TWI696733B - Manufacturing method of blended yarn, blended yarn, and manufacturing method of woven fabric or knitted fabric - Google Patents

Abstract

The present invention provides a manufacturing method capable of obtaining a blended yarn which is capable of manufacturing a fiber-reinforced resin molded article having an arbitrary shape and excellent in strength, and a manufacturing method capable of obtaining woven fabric or knitted fabric.

The manufacturing method of blended yarn of the present invention is a method for manufacturing a blended yarn composed of at least of a thermoplastic resin fiber and a reinforcing fiber, the manufacturing method including a step of blending the thermoplastic resin fiber and the reinforcing fiber in the presence of liquid and by a fluid entangling method with gas. In addition, the blended yarn of the present invention is a blended yarn composed of at least of a thermoplastic resin fiber and a reinforcing fiber, the blended yarn containing at least two or more types of organic substances, wherein the organic substances are adhered to both of the reinforcing fiber and the thermoplastic resin fiber. Also, the manufacturing method of woven fabric or knitted fabric of the present invention is a method for manufacturing a woven fabric or a knitted fabric composed of at least of a thermoplastic resin and a reinforcing fiber, the liquid content of the reinforcing fiber in the weaving step or knitting step of the reinforcing fiber being 0.1 to 5 mass%.

Description

Manufacturing method of mixed fiber yarn, manufacturing method of mixed fiber yarn and fabric or knitted fabric

The present invention relates to a method for manufacturing mixed fiber yarn, a method for manufacturing mixed fiber yarn, and a fabric or knitted fabric.

Among various structural parts of machinery, automobiles, etc., pressure vessels, and tubular structures, composite material molded bodies obtained by adding reinforcing materials such as glass fibers and carbon fibers to resin materials are used. In order to have both light weight and strength, composite molded bodies are required to be able to follow any shape.

As a material constituting the composite molded body, a mixed fiber yarn or a fabric made of the mixed fiber yarn in which the reinforcing fiber and the thermoplastic resin fiber are mixed by fluid and continuously and uniformly mixed is proposed (for example, Patent Document 1) . In order to improve the impregnation at the time of molding, the improvement of the degree of fiber blending (the degree of mixing of fibers) is reviewed as the focus of the fiber blending conditions (for example, refer to Patent Document 2). In addition, unlike general organic fibers, since reinforcing fibers are easily damaged and fluffed, it is necessary to precisely control the conditions for fiber opening and mixing (for example, refer to Patent Document 3). It is also known that when processing reinforced fibers, high humidity makes it difficult to increase bulkiness, that is, it is difficult to open fibers (see, for example, Patent Document 4).

As described above, when manufacturing a blended yarn using reinforcing fibers, from the viewpoint of suppressing damage to the reinforcing fibers and improving the degree of blending, so-called moisture removal is performed on the blended fibers. In addition, from the viewpoint of suppressing the adsorption of moisture that becomes an obstacle when heating a mixed fiber yarn to obtain a molded body, it is also common sense to require treatment in a dry environment.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-112916

[Patent Document 2] Japanese Patent Laid-Open No. 3-275729

[Patent Document 3] Japanese Patent Laid-Open No. 4-222246

[Patent Document 4] Japanese Patent Laid-Open No. 59-43141

However, the conventionally known blended yarns or fabrics mainly focus on preventing damage to the reinforcing fibers during blending, and improving the blending state in order to improve the impregnability during molding, but only for application in automotive materials, etc. Among the construction materials, it is required to have higher strength.

In order to solve the above-mentioned problems of the conventional technology, the present inventors have conducted repeated detailed examinations and found that mixing thermoplastic fibers and reinforcing fibers in the presence of a liquid with gas can exhibit high strength and high interface of the molded body. Strength, and completed the present invention.

That is, the method of manufacturing the mixed yarn of the present invention is a method of manufacturing the mixed yarn composed of at least a thermoplastic resin fiber and a reinforcing fiber, which includes: in the presence of a liquid, a fluid by gas The entanglement method is a manufacturing method in which a thermoplastic resin fiber and a reinforcing fiber are mixed in a fiber mixing step.

Reinforcing fibers are preferably those containing less than 300% by mass of liquid.

The fluid entanglement method is preferably a fluid agitation method.

The reinforcing fiber system preferably contains 0.1 to 5% by mass of a water-soluble component relative to the reinforcing fiber.

The hydrophilicity index of the reinforcing fiber is preferably 8 degrees or more.

As another aspect, the method for manufacturing a blended yarn of the present invention is a method for manufacturing a blended yarn composed of at least a thermoplastic resin fiber and a reinforcing fiber, which includes: performing thermoplastic resin fiber and/or reinforcing fiber in a liquid After the treatment step, the fiber blending step by the fluid entanglement method by gas.

The liquid system is preferably one containing organic matter.

When an organic substance is mixed with thermoplastic resin fibers by 10% by mass, the change rate of the surface tension of the thermoplastic resin fibers is preferably 30% or less.

It is preferable to mix the liquid recovered in the fiber mixing step by the fluid entanglement method with the liquid in the liquid treatment step.

The mixed fiber yarn of the present invention is a mixed fiber yarn composed of at least a thermoplastic resin fiber and a reinforcing fiber, which contains at least two kinds of organic substances, and the two or more kinds of organic substances adhere to both the reinforcing fiber and the thermoplastic resin fiber.

On the surface of the reinforcing fiber and the thermoplastic resin fiber, the degree of dispersion of the organic matter is preferably 5% or more.

The softness of the blended yarn is preferably at least 20 degrees.

The porosity of the blended yarn is preferably at least 20%.

Relative to the blended yarn, the total amount of organic matter is preferably less than 2% by mass.

The method for manufacturing a fabric or knitted fabric of the present invention is a method for manufacturing a fabric or knitted fabric composed of at least a thermoplastic resin and reinforcing fibers. In the step of weaving reinforcing fibers, the liquid content of the reinforcing fibers is 0.1 to 5 mass% get on.

According to the method for manufacturing a mixed fiber yarn, a mixed fiber yarn, or a method for manufacturing a woven fabric or knitted fabric according to the present invention, a mixed fiber yarn, woven fabric or knitted fabric that can produce a fiber-reinforced resin molded body having an arbitrary shape and excellent strength is obtained.

1: core wire

2: floating silk thread

4: Nozzle

5: blended yarn

6: Template

7: COR (core)

8: CAV (cavity)

Fig. 1 is a schematic diagram for explaining Taslan processing.

Fig. 2 is a schematic diagram showing the state in which the synthetic yarn is wound around in the aluminum mold frame used in the embodiment.

Fig. 3 is a schematic diagram showing a mold used in the examples.

The following is a detailed description of the present invention. In addition, the present invention is not limited to the following, and various modifications can be made within the scope of the gist thereof.

<blend yarn>

The mixed yarn of the present invention refers to a yarn composed of at least reinforcing fibers and thermoplastic resin fibers. If the reinforcing fibers and/or thermoplastic resin fibers are multifilament fibers, it is preferred from the viewpoint of the strength and handleability of the yarn. Although it is possible to cut a part of the monofilament of the reinforcing fiber multifilament fiber, from the viewpoint of strength, the continuous fiber is preferable as the reinforcing fiber bundle. Although the thermoplastic resin fibers may be in any form, from the viewpoint of the stability of the blending step, continuous fibers are preferred.

