastic resin material according to claim 1 or 2, wherein a pressure of 5 kg / cm 2 or more is applied during the resin impregnation. (Claim 4) Prior to coating the reinforcing fiber bundle with the thermoplastic resin, the fiber-reinforced thermoplastic resin according to any one of claims 1, 2 and 3 including a step of heat treatment in advance at a temperature higher than a melting temperature of the thermoplastic resin. Material manufacturing method. (Claim 5) 3 to 50 on the surface of the thermoplastic resin coated with fiber bundles
A method for producing a fiber reinforced thermoplastic resin material, wherein fine irregularities within a μm range are formed. ".

The reinforcing fiber bundle used in the present invention includes polyacrylonitrile-based, rayon-based, glass fiber, poly- (P-phenylene terephthalamide), which is a generic name for aromatic polyamide fiber, and poly- (m-. (Phenylene terephthalamide) and a copolymer having the skeleton thereof, and one or a combination of two or more kinds of various inorganic and organic fibers. In addition, in each combination of the fiber and the resin, the fiber may be subjected to an appropriate surface treatment such as an appropriate sizing treatment or a coupling agent treatment. As the thermoplastic resin used for coating, polyamide, polyethylene, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyether nitrile,
Examples include rigid resins such as polysulfone, polyarylene sulfide, polyether sulfone, polyetherimide, polyamideimide, polyacrylonitrile, polycarbonate, polyolefin, polyacetal, polystyrene, and mixtures or copolymers thereof.

Further, these thermoplastic resins are added with various additives such as heat resistance agents, light resistance improvers, UV deterioration inhibitors, antistatic agents, lubricants, release agents, in order to improve their properties.
Colorants such as dyes and pigments, crystallization accelerators, flame retardants, and the like, and inorganic, organic, and metal powders such as calcium carbonate as the third component can be easily added.

Next, the present invention will be described with reference to the drawings.

FIG. 1 shows an example of a manufacturing apparatus used for manufacturing the fiber-reinforced thermoplastic resin material of the present invention. A plurality of continuous reinforcing fiber bundles 1 are wound from the bobbin 2 via the guide guide 3 by the front tension control device 4 at least one required time, guided to the preheating heater 5, and subjected to heat treatment there. After vaporizing and vaporizing components that are harmful at the time of molding, the fiber bundle introduction side die 7 is passed through the guide 6
Is introduced into the polymer reservoir 8. The reinforcing fiber bundle was melt-pressed with the screw 11, covered with the molten thermoplastic resin extruded through the throat 10, passed through the lead-out die 9, and subsequently heated above the melting temperature of the thermoplastic resin. After the excessive resin is squeezed by the remolding nozzle 13, while being cooled by the cooling bath 15, the resin surface unevenness forming device 16 forms fine unevenness on the coated resin surface via the guide guide roller 14 and After the tension is controlled by the side tension control device 17, the material is taken up by a take-up roll 18 and wound on a winder 19 to obtain a continuous filament-reinforced thermoplastic resin coating material having a target filament mixture ratio and cross-sectional shape.

Instead of winding the fiber-reinforced thermoplastic resin material coated with a resin in the form of a strand with the winding machine 19, the fiber-reinforced thermoplastic resin material is cut into a desired length with a stride cutter or a pelletizer, so that reinforcement equal to the cut length is obtained in the resin. It is also possible to obtain a pellet-shaped fiber-reinforced thermoplastic resin raw material in which the fibers for use are monofilaments or uniformly dispersed in a state close to the monofilaments.

