JP6297311B2 - Cloth - Google Patents

Description

  The present invention relates to a fabric.

A preform is used as a reinforcing material for a composite material molded body used in various parts such as machines and automobiles, pressure vessels, tubular structures, and the like.
Examples of the preform that is one of the intermediate materials of the composite material molded body include a fabric using a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed. A non-woven fabric that is made by knitting or knitting a composite yarn together with other fibers into a knitted fabric or woven fabric, or laminating at random, creating a web, and then integrating by heat fusion using an embossing roll or entanglement using a needle punch The fabric obtained by making it into an intermediate material is used as an intermediate material. The resulting fabric-like preform is subjected to compression heating or internal pressure heating to melt and mold the thermoplastic resin fibers in the composite yarn contained in the fabric, thereby obtaining a composite material molded body. Moreover, after impregnating the obtained preform with a thermosetting resin, the composite material molded body can be obtained by heating under pressure.

  When obtaining a preform and a composite material molded body, it is important that the composite yarn is excellent in handleability so that the continuous reinforcing fiber is not easily damaged. For that purpose, the composite yarn is uniformly dispersed in the composite yarn. It is important to mix and maintain the state in the preform production step and the composite material molding step. Further, when obtaining a composite material molded body, in order to exhibit sufficient mechanical properties by molding in a short time, in the composite yarn included in the fabric, the continuous reinforcing fiber is not damaged, It is very important that both the continuous thermoplastic resin fibers can be uniformly dispersed and mixed.

As a method for uniformly dispersing and mixing the continuous reinforcing fiber and the continuous thermoplastic resin fiber, Patent Document 1 discloses a method in which gas (air) is collided with the mixed yarn, and Patent Document 2 describes a crimping property. A method of blending taslan fibers with thermoplastic resin fiber bundles having reinforcing fibers and reinforcing fibers, Patent Document 3 discloses a method for specifying the amount of sizing agent applied to each fiber bundle, and Patent Document 4 discloses an electroopening method. A method of mixing fibers by a fiber method and an interlace method is disclosed.
Further, Patent Documents 5 and 6 describe a method of mixing fiber bundles in a liquid in order to suppress the occurrence of single fiber breakage, and Patent Document 7 widely applies a suction air flow to a deflected fiber bundle. A method of mixing fibers by combining the fiber bundles after opening is disclosed.

JP 60-209034 A JP-A-2-308824 JP-A-3-33237 JP-A-7-109640 JP-A-2-28219 JP-A-4-73227 Japanese Patent Laid-Open No. 9-324331

However, according to any of the methods of Patent Documents 1 to 7, the continuous reinforcing fibers and the continuous thermoplastic resin fibers are uniformly dispersed and mixed in the composite yarn included in the fabric, and the continuous reinforcing fibers are damaged. Both the unacceptable and unsatisfactory results were not achieved, and the handling of the composite yarn was not sufficient.
Specifically, in any of the methods disclosed in Patent Documents 1 to 4 in which continuous reinforcing fibers and continuous thermoplastic resin fibers are dispersed and mixed, the continuous reinforcing fibers and the continuous thermoplastic resin fibers are uniformly mixed. In addition, it is difficult to obtain a sufficiently spread state and a mixed state, and there is a problem that a single yarn breakage of continuous reinforcing fibers tends to occur, and the original mechanical properties of continuous reinforcing fibers cannot be obtained. When trying to prevent single yarn breakage, a sufficient mixed fiber state cannot be obtained, and as a handleability of the composite material, the processability when creating a fabric from the composite yarn is good, and the continuous reinforcing fiber is used in the process. Although it is required to be hard to damage, it is inferior in handleability, that is, when a composite material molded body is formed by short-time molding, sufficient mechanical properties cannot be obtained due to the generation of voids, etc. In order to obtain mechanical properties, there is a problem that it is necessary to perform molding for a long time of 10 minutes or more.

  In Patent Document 4, it is important that the matrix fibers and the reinforcing fibers are in a mixed state at a single fiber level, and the matrix fibers are uniformly dispersed in the reinforcing fiber gaps. Examples of the fiber method include so-called Taslan method, electric fiber opening method, interlace method and the like. However, the properties required for the reinforcing fiber and the matrix fiber to achieve such a mixed state are only described as fineness and single yarn fineness, and other properties and appropriate ranges of the properties are described. Is not described at all, and there is a problem in that it cannot always be guaranteed that a uniformly dispersed mixed state can be achieved even if the fiber mixing method is used.