The mixed state of the two fibers is not particularly limited, and examples include a state in which the two fibers are aligned, a state in which the two fibers are mixed in units of monofilaments, a state in which one fiber covers the periphery of the other fiber, and a twisted state. In order to improve the impregnability and exhibit high strength during forming, it is preferable to mix only a part of the two fibers in a single-filament unit. Since the less the mixing, the higher the straightness of the reinforcing fibers, so there is a tendency to show high strength. If there is a minimum mixing portion and this is used as a starting point, it can be impregnated quickly. The mixing ratio of reinforcing fibers is preferably from 0.1 to 20%, more preferably from 0.2 to 15%, and even more preferably from 0.3 to 10%. The degree of mixing is defined as the ratio of the number of reinforcing fibers adjacent to the thermoplastic resin fiber to the total number of reinforcing fiber bundles, and is calculated by observing the cross section of the 20-point mixed yarn at any position.

From the viewpoint of achieving high strength and beautiful appearance, the volume ratio of the reinforcing fiber to the thermoplastic resin fiber in the blended yarn is preferably 50 to 900% by volume, more preferably 66 to 400% by volume, and 81 to 233% by volume is better.

The mixed fiber yarn of the present invention contains at least two or more kinds of organic substances, and the two or more kinds of organic substances adhere to both the reinforcing fiber and the thermoplastic resin fiber. Since both the reinforcing fiber and the thermoplastic resin fiber have two or more kinds of the same organic substance, the affinity of the two fibers is high, and the handling property in terms of the thread is excellent, and the effect of high impregnation can be obtained during molding. In order to make it easier to improve these effects, at least one type of organic matter is preferably water-soluble. In addition, when the total amount of organic matter is too much, the handling property may be reduced. Therefore, the total amount of these organic matters is preferably less than 2% by mass relative to the mixed filament yarn, more preferably 1.7% by mass or less, and 1.4% by mass It is better if it is below %, and it is best to be below 1.1% by mass.

The number of types of organic matter attached to the mixed filament yarn can be extracted from the mixed filament yarn using an appropriate solvent and calculated by the liquid chromatography analyzer mass analysis method. The amount of organic matter attached to the reinforcing fibers and thermoplastic resin fibers in the blended yarn can be separated from the blended yarn by reinforcing fibers and thermoplastic resin fibers. After extracting each fiber with water, the amount of water-soluble components extracted by the solvent Quantify the amount of water-insoluble components. In addition, by performing NMR measurement of the extracted components, it can be separated according to the origin of the components, and the components (A) contained in the reinforcing fibers of the raw materials and the components (B) contained in the thermoplastic resin fibers of the raw materials can also be separated. ), and the component (C) contained in the liquid used in the blended fiber. From the viewpoints of impregnation characteristics and strength at the time of molding, it is desirable that the reinforcing fiber and the thermoplastic resin fiber each contain both components (A) and (B).

From the viewpoint of impregnation at the time of molding and improving the final interface strength in the molded body, it is preferable that these organic substances are attached in a state where the degree of dispersion in the surface of the reinforcing fiber or thermoplastic resin fiber is 5% or more. The degree of dispersion is more preferably 10% or more, and more preferably 15% or more. The degree of dispersion can be calculated as follows. The mass was measured after extracting the organic matter from the blended yarn, and the mass ratio of the organic matter was calculated relative to the mass of the blended yarn. Perform the same measurement at any 20 places and calculate the average value and the standard deviation, and divide the standard deviation by the average value as the degree of dispersion.

From the viewpoint of handling when weaving, knitting, and combining the mixed yarn, the softness of the mixed yarn is preferably 20 degrees or more, more preferably 40 degrees or more, and even more preferably 60 degrees or more, especially More than 80 degrees is the best. Regarding the softness of the blended yarn, the blended yarn is cut into 20 cm, and the edges and the edges are fixed with a 1.5 cm wide tape to form a loop. Hold the part fixed with tape and hang vertically. At this time, if vertical cannot be formed, press lightly with your hand to make it vertical. While maintaining the gripping tape portion, turn it 180 degrees in the vertical direction, with the tape portion facing down to make the mixed yarn stand vertically. Maintain no contact with the mixed yarn for 1 minute, and measure the sagging angle of the mixed yarn with respect to the vertical direction. Also, in the case of bending into two stages, the larger angle is used.

From the viewpoint of the balance between the handleability of the process of weaving, knitting, and combining the blended yarns, and the handleability of the fabrics, knitted fabrics, and compositions made afterwards, the flexibility of the blended yarns can be achieved through moisture absorption. Those with varying values are better. The amount of change in the softness of the mixed yarn before and after moisture absorption is preferably above 30 degrees, more preferably above 40 degrees, and even more preferably above 50 degrees.

From the point of view of the handleability when weaving, knitting, and combining the mixed fiber yarn, and the suppression of damage during the treatment, the mixed fiber yarn preferably contains pores inside, and the porosity is preferably 20% or more. More than 25% is better, and more than 30% is better. The porosity can be obtained by wrapping a mixed fiber yarn in a shrink tube, injecting a colored epoxy resin into the tube to harden it, cutting, grinding, and observing the cross section.

Porosity = area of the void / area of the inside of the outer periphery of the mixed yarn × 100

The area of the pores is the area of the colored epoxy resin inside the outer circumference of the mixed filament yarn, and the outer circumference of the mixed filament yarn is drawn by the line connecting the outermost fibers.

The blended yarn may contain substances other than reinforcing fibers, thermoplastic resin fibers, and organic substances. Depending on the environment in which the molded body is used, it is preferable to add antioxidants, ultraviolet absorbers, colorants, heat transfer agents, heat stabilizers, etc.

<Manufacturing method of blended yarn>

The mixed fiber yarn of the present invention is produced by mixing reinforcing fibers and thermoplastic resin fibers by gas in the presence of a liquid. This liquid refers to a liquid under the processing conditions of temperature and pressure. The type of liquid can be appropriately selected according to the processing conditions, and water, organic solvents, etc. can be appropriately used. From the viewpoint of stability, water is particularly preferred. Gas refers to a gaseous state before contacting with the reinforcing fibers and/or thermoplastic resin fibers. The type of gas can be appropriately selected according to the processing conditions, and air, steam, organic gas, etc. can be appropriately used. From the viewpoint of stability, air is ideal.

By actively adding liquid, the damage of the reinforcing fiber during blending can be suppressed, and even in the low mixing state, the resin can be quickly impregnated into the reinforcing fiber during molding, and will exhibit high tensile strength or Interface strength. The amount of liquid is not particularly limited, and the optimum amount can be adjusted according to the type of reinforcing fiber, thermoplastic resin, monofilament diameter, and fineness to be used. Examples of the method of adding the liquid include a method of adding vapor and a method of adding liquid. From the viewpoint of the impregnability during molding and the strength of the molded body, it is preferable to add a liquid. Although either the reinforcing fiber or the thermoplastic resin fiber may contain liquid, at least the reinforcing fiber containing liquid is preferred, and the liquid containing both fibers is more preferred. Since it is better to have liquid at the time of fiber blending, it is better to include the step of containing liquid immediately before fiber blending. It is not necessary to perform the step of containing both the reinforcing fiber and the thermoplastic resin fiber, for example, the reinforcing fiber may be subjected to a liquid-containing step and then aligned with the thermoplastic resin fiber to make the reinforcing fiber liquid Move into thermoplastic resin fiber.