If the preheater 5 in FIG. 1 is capable of evaporating and evaporating water, which adheres to or is adsorbed to the fibers and which is harmful during molding, processing oils, adhesives, etc. The shape and type are not particularly limited, but it is desirable to use a non-contact type heater in order to minimize damage to the fiber bundle. Further, the heater is preferably arranged below the fiber bundle in order to prevent contamination by evaporative substances and gasification products rising from the fiber bundle. Further, in order to heat-treat a plurality of fiber bundles uniformly, it is desirable to provide a reflecting plate and make the temperature between the fiber bundles uniform. The heat treatment temperature of the fiber bundle in the preheater 5 depends on the heat treatment time, but it is higher than the temperature at which the substance adhering to or adsorbing to the fibers is vaporized or gasified, that is, 100 ° C or higher if the adsorbed water is vaporized. 230 ° C. or higher is required for the decomposition and removal of the oil agent, and more preferably, it is set higher than the melting temperature of the thermoplastic resin to be impregnated into the fiber bundle to remove the vaporized matter or gasified matter which is a problem during molding in advance. In order to obtain this effect at a high take-up speed, the preheat treatment temperature is 20% higher than the melting temperature of the thermoplastic resin.
Higher than ℃ is desirable. However, if the temperature is increased, not only the energy loss for heating is large, but also the fibers may be damaged by heat and mechanical strength may be lowered, which is not preferable. Therefore, for example, in the case of aramid fiber which is an organic fiber, the temperature is 150 ° C. higher than the melting temperature of the thermoplastic resin, and in the case of inorganic fiber, the temperature is 200 ° C. or higher higher than the melting temperature, and the aramid fiber starts to decompose. It is desirable to perform the heat treatment at a temperature of 485 ° C. or lower at the beginning. Further, the processing time varies depending on the processing temperature, but if the processing time is 10 seconds or more, it is possible to suppress gas generation during molding.

When the reinforcing fiber preheated in this way is used, surprising facts have been discovered in addition to the effect of suppressing gas generation during molding. This is a phenomenon that is particularly prominent in para-aramid fibers, but in the fiber bundle from which the adsorbed moisture of the fiber bundle and the surface treatment agent that is mainly an oil agent have been removed by the preheat treatment, the interface between the fiber and the thermoplastic resin This is a phenomenon that the adhesiveness is improved. That is, when the molten thermoplastic resin is attached to the fiber bundle that is not preheated, the attachment of the resin cannot catch up if the take-up speed becomes a certain value or more, and resin adhesion unevenness occurs in the length direction of the fiber bundle. In the case of the preheated fiber bundle, resin adhesion unevenness does not occur even at a take-up speed of 1.5 times or more faster than in the case of no preheat treatment, which is effective in improving productivity and quality. I understood. That is, the pre-heat treatment removes the water or oil adhering to or adsorbed on the fiber surface, and oxidizes the outermost surface layer of the fiber to improve the wettability with the resin, resulting in adhesiveness (adhesiveness). Is expected to improve.

The introduction die 7 in FIG. 1 is fixed to the die head 12 by bolts. The details of the die 7 are shown in FIG. 2, but it is desirable to provide a taper on the upper side, which is the entrance side of the fiber bundle, so that the fiber bundle can pass through easily. Moreover, the introduction hole 20 of the reinforcing fiber facilitates pressurization in the polymer reservoir 8,
In order to prevent the molten thermoplastic resin from flowing out of the system from the introduction hole 20, it is desirable to bring it close to the cross-sectional area of the fiber bundle, but if it is too close, the resistance between the fiber bundle and the introduction hole 20 becomes large and the fiber bundle Since it becomes difficult to pull out, it is desirable that the cross-sectional area of the introduction hole is 1.02 times or more the cross-sectional area of the fiber bundle.
On the other hand, if it is too large, the molten thermoplastic resin tends to flow out, and it becomes difficult to pressurize the resin. Therefore, the ratio is preferably 1.70 times or less. Further, the length of the introduction hole 20 is preferably long in order to improve the pressing force and prevent the molten thermoplastic resin from flowing out from the introduction hole 20 due to the pressurization. To 3 mm to 20 mm is desirable.

The delivery die 9 is attached to the die head 12 by bolts.
It is fixed to. The details of the die 9 are shown in FIG. 3. A point is provided on the upper side, which is the entrance side of the fiber bundle, and the molten thermoplastic resin adhered and impregnated to the reinforcing fiber is drawn out while being squeezed to improve impregnation of the resin. From desirable.
Further, the introduction hole 21 of the reinforcing fiber bundle which is coated and impregnated with the molten thermoplastic resin is provided with an undesired resin outflow from the introduction hole 20 to the outside due to the pressing force in the polymer reservoir 8 and the pressure of the molten thermoplastic resin. From the viewpoint of prevention, it is desirable that the cross-sectional area of the introduction hole 20 be equal to or larger than that. In addition, the length of the introduction hole 21 is determined from the viewpoints of pressurization in the polymer reservoir 8, prevention of outflow from the introduction hole 20 due to pressurization of the molten thermoplastic resin, and mobility of the resin-impregnated fiber. It is desirable that it is less than or equal to the length.