  The method of mixing fibers in liquids disclosed in Patent Documents 5 and 6 has a problem that an extra step of removing the liquid is required, and the fiber bundles that are widely opened disclosed in Patent Document 7 are combined. According to the method of mixing fibers, it is not possible to obtain a sufficient mixed state as a whole, although uniform fiber mixing can be obtained only by combining the spread fiber bundles.

  The problem to be solved by the present invention is that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are mixed uniformly and continuously without damaging the continuous reinforcing fiber, and the handleability for obtaining the fabric is excellent. An object of the present invention is to provide a fabric using a composite yarn optimal for obtaining a composite material molded body that exhibits sufficient mechanical properties even in molding.

As a result of intensive studies, the inventors of the present invention have excellent handling properties by mixing continuous reinforcing fibers having specific characteristics and continuous thermoplastic resin fibers having specific characteristics, so that both fibers are uniformly mixed. A matching composite yarn was obtained, and by using the composite yarn, it was found that a fabric that would be a composite material molded body having excellent mechanical properties could be obtained by molding in a short time, and the present invention was completed.
That is, the present invention is as follows.

[1]
A fabric comprising a composite yarn,
The composite yarn is a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed, and there is a difference in boiling water shrinkage between the continuous reinforcing fibers taken out from the composite yarn and the continuous thermoplastic resin fibers. A fabric having 0 to 10% and a difference in crimp ratio between continuous reinforcing fibers taken out from the composite yarn and continuous thermoplastic resin fibers of 0.5 to 20%.
[2]
The fabric according to [1], wherein the composite yarn is 50% by mass or more of fibers constituting the fabric.
[3]
The fabric according to [1] or [2], wherein the fabric is a woven fabric composed of warp and weft.
[4]
The fabric according to [3], wherein the composite yarn is 50% by mass or more of the fibers constituting the warp.
[5]
The fabric according to [3] or [4], wherein a fiber-fiber static friction coefficient between the warp and the weft is 0.2 to 3.0.
[6]
The fabric according to any one of [3] to [5], which is a plain fabric or an oblique fabric.
[7]
The fabric according to any one of [3] to [6], wherein the composite yarn is 50% by mass or more of fibers constituting the weft.
[8]
The fabric according to any one of [3] to [5], which is a bamboo woven fabric.
[9]
The fabric according to [8], wherein the composite yarn is 70% by mass or more of the fibers constituting the warp.
[10]
The fabric according to [8] or [9], wherein the ratio of warp density / weft density is 2 to 20.
[11]
The fabric according to any one of [1] to [10], wherein a difference in boiling water shrinkage between the continuous reinforcing fiber taken out from the composite yarn and the continuous thermoplastic resin fiber is 0 to 2.5%.
[12]
The boiling water shrinkage rate of the continuous thermoplastic resin fiber taken out from the composite yarn is 0 to 10%, and the crimp rate of the continuous thermoplastic resin fiber taken out from the composite yarn is 0.5 to 20%. %, The fabric according to any one of [1] to [11].
[13]
The continuous reinforcing fiber is at least one selected from the group consisting of glass fiber, carbon fiber, aramid fiber, ultrahigh strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber. , [1] to [12].
[14]
The continuous thermoplastic resin fiber is a group consisting of polyolefin resin, polyamide resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, and thermoplastic fluorine resin. The fabric [15] according to any one of [1] to [13], which is a continuous fiber obtained by melt spinning at least one thermoplastic resin selected from
The fabric according to any one of [1] to [14], wherein the composite yarn is a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed by a fluid entanglement method.
[16]
The composite yarn is continuous with a continuous thermoplastic resin fiber processed in a process including heat processing after the continuous thermoplastic resin fiber is processed in a process including heat processing alone and continuously in the same apparatus. The fabric according to [15], which is a composite yarn in which the reinforcing fibers are drawn and supplied to the fluid entanglement nozzle and the continuous reinforcing fibers and the continuous thermoplastic resin fibers are mixed.
[17]
The composite yarn is substantially perpendicular to the introduction hole surface of the fluid entanglement nozzle, in which the continuous reinforcing fibers are single or continuous thermoplastic fibers processed in a process including the continuous reinforcing fibers and heat processing are aligned. The fabric according to [15], which is a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed.

  According to the present invention, the continuous reinforcing fiber and the continuous thermoplastic resin fiber are continuously and uniformly mixed without damaging the continuous reinforcing fiber, and a composite yarn excellent in handleability for obtaining a fabric is obtained. By using the composite yarn, it is possible to obtain a fabric that becomes a composite material molded body that exhibits sufficient mechanical properties even in a short time.