The liquid system preferably contains organic matter. In the liquid-containing step, the liquid may contain organic substances of different kinds from the organic substances contained in the liquid. In this case, the organic material is added by: those who increase the affinity of the reinforcing fibers and the thermoplastic resin fibers, those who impart hydrophilicity and can suppress the generation of static electricity, and impart coloring, flame resistance, heat resistance, weather resistance, etc. to the molded body Those who are functional are those that promote the opening of reinforcing fibers during molding and improve impregnation, etc., which are initially difficult to impart to reinforcing fibers or thermoplastic resin fibers. Considering the residual efficiency of the organic fiber blended yarn after the fiber blending step, it is preferable that the organic material is finely dispersed in the liquid, and the latex state of the aqueous dispersion is better.

In order to achieve high physical properties by impregnation during short-time molding, when 10% by mass of organic matter is blended with the thermoplastic resin fiber, the organic matter is preferably the one having a change rate of the surface tension of the thermoplastic resin fiber of 30% or less, more preferably 20% or less It's better, it's better to be below 15%, and it's better to be below 10%.

In addition, the difference between the surface tension of the organic substance and the thermoplastic fiber is preferably less than 22, more preferably less than 17, more preferably less than 12, and most preferably less than 7. Among the melting points of organic matter and thermoplastic resin fibers, the surface tension is measured at a temperature 45°C higher than the high temperature.

In order to exhibit good physical properties after impregnation, the difference between the SP value (solubility parameter) of the thermoplastic resin fiber and the organic matter is preferably less than 3 (cal/cm ³ ), more preferably less than 2 and less than 1.5 Even better, with less than 1 being the best.

It is particularly preferable to use polymers or oligomers in the same series as the thermoplastic resin fibers as the ideal organic substance satisfying these requirements. The homologous system here refers to those in which the organic substance holds the functional group of the repeating unit of the thermoplastic resin fiber. For example, if the thermoplastic resin fiber is polyamide 66, an organic substance having an amide bond is suitable.

From the viewpoint of controlling the amount of organic matter added, the liquid containing step is preferably a method of spraying the liquid containing the organic matter to recover the residual amount, and a method of impregnating the liquid in the circulating state and managing the concentration. In the fiber mixing step by gas, since the remaining liquid and the remaining organic matter are recovered together, it is better to reuse this recovered matter in the liquid-containing step.

The liquid content is not particularly limited, and an amount that can achieve the above effect can be appropriately selected, but from the viewpoint of improving productivity or suppressing waste liquid, the liquid content of the liquid relative to the reinforcing fiber is 300 Mass% or less is better, 250 mass% or less is better, 200 mass% or less is better, and 150 mass% or less is best. Regarding the liquid content, the production line is stopped when the process is stable. The part before the fiber blending step can be cut to measure the weight, and then the weight can be obtained by removing the liquid.

The interfacial shear stress of the reinforcing fibers in the blended yarn is preferably changed with respect to the interfacial shear stress of the reinforcing fibers of the raw materials. The interfacial shear stress of the reinforcing fibers relative to the raw materials is increased by more than 5%. It is better to increase by more than 10%, and it is better to increase by more than 15%. In order to change the interfacial shear stress, the components such as the sizing agent attached to the reinforcing fibers can be moved by the liquid. The interfacial shear stress can be measured by the microdrop method.

The unwinding method of the reinforcing fiber can be appropriately selected, and examples include internal removal, external removal, rolling removal, and the like. From the viewpoint of suppressing damage in the silk path, the reinforcing fiber system before unwinding is preferably in a liquid-containing state. The sizing agent may be applied to maintain the liquid-containing state when the reinforcing fiber is produced, or may be used after being liquid-containing at the time of use. The liquid-containing method can be impregnated in a predetermined liquid, and can also be sprayed with a mist blower or the like, or it can be kept in a high humidity for a predetermined time. When it is difficult to use after the liquid state, it is better to perform unrollable rolling removal without twisting the reinforcing fibers. Although the liquid content during unwinding is not particularly limited, the softness of the reinforcing fiber immediately after unwinding is preferably above 5 degrees, more preferably above 10 degrees, and even more preferably above 15 degrees. The softness can be measured by the same method as the softness of the above-mentioned mixed yarn.

For the method of blending fibers, a conventional method can be used according to the structure of the blended yarn, and several steps of blending fibers can be used in combination. The following describes a method for manufacturing a mixed fiber yarn of a reinforcing fiber and a thermoplastic resin fiber, which is a preferred form of a mixed fiber yarn, or a mixture of reinforcing fiber and thermoplastic resin fiber in a monofilament unit.

For example, after opening fibers by external force such as electrostatic force or fluid spray pressure, squeezing pressure by rollers, etc., the reinforcing fiber bundle and the thermoplastic resin fibers are opened in a fiber-opened state and aligned. Fibre filament method, fluid entanglement method. It is advisable to use a fluid entanglement method where one side is mixed with the other side and the remaining liquid can be removed by gas. The fluid entanglement method refers to a method in which fibers are entangled with each other by the action of a fluid, and examples thereof include a fluid agitation method or an interweaving method (applying air transversely to the yarn). When using carbon fibers that can be easily damaged due to external forces from the side of the reinforcing fibers, the fluid agitation method is preferred, and the Taslan (registered trademark) method that applies air to the thread in the same direction is particularly applicable. The thickness and count of the reinforcing fiber bundle of the raw material can be adjusted appropriately, and the manufacturing conditions can be adjusted together.

Hereinafter, Taslan processing of a preferred embodiment of the present invention will be described. Taslan processing refers to the method of making the wire transmitted by the core wire and the floating wire loosen by the force of air, and strongly bundled into a loop. For example, when the core wire 1 and the floating wire 2 sent by the rotation of the roller shown in FIG. 1 pass through the nozzle 4 installed in the Taslan box, the wires are agitated by air force to form a bundle. The core wire 1 is a core wire that becomes a Taslan wire, and a floating wire 2 is tightly wound around this. Supply of thread by roller It is usually appropriate to set the floating side to be more than the core side. The nozzle 4 is mainly composed of a shell and a core, and a hole called a spout located inside the core ejects air to make it into a bundle.

Although the core yarn 1 and the floating yarn 2 may be either reinforcing fibers or thermoplastic resin fibers, from the viewpoint of strength, it is preferable to use the reinforcing fibers for the core yarn 1 and the thermoplastic resin fibers for the floating yarn 2. From the viewpoint of the strength and productivity of the blended yarn, the yarn speed is preferably from 10 to 1000 m/min, more preferably from 20 to 700 m/min, and even more preferably from 30 to 500 m/min, and from 50 to 300 m /Min is best.