By supplying the molten thermoplastic resin from the screw 11 into the polymer reservoir 8 formed by the introduction side die 7 and the discharge side die 9, pressurization in the polymer reservoir 8 becomes possible and the reinforcing fiber bundle is obtained. It becomes possible to impregnate the reinforcing fiber with the molten thermoplastic resin while eliminating the bubbles. Since the viscosity of the molten thermoplastic resin is as high as 100,000 centipoise, if the applied pressure is low, the thermoplastic resin cannot enter the fiber bundle 1 and sufficient impregnability cannot be obtained. However, when the resin is pressed at a pressure of 25 kg / cm ² or more, preferably 50 kg / cm ² or more, the molten thermoplastic resin uniformly enters the reinforcing fiber bundle,
As a result, the reinforcing fibers are uniformly dispersed in the resin in a monofilament or a state close thereto,
The adhesion between the fiber and the resin is enhanced, and a good fiber-reinforced thermoplastic resin material can be obtained. Further, the higher the pressure is, the more quickly the molten thermoplastic resin can be impregnated into the inside of the fiber bundle, but in consideration of the rotational energy of the screw 11 for pressurization and the working accuracy of the dies 7 and 9, 200 kg /
It is desirable to set the pressure to cm ² or less.

FIG. 4 shows the details of the remolding nozzle 13, but it is desirable to provide a taper on the entrance side of the reinforcing fiber bundle covered with the thermoplastic resin. By providing this taper, the thermoplastic resin is narrowed down, and this taper portion plays a role of a polymer reservoir of the resin removed by the narrowing down, so that the thermoplastic resin is uniformly coated and impregnated in the length direction. It becomes possible to do. The molding hole 22 has a target filament mixture ratio and cross-sectional shape,
That is, it can be re-formed into any shape such as a circle, a triangle, and a square. Furthermore, what is important in this re-molding nozzle 13 is that the fiber bundle is heated to a temperature above the melting temperature of the thermoplastic resin impregnated with the coating. When the thermoplastic resin is squeezed at a temperature not higher than the melting temperature of the thermoplastic resin, not only high drawing tension is required, but also peeling occurs between the thermoplastic resin already impregnated with the reinforcing fiber and the reinforcing fiber. This causes the impregnating property to be deteriorated and causes the internal strain to remain. Further, when the temperature of the nozzle 13 is significantly higher than the melting temperature of the thermoplastic resin, the viscosity of the thermoplastic resin decreases, so that not only the narrowing effect decreases but also the deterioration of the thermoplastic resin occurs. It is accelerated and the mechanical properties of the resulting fiber reinforced thermoplastic resin are deteriorated.

The lead-out die 9 and the re-forming nozzle 13 can be freely separated, but it is desirable to make them as close as possible in order to prevent the reinforcing fiber bundle coated with the thermoplastic resin from being cooled and solidified.

Further, in the resin surface unevenness forming step in the thermoplastic resin coating step of the present invention, it is possible to form as fine and uniform unevenness as possible on the surface of the thermoplastic resin covering the fiber bundle surface. desirable. The reason for this is that when the fiber-reinforced thermoplastic resin coating material is subsequently processed with various surface-treating agents depending on the application, the unevenness formed on the surface of the coating resin is non-uniform, and if the surface-treating agent is too large, adhesion of the treating agent will occur. Not only is unevenness generated, but stress concentration is also caused in specific recesses and the like, resulting in a decrease in tensile breaking strength and bending strength, which is not preferable. On the other hand, if the unevenness is too small, the surface expansion effect and anchor effect of the coating resin cannot be fully exerted,
It is not preferable because the adhesiveness with the processing agent cannot be improved. According to the results of our study, when fine irregularities within a range of 3 to 50 μm, more preferably within a range of 5 to 25 μm are formed on the coating resin surface, the occurrence of adhesion unevenness of the processing agent is small, the adhesiveness is good, and the physical properties are good. I have confirmed that there is no problem. The fine irregularities can be formed by, for example, a method of passing through fine sand with a specific load applied, a sandblasting method, or a method of using a plurality of rolls having specific fine irregularities. However, the method is not particularly limited, and any other method may be used.

Further, the manufacturing apparatus and manufacturing process shown in FIGS. 1, 2, 3 and 4 are merely examples for producing the material of the present invention, and the manufacturing apparatus and process capable of exhibiting the same effects as described above are provided. If so, there is no limitation.