It is a schematic side view which shows an example of a fluid entanglement apparatus. It is the schematic which shows an example of the supply state of the aligning yarn to the fluid entanglement nozzle in the fluid entanglement apparatus shown in FIG. It is the schematic which shows another example of the supply state of the aligning yarn to the fluid entanglement nozzle in the fluid entanglement apparatus shown in FIG. It is the schematic of the measuring apparatus of the static friction coefficient (microsecond) between a warp and a weft. An example of an organization chart of plain fabric An example of the structure diagram of a 2/2 twill fabric is shown. An example of the organization chart of 3/3 twill fabric is shown. An example of the organization chart of 2x2 silk fabric is shown.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

The fabric of this embodiment is a fabric including a composite yarn, and the composite yarn is a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed. The difference in boiling water shrinkage between the continuous reinforcing fiber taken out from the composite yarn and the continuous thermoplastic resin fiber is 0 to 10%, and the continuous reinforcing fiber taken out from the composite yarn and the continuous thermoplastic resin fiber are taken out. This is a fabric having a difference in crimping ratio of 0.5 to 20%.
If the difference in the boiling water shrinkage is 0 to 10% and the difference in the crimping rate is 0.5 to 20%, the composite material molded body in which the composite yarn is made into a fabric by weaving, knitting or the like is used. Even when a process including heating is performed when the intermediate material is dyed, or when the continuous thermoplastic resin fiber is melted in order to compress-mold the cloth which is the intermediate material for the composite material molded body, the continuous reinforcing fiber The continuous thermoplastic resin fibers are not separated from each other, and it is possible to maintain a continuous and uniform mixed state obtained by blending. Furthermore, it is possible to suppress the continuous reinforcing fiber from being bent and the mechanical properties from being lowered due to the separation of both the continuous reinforcing fiber and the continuous thermoplastic resin fiber.
From the viewpoint of suppression of separation of both fibers and continuous uniform mixing due to blending, the difference in boiling water shrinkage is preferably 0 to 7%, more preferably 0 to 5%, and even more preferably 0 to 2.5%. It is. From the viewpoint of suppression of separation of both fibers and continuous uniform mixing due to fiber mixing, the difference in crimp rate is preferably 2 to 20%, more preferably 5 to 15%.

In order to make the difference in boiling water shrinkage within a predetermined range, a composite yarn obtained by appropriately selecting from commercially available continuous reinforcing fibers and continuous thermoplastic resin fibers may be used. It is preferable to control the boiling water shrinkage rate by performing a process including thermal processing on the continuous thermoplastic resin fiber so as to be compatible with the fiber. The process including thermal processing may be performed in the spinning-drawing process of continuous thermoplastic resin fibers, or in a state of being wound after spinning-stretching, and is a pre-process for mixing continuous reinforcing fibers and continuous thermoplastic resin fibers. You may go on. When performing the process including heat processing in the pre-process of blending, you may perform simultaneously with a false twist process. It is preferable to perform a process including thermal processing alone or simultaneously with false twisting, in a pre-mixing process that enables efficient thermal processing according to the type of continuous reinforcing fiber.
The thermal processing temperature is preferably not less than the glass transition temperature (Tg) of the continuous thermoplastic resin fiber and not more than the melting point, more preferably not less than (Tg + 15 ° C.) and not more than the melting point, more preferably not less than (Tg + 20 ° C.) and not more than (melting point−10 ° C.). is there. The heat processing time may be appropriately set according to the heat processing method and the heat processing temperature so as to achieve the desired boiling water shrinkage, but is preferably 10 seconds to 60 minutes.

In order to set the difference in the crimp ratio within a predetermined range, it is preferable that the continuous reinforcing fiber is not crimped and the continuous thermoplastic resin fiber is crimped.
For imparting crimps, known methods can be used, and examples thereof include irregular cross sections, partial cooling during spinning, side-by-side type composite spinning, eccentric sea core type composite spinning, and methods for imparting mechanical crimping. . A method of imparting mechanical crimping is preferred from the viewpoint of versatility, and examples of the crimping imparting method in this case include false twisting method, knit deniting method, air stuffing box method, steam stuffing box method and the like. . Mixing may be performed continuously from false twisting, or heat may be applied to suppress shrinkage using a heater portion of a false twisting machine, and then mixed continuously. In the case of false twisting machine, either a 1 heater system or a 2 heater system may be used. In the case of using a false twisting machine, the false twist heater temperature is preferably (Tg + 15 ° C.) or higher and a melting point or lower, more preferably (Tg + 20 ° C.) or higher and (melting point −10 ° C.) or lower. In this case, the first heater temperature is preferably in the above temperature range, and the second heater temperature is preferably in the range of −30 ° C. to + 50 ° C. with respect to the first heater temperature.