Regarding the transmission of the reinforcing fiber, from the viewpoint of improving the linearity of the thread and increasing the strength of the molded body, it is preferably 0 to 10%, more preferably 0.1 to 5%, and 0.2 to 3% relative to the thread speed. Even better, with 0.3 to 1.8% being the best. The transmission of thermoplastic resin fibers can be adjusted arbitrarily from the viewpoint of adjustment and entanglement of reinforcing fibers, preferably 1 to 15%, more preferably 2 to 10%, more preferably 3 to 7%, and 4 Up to 6% is the best. Compared with the core wire 1, the transfer rate of the floating wire 2 is preferably 100 to 600%, more preferably 110 to 500%, and most preferably 150 to 400%. From the viewpoint of suppressing the damage of the reinforcing fiber and making a moderate entanglement state while blowing off the liquid moderately, the air pressure is preferably 0.5 to 10 kgf/cm ^{2, more} preferably 1 to 5 kgf/cm ² , 1.5 to 3kgf/cm ² is even better. Before the Taslan box, the reinforcing fibers and/or thermoplastic resin fibers are made to contain liquid, and the liquid content can be controlled by blowing the liquid while mixing the fibers on the air side.

<About water soluble ingredients>

The blended yarn of the present invention preferably contains water-soluble components. The water-soluble component means a compound having a solubility of 10 g or more with respect to 100 g of water at 23°C. For example, it is suitable to use: water-soluble polymer polyvinylpyrrolidone, polyethylene glycol or its derivatives or copolymers thereof, polyacrylic acid, polysulfonic acid, polyvinyl alcohol, polyvinylacetamide, cellulose Derivatives, starch derivatives, etc., low molecular weight compounds with reactive groups such as epoxy resins and acrylate resins.

The water-soluble component may be contained in the reinforcing fiber and/or thermoplastic resin fiber in the blended yarn, but when contained in both, it is preferable because the adhesion between the two is high and it is easily impregnated during molding. . In addition, when unevenly adhered to the surface of the reinforcing fiber, the interface strength between the reinforcing fiber and the thermoplastic resin serving as a matrix in the molded body tends to increase, which is preferable. From the viewpoint of the balance between impregnation and interfacial strength, the water-soluble component is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and more preferably 0.5 to 3% by mass relative to the reinforcing fiber system. 1 to 2 mass% is the best.

The water-soluble component can be added to the raw material, or it can be added when blending fibers, or after manufacturing the blended yarn. From the viewpoint of easily attaching unevenly to the surface of the reinforcing fiber, it is preferably added to the reinforcing fiber of the raw material. When the reinforcing fiber contains a water-soluble component, the water-soluble component will move through the liquid when it comes into contact with the liquid in the fiber mixing step. Therefore, the water-soluble component forms a distribution on the surface of the reinforcing fiber and simultaneously moves into the thermoplastic resin fiber.

<About reinforced fiber>

Reinforced fibers can be used in general reinforced fiber composite material molded body, and the following materials are not limited, but can be selected from, for example, selected from: glass fiber, carbon fiber, amide fiber, ultra-high-strength polyethylene fiber, polyindene Indole (PBZ: polybenzazole)-based fibers, liquid crystal polyester fibers, polyketone fibers, metal fibers, and ceramic fibers are preferably at least one type. From the viewpoints of mechanical properties, thermal properties, and versatility, glass fibers, carbon fibers, and aromatic polyamide fibers are preferred, and from the viewpoint of elastic modulus, carbon fibers are preferred.

The monofilament diameter of the reinforcing fiber is not particularly limited, but from the viewpoint of strength handling with the molded body, it is preferably 1 to 22 μm, more preferably 3 to 17 μm, and even more preferably 5 to 12 μm. The number of filamentary fibers of the reinforcing fiber bundle can be appropriately set according to the needs of handling properties, and it is preferable to use 3000, 6000, 12000, and 24000.

It is better to use a sizing agent in the reinforcing fiber. It is better to use a coupling agent to form the interface between the reinforcing fiber and the thermoplastic resin, to improve the handleability of the reinforcing fiber and to help form the interface between the thermoplastic resin and the coupling agent. Lubricants that enhance fiber handling.

The surface state of the reinforcing fiber will change due to the sizing agent. From the viewpoint of the strength of the blended yarn and the strength of the molded body, the reinforcing fiber is preferably in a state of having a high affinity with the liquid used in the blending step. Here, the state in which the reinforcing fiber has a high affinity with the liquid means that when the reinforcing fiber bundle is cut into about 5 cm and placed in the liquid tank, the reinforcing fiber bundle is in a state of falling apart.

From the viewpoint of uniformly coating the reinforcing fibers, the sizing agent is preferably applied in liquid or gas form. When using a compound with a high melting point and a high boiling point, it can be applied while being heated, or it can be applied by being dissolved in a solvent. As other components, antioxidants, ultraviolet absorbers, colorants, heat transfer agents, heat stabilizers, etc. may also be contained.

As a method of selecting the type of the sizing agent, for example, the use of the interface strength with the base resin by the droplet test as described in Japanese Patent Laid-Open No. 2015-67926 can be cited. However, since the sizing agent may be volatilized or deteriorated by heating, it is preferable to conduct this test after applying the heat history during molding. It is preferable to use the water-soluble ingredient disclosed just now as a sizing agent.

The lubricant system helps to strengthen the adjustment of fibers and prevent damage, as well as improve the fiber opening. As a lubricant, any lubricating material suitable for general liquids or solids suitable for the purpose can be used without particular limitation, but animal or plant-based or mineral-based waxes such as carnauba wax or lanolin wax; fatty amides, fats One or more surfactants such as acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

The binder system helps to improve the bundling of reinforcing fibers and improve the interface adhesion strength. As the binder, polymers and thermoplastic resins suitable for the purpose can be used. The polymer is not particularly limited, but examples include epoxy resins such as bisphenol A epoxy resin; phenol resin obtained by reacting various phenols with formalin; urea resin obtained by reacting urea with formalin. ; Thermosetting resin such as melamine resin obtained by the reaction of melamine and formalin. In addition, for example, isocyanates such as m-xylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate, and polyester or polyether glycols Synthetic polyurethane resin.

The thermoplastic resin used as the binder is not particularly limited, but examples thereof include polyolefin resins, polyamide resins, polyacetal resins, polycarboxylate resins, polyester resins, and polyether ketones. , Polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyether amide imide, thermoplastic fluorine-based resin, and these modified modified thermoplastic resins. If it is the same thermoplastic resin and/or modified thermoplastic resin as the thermoplastic resin fiber forming the blended yarn, the adhesion between the reinforcing fiber and the thermoplastic resin fiber will be improved after it becomes a composite molded body, which is preferable.

From the viewpoint of improving the efficiency of the fiber blending step, the hydrophilicity index of the reinforcing fiber used in the present invention is preferably 8 degrees or more, more preferably 30 degrees or more, and even more preferably 60 degrees or more. The so-called hydrophilicity index here refers to a unique index compatible with the blending process of the present invention. The hydropathic index is measured by the same method as the softness of the blended yarn, and as shown in the examples, it is expressed by the difference between the dryness and the wetness.

<About thermoplastic resin fiber>

Thermoplastic resin fibers are generally fiberized by using base resins used in composite materials. For example, it will be selected from: polyolefin-based resins such as polyethylene and polypropylene; polyamide-based resins such as polyamide 6, polyamide 66, and polyamide 46; polyethylene terephthalate, poly-p-phenylene Polyester resins such as butylene dicarboxylate and polytrimethylene terephthalate; polyacetal resins such as polyoxymethylene; polycarbonate resins; polyether ketone; polyether ether ketone; polyether ash; Polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluorine-containing resins such as tetrafluoroethylene-ethylene copolymers and at least one thermoplastic resin in the group consisting of modified thermoplastic resins modified by these, Continuous fibers obtained by melt spinning are preferred.