[0021]

The characteristics of the fiber reinforced thermoplastic resin material produced by the production method of the present invention are as follows. (1) The material produced by the production method of the present invention has good impregnation property of the thermoplastic resin into the reinforcing fiber, has a small amount of voids in the material, and has high interfacial adhesion between the resin and the fiber. It is good. (2) According to the manufacturing process of the present invention, it is possible to provide a fiber-reinforced material having various cross-sectional shapes according to the purpose of use. (3) The fiber-reinforced thermoplastic resin material produced by the production method of the present invention has high strength and low elongation and is excellent in dimensional stability. (4) The fiber-reinforced thermoplastic resin material produced by the production method of the present invention is excellent in interfacial adhesion with various processing agents or various matrices depending on the purpose of use.

The effects of the present invention will be specifically described below with reference to examples. The content (% by weight) of the reinforcing fiber, the wire diameter, the breaking strength, which was performed for the fiber-reinforced thermoplastic resin material,
Elongation at break, presence or absence of gas generation, resin impregnation in fiber bundle,
Evaluations such as observation of irregularities on the surface of the coating resin were carried out according to the following methods.

<Reinforcement Fiber Content> Content (weight%) = (Reinforcement Fiber Weight / Fiber Reinforced Thermoplastic Resin Coating Material Weight) × 100 <Measurement of Wire Diameter> Resin Coated Reinforcement Fiber Using a Measuring Machine 1 /
A load of 20 is applied, and 5 points are measured at intervals of 10 cm in the width of 50 cm, and the average value is shown.

<Strength at break and elongation at break> Measured according to JIS standard, L1013 using INTESCO (Model 2005) manufactured by Intesco Corporation. However, the chuck is for steel fiber.

<Evaluation of Gas Generation in Manufacturing Process> A reinforcing fiber, a thermoplastic resin, and a fiber-reinforced thermoplastic resin raw material which are not surface-treated by a temperature-rising gas chromatography method using a gas chromatographic model G80 manufactured by Yanagimoto Seisakusho Of the fiber-reinforced thermoplastic resin raw material
No gas is generated when the decomposition peaks of the reinforcing fiber not surface-treated and the decomposition peaks of the thermoplastic resin are generated, and the decomposition peaks of the reinforcing fiber not surface-treated and the decomposition peaks other than the decomposition peak of the thermoplastic resin are Gas was generated when it was observed in comparison with the decomposition peak of the fiber-reinforced thermoplastic resin raw material.

The measurement conditions at this time are: Carrier Gas: He, Inject temperature:
Melting point + 15 ° C. (PPS: 300 ° C.) Column: left at 100 ° C. for 10 minutes, heated to 300 ° C. at a rate of 10 ° C./1 minute, and then left for 10 minutes.

<Evaluation of Impregnation of Resin into Fiber Bundle> The cross-section of the fiber-reinforced thermoplastic resin material was observed with an electron microscope (or optical microscope) for dispersibility of the fiber in the resin, and the reinforcing fiber was bundled. If the whole is in a focused state ×
The mark indicates that the reinforcing fibers are not bundled, but the reinforcing fibers are divided and bundled in several places, and the mark indicates that about 50% or more of the reinforcing fibers are dispersed in a single fiber form. Was judged as a circle.

<Observation of irregularities on the surface of the coated resin> The fiber reinforced thermoplastic resin material is cut, and the cut surface is observed with an electron microscope.
After observing at least one place, the unevenness of the resin surface is observed and measured, and the average unevenness amount is calculated in consideration of the magnification.

<Evaluation of drawing strength> RFL-treated fiber reinforced thermoplastic resin material is embedded in unvulcanized rubber in a U-shape to a depth of 1 cm and vulcanized, and then subjected to vulcanization at room temperature with the above tensile tester. The material was pulled out and the strength at that time was measured.