In this embodiment, the boiling water shrinkage (referred to as “boiling water shrinkage” in this paragraph) of the continuous thermoplastic resin fiber taken out from the composite yarn is 0 to 10%, and the continuous thermoplastic resin fiber taken out from the composite yarn is continuous. The crimp rate of the thermoplastic resin fibers (referred to as “crimp rate” in this paragraph) is preferably 0.5 to 20%.
When the boiling water shrinkage is 0 to 10%, it is possible to suppress separation of the continuous reinforcing fiber and the continuous thermoplastic resin fiber even if the process including heating is performed on the fabric.
If the crimp rate is 0.5 to 20%, the contact between the continuous thermoplastic resin fibers and / or the continuous thermoplastic resin fibers and the continuous reinforcing fibers decreases, and the apparent frictional force between the fibers decreases, Since the fiber is easily opened and mixed, the continuous reinforcing fiber and the continuous thermoplastic resin fiber are easily and continuously mixed. Further, since the continuous thermoplastic resin fibers have crimps, even if the continuous thermoplastic resin fibers contract in the composite yarn, there is an effect that it is difficult to separate from the continuous reinforcing fibers.
From the viewpoint of dimensional stability of the composite yarn in the process including heating, the boiling water shrinkage is more preferably 0 to 7%, further preferably 0 to 5%, and still more preferably 0 to 2.5%. From the viewpoint of suppressing damage to the continuous reinforcing fibers in the composite yarn due to the cushioning property due to crimping, the crimp rate is more preferably 2 to 20%, and further preferably 5 to 15%.

Product RD single filament diameter R of the continuous reinforcing fibers ([mu] m) and density D (g / cm ³⁾ are preferably 5~100μm · g / cm ^3, more preferably 10~50μm · g / cm ^3, more preferably the 15~45μm · g / cm ^3, even more preferably 20~45μm · g / cm ^3.
If the product RD of continuous reinforcing fibers is 5 to 100 μm · g / cm ³ , continuous reinforcement without damaging the continuous reinforcing fibers when mixing both continuous reinforcing fibers and continuous thermoplastic resin fibers. The fibers can be easily opened, and both fibers can be mixed uniformly and continuously.
If the product RD of the continuous reinforcing fibers is 5 μm · g / cm ³ or more, the continuous reinforcing fibers are not easily damaged during the fiber mixing, the processing process of the fiber mixing is excellent, and the composite material molded body obtained from the fabric is sufficient. Demonstrate mechanical properties.
If the product RD of continuous reinforcing fibers is 100 μm · g / cm ³ or less, the continuous reinforcing fibers are easy to open, and both fibers are easily mixed uniformly. Therefore, a composite material molded body that exhibits sufficient mechanical properties can be obtained in a short time.

If the product RD of continuous reinforcing fibers is 5 to 100 μm · g / cm ³ , the continuous reinforcing fibers can be easily opened without damaging the continuous reinforcing fibers when both fibers are mixed, and both fibers The reason why it is possible to mix continuously and uniformly is not necessarily clear, but it is presumed that the reason is as follows. That is, when an external force is applied to the continuous reinforcing fiber, it is assumed that an external force proportional to the peripheral diameter, that is, the single yarn diameter is applied to one single yarn. On the other hand, the inertial mass per unit length per single yarn is proportional to the product of the square of the single yarn diameter and the density. According to the equation of motion, the acceleration generated in the single yarn is proportional to the value obtained by dividing the external force by the inertial mass. Inferred to be inversely proportional. Therefore, when the product RD is too small from a certain range, it is assumed that the continuous reinforcing fiber is easily damaged because the acceleration becomes excessive. On the other hand, when the product RD is excessively larger than a certain range, it is estimated that the continuous reinforcing fiber is difficult to open because the acceleration is excessively small.