Among these thermoplastic resins, they are: polyolefin resin, polyamide resin, polyester resin, polyether ketone, polyether ether ketone, polyether ballast, polyphenylene sulfide, thermoplastic polyether amide imine , And thermoplastic fluorine resins are preferred, and from the viewpoint of mechanical properties and versatility, polyolefin resins, modified polyolefin resins, polyamide resins, and polyester resins are preferred, plus From the viewpoint of thermal physical properties, polyamide resins and polyester resins are more preferable. In addition, from the viewpoint of durability against repeated loading, polyamide resins are more preferable, and aliphatic polyamide resins, especially polyamide 6 and polyamide 66 are suitable.

The thermoplastic resin fiber system may contain: lubricants, antioxidants, ultraviolet absorbers, colorants, heat transfer agents, heat stabilizers, etc. Compounds previously imparted with high affinity with the liquid at the time of fiber blending can improve fiber blending efficiency, and It is better to share this compound with reinforcing fibers to improve the impregnation.

<About fabrics and knitting>

The blended yarn of the present invention is used and processed into a cloth shape, and it is preferable for the user as an intermediate material for obtaining a fiber-reinforced resin molded body. The form of the cloth is not particularly limited, but it can be exemplified by unidirectional reinforcing materials obtained by aligning the mixed yarns in a specific direction, and fabrics using composite yarns, such as fabrics or knitted fabrics, laces, felts, non-woven fabrics, films, or Plate-like body. As an intermediate material, when manufacturing a fiber-reinforced resin molded body, from the viewpoint of following the nature of the shape in the mold, a unidirectional reinforcing material, woven fabric, knitted fabric, lace, felt, non-woven fabric with flexibility is preferred. The fiber has less bending and tends to show strength, so the shape of the knitted fabric, unidirectional reinforcement, and fabric is better, and the shape of the knitted fabric and fabric is better from the viewpoint of form stability.

The fabric can be a biaxial fabric or a triaxial fabric. The weaving method of the fabric is not particularly limited, and examples include plain weave, twill weave, satin weave, rib weave, and gauze.

From the viewpoint of the strength of the fiber-reinforced resin molded body, a twill weave that can reduce the shrinkage rate of the reinforced fiber is better.

For example, from the viewpoint of strength, the knitted fabric is preferably a multi-axial insert knitted fabric called a non-crimped fabric. The knitted fabric stitches may include tricots, conbinations, and the like.

<About weaving and knitting steps>

The method of obtaining the cloth-like intermediate material is not particularly limited, and can be selected according to the application and purpose.

For example, fabrics are used: shuttle looms, sword loom looms, air-jet looms, water-jet looms and other looms, at least a part of which contains blended yarns. For example, a method obtained by weaving a weft yarn in a warp yarn in which fibers containing mixed yarns are arranged is preferred. Among them, a sword-mast loom is preferred from the viewpoint of suppressing damage to the reinforcing fibers and stably obtaining the fabric. Since the tension of the fabric is stabilized and uniform quality fabric is easily obtained, the width of the sword mast loom is preferably 60 cm or more, more preferably 80 cm or more, and more than 100 cm. If the width is more than a certain size, the quality will be stable, but it is better to set the line used for the deployment to a width that is easy to use. When glass fiber or carbon fiber is used in the reinforcing fiber bundle, the width is preferably 6 m or less, more preferably 5 m or less, even more preferably 4 m or less, and most preferably 3 m or less.

The knitted fabric is obtained by using at least a part of a knitting machine such as a circular knitting machine, a flat knitting machine, a warp knitting machine, a raschel machine (raschel machine), etc., into fibers containing composite yarns.

The non-woven fabric is formed by embossing rolls by physical action of a needle punching machine, sewing machine, cylindrical flow machine, etc. after forming at least a part of the fibers containing the composite yarn into a sheet-like fiber assembly called a web. Those who get the fiber combined with each other by heat or adhesive.

Regarding the form of other intermediate materials, etc., the method described in Japanese Patent Laid-Open No. 2015-101794 can be used as appropriate.

In the present invention, the step of obtaining the woven fabric or knitted fabric is preferably carried out in a state where the reinforcing fiber is in a liquid state. By treating in a liquid state, not only can it prevent fluffing, but it can also improve the linear running state of the reinforcing fibers in fabrics and knitted fabrics. As a result, the strength of the molded body can be improved. Due to the relationship between strength and handleability, the liquid content is preferably 0.1 to 5 mass%, more preferably 0.2 to 4 mass%, and 0.3 to 3 mass% relative to the reinforced fiber system.

The reinforcing fiber may contain liquid at any point, or may be produced in the process of manufacturing the mixed fiber yarn, or may be carried out in the state where the mixed fiber yarn is wound, and a liquid addition step may be provided as an additional step after winding. In addition, it may be carried out in the warping step as a preparation step for weaving or weaving, or it may be carried out before the weft yarn is inserted in the step of the warp or reed, or in the weft. From the viewpoint of strength and impregnability, it is preferable to make the reinforcing fibers liquid before manufacturing the mixed fiber yarn, adjust the amount of liquid during fiber mixing, and then perform the weaving and knitting steps.

In the present invention, after fabrics or knitted fabrics are manufactured, by impregnating these cloths with a liquid, the impregnability can also be improved, the interface strength, and the strength of the molded body can also be improved. The cloth at this time may be composed only of reinforcing fibers, or may be composed of reinforcing fibers and thermoplastic resin. The thermoplastic resin may be in any form of powder, film, braid, or fiber, but from the viewpoint of shortening the distance to the reinforcing fiber, it is preferably powder or fiber, and from the viewpoint of the stability of the cloth In other words, it is better to be fibrous. The fibrous thermoplastic resin may be a mixed fiber with a reinforcing fiber, or may be in a state of mixed weaving or knitting. When impregnated with liquid, the state of the reinforcing fiber can be adjusted appropriately by squeezing.

<Forming method>

The fiber-reinforced resin molded body can be manufactured using the above-mentioned mixed yarn or intermediate material as a constituent material. In addition, the method of manufacturing the fiber-reinforced resin molded body is not limited to the following, and various methods can be applied.

For example, the base material constituting the fiber-reinforced resin molded body (preferably a base material in the shape of a fabric or a braid) is cut according to a desired molded body, and the number of necessary layers for the thickness of the target product is considered, and the shape of the mold install. In this case, by using the above-mentioned intermediate material, the degree of freedom of the mold can be improved compared to the conventional composite board in which the reinforcing fiber is impregnated with the resin, and the shape can be improved even in the case of a height difference in the molded body Freely shape. The step of drying the base material may be included before being placed in the mold. The drying step can be performed before cutting, and/or after cutting.

The cutting of the base material may be performed one by one, or may be performed by overlapping a desired number of sheets. From the viewpoint of productivity, it is preferable to cut in an overlapping state. Any method can be used for the cutting method, and examples thereof include water jet, blade press, hot blade press, laser, and plotter.

After installing the substrate in the mold, the mold is closed and compressed. Then, at a temperature above the melting point of the thermoplastic resin constituting the fiber-reinforced resin molded body, the temperature of the mold is adjusted to melt and shape the thermoplastic resin. Although there is no special regulation on the clamping pressure, it is preferably 1 MPa or more, and more preferably 3 MPa or more.