[0030]

Example 1 In carrying out the production method of the present invention, this time, a para-aramid fiber composed of 1500 denier / 1000 filaments (Technora: manufactured by Teijin Ltd.) 4
Using a fiber bundle in which a book is pre-twisted at 40 t / m on one side, 3
After passing through a preheater heated to 50 ° C and performing heat treatment for 15 seconds, it was introduced into a polymer reservoir through an introduction hole with an inner diameter of 0.9mmφ and a length of 20mm, and the molten thermoplastic at 290 ° C extruded from the screw here. Resin is impregnated in the fiber (applying pressure 30 kg / cm ² ) and further 290
A fiber-reinforced thermoplastic resin material having a reinforcing fiber content of 68.5% after being molded by a molding nozzle having an inner diameter of 1.0 mm and a length of 5 mm heated to 0 ° C. and then subjected to resin surface unevenness forming treatment. Got The pick-up speed at this time is 10
It was m / min. Polyamide 66 (Asahi Kasei Co., Ltd.) was used as the coating thermoplastic resin. The results of measuring the breaking strength and the breaking elongation of the obtained fiber-reinforced thermoplastic resin material are shown in Table 1. Further, in order to improve the adhesiveness of the obtained fiber reinforced thermoplastic material with rubber, the main component having a liquid concentration of 18.3% for interfacial adhesion reinforcement is V
An adhesive-treated fiber-reinforced thermoplastic material having a reinforcing fiber content of 70% after being dipped in a pretreatment agent containing P-containing latex and subsequently dried at 100 ° C. for 24 seconds and then cured at 195 ° C. for 48 seconds. Got The obtained material was pressed into an unvulcanized rubber sheet and vulcanized under a pressure of 42 kg / cm ² at 180 ° C. for 30 minutes using a press processor. The peel strength between the adhesive-treated fiber-reinforced thermoplastic material and rubber was measured for this vulcanized sample. The results are also shown in Tables 1 and 2.

[0031]

[Example 2] The unevenness of the resin surface coated with the fiber bundle was set to about 20 μm.
The same procedure as in Example 1 was carried out to obtain a fiber-reinforced thermoplastic resin material, and the properties of this material were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. It was

[0032]

[Embodiment 3] The amount of irregularities on the surface of the resin coated with the fiber bundle is about 40 μm.
The same procedure as in Example 1 was carried out to obtain a fiber-reinforced thermoplastic resin material, and the properties of this material were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. It was

[0033]

[Embodiment 4] The applied pressure during resin coating is 55 kg / c.
A fiber reinforced thermoplastic resin material was obtained in the same manner as in Example 1 except that m ² was changed, and the properties of this material were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. .

[0034]

[Example 5] The same procedure as in Example 1 was carried out except that a remolding nozzle was not used to obtain a fiber-reinforced thermoplastic resin material.
The properties of this were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

[0035]

[Example 6] The same procedure as in Example 4 was carried out except that a remolding nozzle was not used to obtain a fiber-reinforced thermoplastic resin material.
The properties of this were evaluated in the same manner as in Example 4, and the results are shown in Tables 1 and 2.

[0036]

Example 7: Preheat treatment temperature is 120 ° C., coating resin is Ny
A fiber reinforced thermoplastic resin material was obtained in the same manner as in Example 1 except that the value was changed to 6, and the characteristics of this material were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 and 2.

[0037]

[Example 8] The same procedure as in Example 7 was carried out except that the preheat treatment temperature was changed to 180 ° C to obtain a fiber-reinforced thermoplastic resin material, the characteristics of which were evaluated in the same manner as in Example 7, and the results were obtained. Are shown in Tables 1 and 2.

[0038]

[Example 9] The same procedure as in Example 7 was carried out except that the preheat treatment temperature was changed to 230 ° C to obtain a fiber-reinforced thermoplastic resin material, the characteristics of which were evaluated in the same manner as in Example 7, and the results were obtained. Are shown in Tables 1 and 2.

[0039]

[Example 10] A fiber-reinforced thermoplastic resin material was obtained in the same manner as in Example 7 except that the preheat treatment temperature was changed to 280 ° C, and the properties thereof were evaluated in the same manner as in Example 7,
The results are shown in Tables 1 and 2.

[0040]

Example 11 A fiber reinforced thermoplastic resin material was obtained in the same manner as in Example 10 except that the remolding nozzle was not used, and the characteristics of this fiber reinforced thermoplastic resin material were evaluated in the same manner as in Example 10 and the results are shown in Table 1. 1, shown in Table 2.

[0041]

Example 12 The same procedure as in Example 7 was carried out except that the preheat treatment temperature was changed to 350 ° C. to obtain a fiber reinforced thermoplastic resin material, the characteristics of which were evaluated in the same manner as in Example 7,
The results are shown in Tables 1 and 2.