In this embodiment, the catalog value is used for the density of the continuous reinforcing fiber, and the single yarn diameter R (μm) is the fineness T (dtex), the number of single yarns F (the number), and the density D (g / cm ³ ) of the continuous reinforcing fiber. And is calculated by the following formula (1).
R = 20 × (T / π · F · D) ^0.5 (1)

In order to set the continuous reinforcing fiber product RD within a predetermined range, the fineness T (dtex) and the number of single yarns F (the number) are appropriately selected for commercially available continuous reinforcing fibers according to the density of the continuous reinforcing fibers. do it. For example, when glass fiber is used as the continuous reinforcing fiber, the density is about 2.5 g / cm ³ , so that a single yarn diameter of 2 to 40 μm may be selected. Specifically, when the single fiber diameter of the glass fiber is 9 μm, the product RD becomes 23 by selecting the glass fiber having a fineness of 660 dtex and 400 single yarns. When the single fiber diameter of the glass fiber is 17 μm, the product RD is 43 by selecting the glass fiber having the fineness of 11,500 dtex and the number of single yarns of 2,000. When carbon fiber is used as the continuous reinforcing fiber, the density is about 1.8 g / cm ³ , so that a single yarn diameter of 2.8 to 55 μm may be selected. Specifically, when the single yarn diameter of the carbon fiber is 7 μm, the product RD is 13 by selecting the carbon fiber having a fineness of 2,000 dtex and a single yarn number of 3,000. When an aramid fiber is used as the continuous reinforcing fiber, the density is about 1.45 g / cm ³ , so that a single yarn diameter of 3.4 to 68 μm may be selected. Specifically, when the single yarn diameter of the aramid fiber is 12 μm, the product RD is 17 by selecting the aramid fiber having a fineness of 1,670 dtex and 1,000 single yarns.
In order to make the product RD within a preferable range, for example, a glass fiber having a single fiber diameter of 9 μm and a fineness of 660 dtex and 400 single yarns may be used.

[Composition of fabric]
50% by mass or more of the fibers constituting the fabric is a mixture of continuous reinforcing fibers and continuous thermoplastic resin fibers, and the boiling water shrinkage of the continuous reinforcing fibers and the continuous thermoplastic resin fibers taken out from the composite yarn. It is preferable that the difference between the continuous reinforcing fibers taken out from the composite yarn and the continuous thermoplastic resin fibers is 0.5 to 20%. Preferably it is 70 mass% or more, More preferably, 90 mass% or more is used.
By using the above-mentioned composite yarn, continuous reinforcing fibers and continuous thermoplastic resin fibers can be continuously and uniformly mixed, and the handle obtained in the process of knitting or the like to fabricate is excellent. Even in a short time, it is possible to obtain a composite material molded body that exhibits sufficient mechanical properties.
As a form of the fabric, a known one can be used, and is not particularly limited. For example, a knitted fabric or a woven fabric obtained by knitting a composite yarn alone or with other fibers is exemplified. And / or non-woven fabrics, etc., which are integrally laminated by thermal fusion using embossing rolls or entanglement using needle punches after laminating the cut composite yarns individually or together with other fibers and creating a web . Since the linearity of the composite yarn in the fabric can be increased and the apparent density of the fabric can be increased, a composite material molded body having excellent mechanical properties can be easily obtained in a short period of time. Is preferred.

〔fabric〕
The fabric is composed of warp and weft. The composite yarn is preferably used for 50% by mass or more of the fibers constituting the warp. The composite yarn is preferably used in an amount of 70% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass. From the viewpoint of satisfying mechanical properties such as strength and rigidity at a high level, it is preferable that 50% by mass or more of the fibers constituting the warp is a composite yarn.

  The types of warp used in the woven fabric include, for example, (a) a strand composed only of a composite yarn of continuous reinforcing fiber and continuous thermoplastic resin fiber, and (b) a composite yarn of continuous reinforcing fiber and continuous thermoplastic resin fiber. Examples thereof include strands obtained by twisting or arranging fibers other than the composite yarn, and (c) strands made of fibers other than the composite yarn of continuous reinforcing fibers and continuous thermoplastic resin fibers. A strand is a yarn in which a bundle of composite yarns is untwisted or lightly twisted 100 times / m or less, and it is preferable to use a strand from the viewpoint of increasing fiber linearity, and more preferably the number of twists Is preferably 50 times / m or less, particularly preferably 30 times / m or less. Hereinafter, the above (a) is referred to as “composite yarn strand”, and (b) is referred to as “strand made of composite yarn”.

In the case of (b), it is desirable that a composite yarn of continuous reinforcing fibers and continuous thermoplastic resin fibers is contained in one strand in an amount of 50% by mass or more, more preferably 70% by mass or more.
The warp may be composed of at least one selected from (a) and (b), or at least one selected from (a) and (b) and (c). In any case, the composite yarn is used in an amount of 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass in the total warp in the woven fabric. The fiber other than the composite yarn is not particularly limited as long as the ratio in the total warp is less than 50% by mass, and a known fiber can be used depending on the application and purpose. For example, a continuous thermoplastic resin described later is used. Fiber. In particular, the same type of fibers as the continuous thermoplastic resin fibers used for the composite yarn are preferable because they can suppress the deterioration of the thermoplastic resin during molding.