In the manufacturing process of the fiber-reinforced resin molded body, an intermediate material is installed in the mold and the mold is closed and pressurized. After a predetermined time, the predetermined thermoplastic resin composition is further injected and filled to form, by joining the thermoplastic resin The fiber and the predetermined thermoplastic resin composition can be used to produce a hybrid molded body.

<use>

The fiber-reinforced resin molding system is suitable for use in construction materials such as airplanes, vehicles, construction materials, and sporting goods.

In the vehicle application, it is not limited by the following, but for example, it can be used in: chassis/frame, chassis, drive train parts, internal components, external parts, functional parts, other parts.

[Example]

Hereinafter, specific examples and comparative examples of the present invention are presented, but the present invention is not limited to the following examples.

<Carbon Fiber (CF)>

Carbon fiber A (CF-A):

In the PAN (polyacrylonitrile) carbon fiber of standard elastic modulus of monofilament diameter 7μm, filament number 12000, density 1.81g/cm ³ , attached as a sizing agent polyvinylpyrrolidone (water-soluble component) 2.9 mass %. When the sizing agent was removed by impregnation in water and separated into monofilament units, when the tensile test was performed at a length of 5 cm, the load at break was 6.2 g. That is, the strength of the tow is calculated to be about 2000 MPa. The hydropathic index is 80.

Carbon fiber B (CF-B):

In the PAN (polyacrylonitrile) carbon fiber with a standard filament modulus of 7 μm in diameter, 12,000 filaments, and a density of 1.81 g/cm ³ , the bisphenol A (polyethylene glycol) as a water-soluble component of the sizing agent is attached. ) Ether (the average repeat number of polyethylene glycol is 9.3) 0.11% by mass, and 0.1% by mass of the long-chain hydrocarbon compound of the water-insoluble component. The strength of the tow is 4500 MPa, and the hydrophilicity index is 12.

Carbon fiber C (CF-C):

Except that the amount of polyvinylpyrrolidone of the sizing agent was changed to 0.08% by mass, the same carbon fiber as the carbon fiber A was prepared. The hydropathic index is 50.

<thermoplastic resin fiber>

Leona (registered trademark) 470/144 BAU (manufactured by Asahi Kasei Fiber Co., Ltd.), fineness of 470 dtex, and number of single filaments 144 Leona are used. Contains 0.9% water-soluble ingredients.

<Molding method of unidirectional material>

With a target of 20 mm in width, 200 mm in length, and 1 mm in thickness, a test piece was obtained by the procedure shown below. In one molding, two test pieces (molded bodies) were obtained. The forming machine used a hydraulic forming machine (manufactured by Shoji Co., Ltd.) with a maximum clamping force of 50 tons.

As shown in Fig. 2, the filament yarn 5 is wound around the aluminum template 6. The thickness of the aluminum template 6 is 5 mm, and the number of windings is the minimum number of times that the total cross-sectional area of the mixed yarn 5 becomes 20 mm ² or more. As shown in Fig. 3, this is installed in a mold with a clearance of 0.5 mm composed of COR (core) 7 and CAV (cavity) 8.

The temperature in the molding machine was heated to 300°C, put into the mold, and then clamped with a clamping force of 5 MPa to perform compression molding. The molding time is 10 minutes from the start of reaching the melting point of the base resin component (265°C for polyamide 66). After the mold is rapidly cooled, the mold is opened and the molded body is taken out.

<Fabric forming method>

The forming machine used a hydraulic forming machine (manufactured by Shose Co., Ltd.) with a maximum clamping force of 50 tons.

In a mold with a height of 10 cm, a width of 20 cm, and a thickness of 2 mm, put a predetermined number of pieces of fabric cut into a height of 9.5 cm and a width of 19.5 cm. In addition, the number of pieces is the minimum number of pieces set so that the volume of the fabric becomes 40 cm ³ or more.

The temperature in the molding machine was heated to 300°C, the mold was put in, followed by clamping with a clamping force of 5 MPa, and compression molding was performed. The molding time is 10 minutes from the start of reaching the melting point of the base resin component (265°C for polyamide 66). After the mold is rapidly cooled, the mold is opened and the molded body is taken out.

<Tensile Strength, Tensile Elastic Modulus, and Strength Presentation Rate of Unidirectional Materials>

The test piece was vacuum-dried at 80°C for 2 days before the test. At both ends of the test piece, a tab made of glass fiber reinforced resin (GFRP) with a thickness of 2 mm, a width of 20 mm, and a length of 50 mm was connected with an instant adhesive so that the tab pitch became 100 mm. A strain gauge (KFGS-5-120-C1-23 manufactured by Kyowa Electric Industry Co., Ltd.) was connected to the center of the test piece.

Using a 100 kN tensile tester manufactured by Instron and a dynamic strain gauge manufactured by Kyowa Electric Industry Co., Ltd., a tensile test was performed at a tensile speed of 1 mm/min. The maximum load is taken as the tensile strength (MPa), and the maximum inclination of the strain-load curve is taken as the tensile elastic modulus.

The measured value of the tensile strength relative to the theoretical strength calculated by the following formula is taken as the strength presentation rate of the unidirectional material.

Theoretical strength = tensile strength of reinforcing fiber bundle × volume ratio of reinforcing fiber + tensile strength of resin × volume ratio of resin

<Tensile Strength, Tensile Modulus of Elasticity, and Strength Presentation Rate>

The test piece was vacuum dried at 80°C for 2 days before the test. The test piece was cut into a dumbbell shape (length 100 mm, parallel portion 6 mm, thickness 2 mm). The protrusions made of glass fiber reinforced resin (GFRP) with a thickness of 2 mm, a width of 13 mm, and a length of 22.5 mm were connected with an instant adhesive so that the tab pitch was 50 mm at both ends of the test piece. A strain gauge (KFGS-5-120-C1-23 manufactured by Kyowa Electric Industry Co., Ltd.) was connected to the center of the test piece.

Using a 10 kN tensile tester manufactured by Instron and a strain gauge manufactured by Kyowa Electric Industry Co., Ltd., a tensile test was performed at a tensile speed of 1 mm/min in the direction of 0 to 90 degrees. The maximum load is taken as the tensile strength (MPa), and the maximum inclination of the strain-load curve is taken as the tensile elastic modulus.

The measured value of the tensile strength relative to the theoretical strength calculated by the following formula was used as the strength presentation ratio. The strength of the composite material in the fiber direction is high, and the strength in the fiber perpendicular direction becomes low. In the present examples and comparative examples, since the density of the warp and weft yarns is the same, the half value of the unidirectional material is used as the theoretical strength of the tensile strength of the fabric.

Theoretical strength = (tensile strength of reinforcing fiber bundle × volume ratio of reinforcing fiber + tensile strength of resin × volume ratio of resin) / 2

<Volume content of reinforcing fiber>

The measurement was performed by the combustion method of JIS K 7075.

<unimpregnated rate>

Cut 5 cross sections from any position of the molded body, embed it in epoxy resin, and carefully grind to avoid damage to the reinforcing fibers. Observed by a microscope, the area occupied by the fiber bundle, the thermoplastic resin, and the pores is determined from the obtained image, and calculated by the ratio of the area of the pores to the total area. In addition, the measurement was performed four times for each cross section, and the median value was taken as the unimpregnated ratio from the data of 20 points in total.