[0042]

[Comparative Example 1] A target sample was obtained in the same manner as in Example 1 except that the irregularities on the surface of the fiber-bundle coating resin were formed to have an average of 1 μm. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Tables 3 and 4.

[0043]

[Comparative Example 2] A target sample was obtained in the same manner as in Example 1 except that the unevenness of the surface of the resin covering the fiber bundle was formed to be 60 μm on average. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Tables 3 and 4.

[0044]

Comparative Example 3 A target sample was obtained in the same manner as in Example 1 except that the pressure applied to the fiber bundle surface coating resin was changed to 18 kg / cm ² , and this sample was used. The physical properties were evaluated in the same manner as in Example 1, and the results are shown in Tables 3 and 4.

[0045]

Comparative Example 4 A target sample was obtained in the same manner as in Comparative Example 3 except that the remolding nozzle was not used. The physical properties of this sample were evaluated in the same manner as in Comparative Example 3 and the results are shown in Table 3 and Table 3. Shown in FIG.

[0046]

Comparative Example 5 A target sample was obtained in the same manner as in Example 7 except that the heat treatment temperature was 80 ° C., and the physical properties of this sample were evaluated in the same manner as in Example 7. The results are shown in Tables 3 and 4.

[0047]

[Comparative Example 6] In Example 7, the heat treatment temperature was 500 ° C.
A target sample was obtained in the same manner as in Example 7 except that the above was performed, and the physical properties of this sample were evaluated in the same manner as in Example 7. The results are shown in Tables 3 and 4.

[0048]

[Comparative Example 7] In Example 7, the heat treatment temperature was 500 ° C.
In the same manner as in Example 7, except that the remolding nozzle is not used, and a target sample is obtained. The physical properties of this sample are evaluated in the same manner as in Example 7, and the results are shown in Table 3. The results are shown in Table 4.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

As shown in Tables 1 and 3, the fiber-reinforced thermoplastic resin material of the present invention has a well-balanced performance in resin impregnation property, tensile strength, adhesiveness, etc. as compared with the comparative examples. Is clear.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an apparatus for producing a fiber-reinforced thermoplastic resin material according to the present invention.

FIG. 2 is a side sectional view of an introduction die.

FIG. 3 is a side sectional view of a lead-out die.

FIG. 4 is an explanatory view of a side sectional view of a molding nozzle.

[Explanation of symbols]

 1 Reinforcing Fiber 2 Bobbin 3 Guide Guide 4 Front Tension Control Device 5 Preheating Heater 6 Guide Guide 7 Introduction Die 8 Resin Reservoir 9 Derivation Side Die 10 Throat 11 Screw 12 Die Head 13 Molding Nozzle 14 Guide Guide Roller 15 Cooling Bath 16 Resin Surface Concavo-convex forming device 17 Rear tension control device 18 Take-up roll 19 Winding machine 20 Reinforcing fiber introduction hole 21 Reinforcing fiber outlet hole 22 Forming hole

Claims (5)

[Claims] 1. A method of coating a reinforcing fiber bundle with a thermoplastic resin, wherein the reinforcing fiber bundle is heat-treated at a temperature of 100 ° C. or higher in advance, and the reinforcing fiber is continuously treated with this step. A method for producing a fiber-reinforced thermoplastic resin material, which comprises a coating step, a subsequent cooling step, and a step of forming irregularities on the surface of the coated thermoplastic resin. 2. The fiber according to claim 1, wherein the fiber bundle coated with the thermoplastic resin is reshaped at a temperature above the melting temperature of the thermoplastic resin by a remolding nozzle and then cooled. A method for producing a reinforced thermoplastic resin material. 3. Covering with a molten thermoplastic resin 2
The method for producing a fiber-reinforced thermoplastic resin material according to claim 1 or ² , wherein a pressure of 5 kg / cm ² or more is applied during impregnation of the resin. 4. The fiber-reinforced thermoplastic resin according to claim 1, further comprising a step of heat-treating at a high temperature equal to or higher than a melting temperature of the thermoplastic resin before coating the reinforcing fiber bundle with the thermoplastic resin. Material manufacturing method. 5. A fiber bundle-covered thermoplastic resin surface with 3 to 50
A method for producing a fiber reinforced thermoplastic resin material, wherein fine irregularities within a μm range are formed.