The woven fabric preferably has a fiber-to-fiber static friction coefficient (hereinafter sometimes referred to as “μs”) of warp and weft 0.2 to 3.0, more preferably 0.25 to 2. 5, More preferably, it is 0.3-2.0.
When μs is 0.2 or more, continuous reinforcement in the composite yarn is caused by fluctuations in the tension applied to the warp during weaving, or slipping of the warp and weft during molding or storage as a fabric after winding. It is possible to prevent the linearity of the fiber from being impaired, and to obtain a composite material molded body having excellent mechanical properties. Further, when μs is 3 or less, a desired composite material molded body shape can be obtained, which is suitable for a molding die shape due to shear deformation of a fabric when molding is performed.
Since μs varies depending on the combination of the fibers constituting the warp, the blending method / condition, the single yarn fineness, the total fineness, and the like, these conditions may be adjusted so as to obtain a desired μs. Among them, it is preferable to adjust the fiber-to-fiber static friction coefficient by adjusting the type of continuous reinforcing fiber, the type of sizing agent corresponding thereto, and the adhesion rate.

The structure of the woven fabric is not particularly limited, and a known structure can be used. For example, a basic structure such as a plain woven fabric, an oblique woven fabric, a satin woven fabric, or a changed structure formed by changing or mixing the basic structure is exemplified. From the viewpoints of warp and weft linearity and weaving efficiency in the woven fabric, plain woven fabric, oblique woven fabric, and changed plain woven fabric and changed woven fabric are preferred, and plain woven fabric having high equivalence in the warp and weft direction. And a change plain fabric is more preferable. A plain woven fabric is a structure in which warps and wefts are alternately crossed one by one, and is a structure having no front and back and high equivalence in the warp and weft directions. As for the changed plain fabric, the weave fabric in which the crossing points are added to the top and bottom or the left and right of the crossing point of the plain fabric, and wrinkles appear on the surface, two or more warps are linked together, and two or more wefts are the same An example is a diagonal fabric that enters. The oblique woven fabric is a structure having oblique lines in which the crossing points run obliquely. As the changed oblique woven fabric, the sharp oblique woven fabric having an oblique line of 45 ° or more, the mountain-shaped oblique woven fabric having a mountain shape, the constant Examples include broken torn textiles in which oblique lines appear in the opposite direction at every interval, and curved oblique textiles in which oblique texts having different inclination angles are combined.
Further, in order to increase the thickness of the woven fabric, a structure using a connecting yarn for warp or weft so as to have a structure in which a plurality of the above plain woven fabrics or oblique woven fabrics are stacked may be used to improve working efficiency. .

  In the plain fabric and the oblique fabric, the respective fibers constituting the warp and the weft are preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and still more preferably 100% by mass. By using the composite yarn in this embodiment, the mechanical properties of the composite material molded body can be improved in both the warp and weft directions. Further, from the viewpoint of equalizing the mechanical properties in the warp and weft directions, the ratio of warp density / weft density is preferably 0.5 to 2.0, more preferably 0.7 to 1.5. Furthermore, it is preferable that the mixing ratio of the composite yarn in the present embodiment in the fibers constituting the warp and the weft is equal.

Another example of the woven fabric is an interwoven fabric. The weave fabric is a fabric in which wefts that play a role of connecting at every required interval in the longitudinal direction are woven into a large number of warps composed of fiber cords, strands, and the like. Since the weave fabric has a high warp density, it is possible to obtain a composite material molded body in which the warp direction is strengthened with priority, and is suitable for unidirectional reinforcement. In order to efficiently perform unidirectional reinforcement, at least 70 mass% of the fibers constituting the warp are the composite yarns in this embodiment, and the ratio of warp density / weft density is 2 to 20 Is preferred. More preferably, 90% by mass or more, more preferably 100% by mass of the fibers constituting the warp is the composite yarn. The ratio of warp density / weft density is preferably 3-20, more preferably 4-8. If the ratio of the warp density / weft density is 2 to 20, the weft driving efficiency is good, the slip between the warp and the weft is suppressed, and the linearity of the warp can be maintained.
There is no restriction | limiting in particular about the kind of weft, and a fineness, Although it can select according to a use and the objective, It is preferable to select so that microseconds may be 0.2-3.0. Furthermore, it is preferable to use the same type of fiber as the warp from the viewpoint of suppressing mixing of impurities such as unmelted material and decomposition product of thermoplastic resin into the composite material molded body.