<Amount of water-soluble components of reinforcing fibers, thermoplastic fibers, and blended yarns>

3.5 g of fiber was immersed in 60 ml of pure water and heated at 80° C. for 8 hours. It was filtered and washed twice with 40 ml of pure water. The entire liquid is recovered and mixed as an analysis liquid, and the components dissolved in the liquid are recovered by freeze-drying, and the mass is measured to quantify the amount of the water-soluble component.

<The amount of components of the reinforcing fibers and thermoplastic resin fibers attached to the blended yarn>

Cut the blended yarn to a proper length and separate it into reinforced fiber and polyamide fiber. Water is extracted from each fiber to quantify the amount of water-soluble components attached to the fiber. After that, the ratio of the component (A) derived from the reinforcing fiber and the component (B) derived from the polyamide fiber was calculated using NMR and quantified. In addition, the amount of components adhering to the reinforcing fibers is expressed as a percentage relative to the mass of the reinforcing fibers, and the amount of components adhering to the thermoplastic fibers is expressed as a percentage relative to the mass of the thermoplastic fibers.

Since only the reinforcing fiber of the raw material of Example 2 contains water-insoluble components, after water extraction, extraction with chloroform is carried out in the same manner to quantify the total amount of water-soluble components.

Only the organic component (C) was added to the liquid of Example 8. (C) in this case is to extract and quantify the reinforcing fiber with hexafluoro-2-propanol. For the polyamide fiber, the weight per unit length was measured, and the amount added to the raw material was taken as the amount of (C).

<Mixed ratio of reinforcing fibers in blended yarn>

The degree of mixing is defined as the ratio of the number of reinforcing fibers adjacent to the thermoplastic resin fibers to the total number of reinforcing fiber bundles. The mixed filament was cut in a state covered with a shrink tube, the cross section was observed with an optical microscope, and the ratio was calculated by image processing. Observe the average value of the cross section 20 at any position.

<Porosity of blended yarn>

After covering the mixed filament with a shrink tube, the colored epoxy resin is injected into the tube to harden it, and then cut and polished to observe the cross section.

Porosity = area of pores/inner area of the outer periphery of the blended yarn×100

The area of the pores is the area of the colored epoxy resin which is inside the outer circumference of the mixed filament yarn, and the outer circumference of the mixed filament yarn is drawn by the line connecting the outermost fibers.

<degree of dispersion of organic matter>

After extracting organic matter from the blended yarn using a solvent, the mass is measured, and the ratio of the mass of the organic matter to the mass of the blended yarn is calculated. The same measurement was performed for 20 arbitrary locations, the average value and the standard deviation were calculated, and the value of the standard deviation divided by the average value was used as the degree of dispersion.

<softness of blended yarn, hydrophilicity index of reinforced fiber>

Cut the mixed fiber yarn just made 20cm, and fix the end to the end with a tape with a width of 1.5cm to make a loop. Hold the part fixed with tape and hang it vertically. At this time, if vertical cannot be formed, press lightly with your hand to make it vertical. While holding a part of the tape, turn it 180 degrees in the vertical direction so that the tape part is facing down to make the mixed yarn stand vertically. Hold the mixed fiber thread for 1 minute without touching it, and measure the sagging angle of the mixed fiber thread with respect to the vertical direction. In the case of bending into two stages, the larger angle is used. 20 arbitrary points were measured and the average value was calculated.

The hydrophilicity index of the reinforcing fiber is measured in the same manner as the softness of the reinforcing fiber when dry and when wet, and the difference is calculated. When drying, it was measured after vacuum drying at 25°C for 2 hours. When it is wet, prepare a Kim Towel4 made of Japanese paper and distribute 50ml of distilled water evenly. Put the sample that has been measured during drying between Kim Towel and let it stand for 10 seconds without applying weight. Determination.

<surface tension, rate of change of surface tension>

The contact angle measuring device DM500 manufactured by Kyowa Interface Science Co., Ltd. was used to measure by the hanging drop method (Laplace method). Since the melting point of polyamide 66 is 265°C, it is measured at 310°C under a nitrogen atmosphere 1 minute after the formation of droplets. The melt density was calculated to be 1 g/cc. In addition, as a pretreatment, sufficient drying is necessary, and the case of polyamide 66 is measured after vacuum drying at 90°C for 2 days.

Relative to polyamide 66 (thermoplastic resin fiber), the organic substance to be mixed was mixed at a rate of 10% by mass using a twin-screw extruder under low shear conditions. The surface tension was measured in the same manner, and the rate of change of the surface tension was calculated.

<Measurement of interface shear stress>

The composite material interface characteristic evaluation device HM410 (manufactured by Dongrong Industry Co., Ltd.) was used and measured by a droplet test.

The monofilament is taken out from the reinforced fiber of the raw material or the reinforced fiber in the blended yarn and placed in the device for evaluating the interface characteristics of the composite material. On the apparatus, droplets obtained by melting thermoplastic resin, which is a raw material of thermoplastic resin fibers, are formed on the reinforcing fiber monofilament, and sufficiently cooled at room temperature to obtain a sample for measurement. Place the measurement sample again in the device, sandwich the droplets between the blades of the device, and run the reinforced fiber monofilament on the device at a speed of 0.06mm/min to measure the maximum tensile load f( N), the interface adhesion strength τ is calculated according to the following formula.

Interface strength τ=f/π. R. l(f: maximum tensile load (N), R: diameter of reinforced fiber monofilament (m), l: particle diameter of droplets in the stretching direction (m))

The rate of change of the interface shear stress is the absolute value of the difference between the interface shear stress of the reinforcing fiber taken out of the mixed fiber and the interface shear stress of the reinforcing fiber of the raw material relative to the interface shear stress of the reinforcing fiber of the raw material. .

(Example 1)

Using 1 carbon fiber A and 10 polyamide yarns, after aligning all the yarns, pass 45 ml/min of flowing water. After passing through the roller, it was introduced into a Taslan box, and Taslan processing was performed under an air pressure of 2.0 kgf/cm ² to obtain a blended yarn. The winding wire speed was set at 65 m/min, and the feed was carried out in such a manner that the raw material carbon fiber was 66 m/min and the raw material polyamide fiber was 68 m/min.

(Example 2)

Except for using carbon fiber B, the same operation as in Example 1 was performed to obtain a blended yarn. Even after fiber blending, water-insoluble components remain in the carbon fiber.

(Example 3)

Except that the amount of water was set to 85 ml/min, the same operation as in Example 1 was performed to obtain a blended yarn.

(Example 4)

Except that the polyamide yarn was changed to 6 yarns, the same operation as in Example 1 was performed to obtain a blended yarn.

(Example 5)

Using 1 carbon fiber A and 10 polyamide yarns, after aligning all the yarns, pass 45 ml/min of flowing water. It was guided to a staggered fluid entanglement nozzle (KC-AJI-L (1.5 mm diameter, propulsion type) manufactured by Kyocera), and operated at an air pressure of 0.5 kg/cm ² and a processing speed of 50 m/min to obtain a blended yarn.

(Example 6)

The mixed fiber yarn obtained in Example 1 was introduced into a water tank and wound, and the amount of polyvinylpyrrolidone was reduced to 0.08% by mass.