[Continuous reinforcing fiber]
<Type>
As the continuous reinforcing fiber used in the present embodiment, those used as a normal fiber-reinforced composite material can be used. For example, glass fiber, carbon fiber, aramid fiber, ultra high strength polyethylene fiber, polybenzazole fiber, Examples thereof include at least one selected from the group consisting of liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber. Glass fibers, carbon fibers, and aramid fibers are preferable from the viewpoint of mechanical properties, thermal properties, and versatility, and glass fibers are more preferable from the viewpoint of price.

<Form>
The number of single yarns of continuous reinforcing fibers is preferably 30 to 15,000 from the viewpoints of fiber opening and handling properties in the fiber mixing process.

<Glass fiber sizing agent>
When glass fiber is selected as the continuous reinforcing fiber, the sizing agent is preferably composed of a silane coupling agent, a lubricant and a binding agent.

(Silane coupling agent)
A silane coupling agent is usually used as a surface treatment agent for glass fibers and contributes to an improvement in interfacial adhesive strength. Although it does not restrict | limit especially as a silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyltriethoxysilane, (gamma) -aminopropyltrimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane One or more selected from the group consisting of mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes, among which aminosilanes are preferred. .

(lubricant)
The lubricant contributes to the improvement of the opening property of the glass fiber. As the lubricant, any ordinary liquid or solid lubricating material suitable for the purpose can be used, and is not particularly limited. For example, animal or plant or mineral wax such as carnauba wax or lanolin wax; fatty acid amide One or more selected from surfactants such as fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers can be used.

(Binder)
The binding agent contributes to the improvement of the converging property and the interfacial adhesive strength of the glass fiber. As the binder, a polymer or a thermoplastic resin suitable for the purpose can be used.
The polymer is not particularly limited, and examples thereof include acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary, and tertiary amines. It is done. Also suitable are polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate, and polyester or polyether diols. used.

  The acrylic acid homopolymer and copolymer preferably have a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The copolymerizable monomer constituting the copolymer of acrylic acid and other copolymerizable monomers is not particularly limited. For example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid, maleic acid, methacrylic acid, vinyl One or more selected from the group consisting of acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid are included (except for acrylic acid alone). As a copolymerizable monomer, it is preferable to have one or more ester monomers.

  The salt of acrylic acid homopolymers and copolymers with primary, secondary and tertiary amines is not particularly limited, and examples thereof include triethylamine salts, triethanolamine salts and glycine salts. The degree of neutralization is preferably 20 to 90%, and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

  The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. 3,000 or more is preferable from the viewpoint of improving the converging property of the glass fiber, and 50,000 or less is preferable from the viewpoint of improving the characteristics when a composite material is formed.

The thermoplastic resin used as the binder is not particularly limited. For example, polyolefin resin, polyamide resin, polyacetal resin, polycarbonate resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone. , Polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these. The same kind of thermoplastic resin and / or modified thermoplastic resin as that of the continuous thermoplastic resin fiber is preferable because the adhesive property between the glass fiber and the thermoplastic resin is improved after the composite material is formed.
Furthermore, in the case of further improving the adhesion of both fibers and attaching the sizing agent to the glass fiber as an aqueous dispersion, from the viewpoint of reducing the ratio of the emulsifier component or eliminating the need for an emulsifier, A modified thermoplastic resin is preferred. Here, the modified thermoplastic resin means that, in addition to the monomer component that can form the main chain of the thermoplastic resin, different monomer components are copolymerized for the purpose of changing the properties of the thermoplastic resin, and hydrophilicity, crystallinity, and the like. Means a modified thermodynamic property.

  The modified thermoplastic resin is not particularly limited, and examples thereof include a modified polyolefin resin, a modified polyamide resin, and a modified polyester resin.

  The modified polyolefin resin is a copolymer of an olefin monomer such as ethylene or propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid, and can be produced by a known method. A random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting an unsaturated carboxylic acid to an olefin may be used.

  Examples of the olefin monomer include ethylene, propylene, 1-butene and the like, and these can be used alone or in combination of two or more. Examples of the monomer copolymerizable with the olefin monomer include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. Saturated carboxylic acid etc. are mentioned, These can also be used individually or in combination of 2 or more types.