(Example 7)

Place the carbon fiber A under the humidity of 95% for 3 angels and use it after absorbing moisture. In addition, even in the production of the blended yarn, 30 ml of water is sprayed and sprayed every 30 minutes per minute, and the carbon fiber bobbin is used while being humidified. One carbon fiber A was passed through 30 ml/min of flowing water. After that, the carbon fiber was aligned with 10 polyamide yarns, and then introduced into a Taslan box and subjected to Taslan processing at an air pressure of 2.0 kgf/cm ² to obtain a blended yarn. The winding wire speed was set to 65 m/min, and the feed was carried out in such a manner that the raw material carbon fiber was 66 m/min and the raw material polyamide fiber was 68 m/min.

(Example 8)

Except that a 5-fold diluted polyamide latex (Sepoljon PA 200 manufactured by Sumitomo Seika Co., Ltd.) was used instead of flowing water, the same operation as in Example 7 was performed to obtain a blended yarn.

The surface tension of polyamide 66 is 29.9mN/m, the surface tension of the solid content in the polyamide latex is 35mN/m, and the surface tension when the solid content of the polyamide latex is mixed in the polyamide 66 is 31.0mN /md, the surface tension change rate is 3.7%.

The forming time is 1 minute after reaching the melting point.

(Example 9)

Except that the amount of flowing water was set to 300 ml/min and was introduced into the Taslan box immediately upon contact with flowing water, the same operation as in Example 1 was performed to obtain a blended yarn.

(Example 10)

Except that 14 polyamide yarns were used, the same operation as in Example 7 was carried out to obtain a blended yarn.

(Example 11)

The same operation as in Example 1 was carried out except that the carbon fiber was used after being dried, and the wound wire speed was 45 m/min, the carbon fiber supply was 46 m/min, and the polyamide yarn supply was 48 m/min. And get the mixed yarn. Since the unwinding is not smooth, the operating speed is reduced.

(Comparative example 1)

Except that water was not used, the same operation as in Example 1 was performed to obtain a blended yarn. CF fluff will be generated in the environment.

(Comparative example 2)

Use 1 carbon fiber A and 10 polyamide yarns, align all the yarns and wind them directly. CF fluff will be generated in the environment.

(Comparative example 3)

Ten pieces of carbon fiber C and polyamide yarn were introduced into a Taslan box, and Taslan processing was performed in an air pressure of 2.0 kgf/cm ² to obtain a blended yarn. The winding wire speed was set at 65 m/min, and the feed was carried out in such a manner that the raw material carbon fiber was 66 m/min and the raw material polyamide fiber was 68 m/min. CF fluff will be generated in the environment.

(Comparative example 4)

After using 1 carbon fiber A and 10 polyamide filaments and aligning all the threads, they are introduced into a water tank filled with water. The pump circulates the water to 20m/min, and the fiber is opened by the water flow. After the spun fibers are superimposed, they are introduced into a water jet nozzle, 10 kg/cm ² of water is supplied, and the fibers are mixed by turbulent flow treatment. The speed of the yarn is set at 20m/min. Carbon fiber A and polyamide yarn are fed at a speed of 22m/min. After winding, drying was performed at 150°C for 10 hours.

(Example 12)

The blended yarn obtained in Example 1 was used to obtain a 4-4 twill woven fabric with a density of 6 counts/inch using a sword-mass loom. The moisture content of the carbon fiber in the weaving step is 5% by mass.

(Comparative example 5)

Using the blended yarn obtained in Comparative Example 3, a fabric was obtained in the same manner as in Example 12.

The test pieces of the mixed fiber yarns of Examples 1 to 11 were excellent in tensile strength, tensile modulus of elasticity, and strength rendering ratio. In addition, the fabric obtained in Comparative Example 5 had a lot of fluff, and scattered carbon fibers were seen in the environment. Compared with the test piece of the fabric passed through Example 12, the tensile strength, tensile elastic modulus, and strength rendering ratio were all reduced. .

[Industry use possibility]

According to the manufacturing method of the mixed fiber yarn, the mixed fiber yarn, and the manufacturing method of the fabric or knitted fabric of the present invention, it is possible to obtain a reinforced material suitable for materials requiring high-level mechanical properties in various mechanical or automobile structural parts, etc. Intermediate materials have industrial applicability.

The drawings in the present invention are only partial illustrations and cannot be used to represent the present invention, so there is no designated representative drawing in this case.

Claims (14)

A method of manufacturing a mixed fiber yarn is a method of manufacturing a mixed fiber yarn composed of at least a thermoplastic resin fiber and a reinforcing fiber, which includes: in the presence of a liquid, and by the fluid entanglement method by gas The step of blending the thermoplastic resin fiber and the reinforcing fiber, wherein the mixing ratio of the reinforcing fiber is 0.2 to 15%. The method for manufacturing a mixed fiber yarn as described in item 1 of the patent application range, wherein the reinforcing fiber contains a liquid of 300% by mass or less. The method for manufacturing a mixed yarn as described in item 1 or 2 of the patent application, wherein the fluid entanglement method is a fluid agitation method. The method for producing a mixed fiber yarn as described in item 3 of the patent application range, wherein the reinforcing fiber contains 0.1 to 5 mass% of a water-soluble component relative to the reinforcing fiber. The method for manufacturing a mixed fiber yarn as described in item 4 of the patent application range, wherein the hydrophilicity index of the reinforcing fiber is 8 degrees or more. A method of manufacturing a mixed fiber yarn is a method of manufacturing a mixed fiber yarn composed of at least a thermoplastic resin fiber and a reinforcing fiber, which comprises: performing the step of treating the thermoplastic resin fiber and/or the reinforcing fiber with a liquid immediately The fiber blending step is performed by a fluid entanglement method using gas, wherein the mixing ratio of the aforementioned reinforcing fibers is 0.2 to 15%. The method for manufacturing a mixed fiber yarn as described in item 6 of the patent application range, wherein the liquid contains an organic substance. The manufacturing method of the blended yarn as described in item 7 of the patent scope, However, when 10 mass% of the organic substance is mixed with the thermoplastic resin fiber, the rate of change in the surface tension of the thermoplastic resin fiber is 30% or less. The method for manufacturing a blended yarn as described in any one of the items 6 to 8 of the patent application scope is to treat the liquid recovered in the blending step by the fluid entanglement method described above with the liquid treatment The liquid in the step is mixed. A mixed fiber yarn is a mixed fiber yarn composed of at least a thermoplastic resin fiber and a reinforcing fiber. The mixed fiber yarn has a porosity of at least 24%, which contains at least two or more organic substances, and the two or more organic substances Adhering to both the reinforcing fiber and the thermoplastic resin fiber, the mixing ratio of the reinforcing fiber is 0.2 to 15%. The mixed yarn as described in item 10 of the patent application range, wherein the degree of dispersion of the organic substance on the surface of the reinforcing fiber and the thermoplastic resin fiber is 5% or more. The mixed yarn as described in item 10 or 11 of the patent application scope, wherein the softness of the mixed yarn is more than 20 degrees. The mixed fiber yarn as described in item 10 or 11 of the patent application range, wherein the total amount of the above-mentioned organic substances is less than 2% by mass relative to the mixed fiber yarn. A method for manufacturing a fabric or a knitted fabric is a method for manufacturing a fabric or a knitted fabric composed of at least a thermoplastic resin and reinforcing fibers. In the step of weaving the reinforcing fibers, the liquid content of the reinforcing fibers is 0.1 to 5 mass% Proceed.

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