  As a copolymerization ratio of the olefin monomer and the monomer copolymerizable with the olefin monomer, the total mass of copolymerization is 100% by mass, the olefin monomer is 60 to 95% by mass, and the monomer copolymerizable with the olefin monomer. The amount is preferably 5 to 40% by mass, more preferably 70 to 85% by mass of the olefin monomer, and 15 to 30% by mass of the monomer copolymerizable with the olefin monomer. If the olefin monomer is 60% by mass or more, the affinity with the matrix is good, and if the olefin monomer is 95% by mass or less, the water dispersibility of the modified polyolefin resin is good. It is easy to uniformly apply to continuous reinforcing fibers.

In the modified polyolefin resin, a modified group such as a carboxyl group introduced by copolymerization may be neutralized with a basic compound. Examples of the basic compound include alkalis such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine.
Although it does not restrict | limit especially as a weight average molecular weight of modified polyolefin resin, 5,000-200,000 are preferable and 50,000-150,000 are more preferable. 5,000 or more is preferable from the viewpoint of improving the converging property of the glass fiber, and 200,000 or less is preferable from the viewpoint of emulsion stability in the case of water dispersibility.

  The modified polyamide resin is a modified polyamide compound in which a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component is introduced into a molecular chain, and can be produced by a known method. In the case of introducing a polyalkylene oxide chain into the molecular chain, for example, it is produced by copolymerizing a part or all of polyethylene glycol, polypropylene glycol or the like modified with diamine or dicarboxylic acid. When a tertiary amine component is introduced, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam and the like are copolymerized.

The modified polyester resin is a copolymer of polycarboxylic acid or its anhydride and polyol, and is a resin having a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of hydrophilic groups include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acid, sulfonate-containing aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and trifunctional or higher polycarboxylic acid.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.
Examples of the sulfonate-containing aromatic dicarboxylic acid include sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate.
As aliphatic dicarboxylic acid or alicyclic dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, anhydrous And maleic acid.
Examples of the tri- or higher functional polycarboxylic acid include trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and the like.

  Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Moreover, from the viewpoint of emulsion stability when the modified polyester resin is used as an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

  Examples of the polyol include diols and trifunctional or higher functional polyols. Diols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene Examples include glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof. Examples of the tri- or higher functional polyol include trimethylolpropane, glycerin, pentaerythritol and the like.

  As a copolymerization ratio of polycarboxylic acid or its anhydride and polyol, polycarboxylic acid or its anhydride is 40 to 60% by mass and polyol is 40 to 60% by mass, where the total mass of copolymerization components is 100% by mass. The polycarboxylic acid or its anhydride is preferably 45 to 55% by mass, and the polyol is more preferably 45 to 55% by mass.

  The weight average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. 3,000 or more are preferable from the viewpoint of improving the converging property of the glass fiber, and 100,000 or less are preferable from the viewpoint of emulsion stability in the case of water dispersibility.

  The polymer and thermoplastic resin used as a binder may be used alone or in combination of two or more. The total amount of the binder was 100% by mass, and was selected from homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these primary, secondary and tertiary amines. It is more preferable to use 50% by mass or more and 60% by mass or more of one or more kinds of polymers.

(composition)
The glass fiber sizing agent preferably contains 0.1 to 2% by mass of the silane coupling agent, 0.01 to 1% by mass of the lubricant, and 1 to 25% by mass of the binding agent. Is diluted with water to adjust the total mass to 100% by mass.

The blending amount of the silane coupling agent is preferably 0.1 to 2% by mass, more preferably 0.1% by mass from the viewpoints of improving the converging property of the glass fiber, improving the interfacial adhesive strength, and improving the mechanical strength of the composite material molded body. It is 1-1 mass%, More preferably, it is 0.2-0.5 mass%.
The blending amount of the lubricant is preferably 0.01% by mass or more from the viewpoint of providing sufficient lubricity, and from the viewpoint of improving the tensile breaking strength of the connecting yarn by the air splicer and improving the opening property in the blending process. The content is preferably 0.02% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less from the viewpoint of improving the interfacial adhesive strength and improving the mechanical strength of the composite material molded body.
The blending amount of the binder is preferably from 1 to 25% by mass, more preferably from 3 to 15% by mass, from the viewpoints of controlling the convergence of glass fibers and improving the interfacial adhesive strength and improving the mechanical strength of the composite material molded body. More preferably, it is 3-10 mass%.

(how to use)
The glass fiber sizing agent may be adjusted to any form, such as an aqueous solution, a colloidal dispersion form, or an emulsion form using an emulsifier, depending on the mode of use. From the viewpoint of improvement, an aqueous solution is preferable.

  The glass fiber used in the present embodiment is obtained by applying the sizing agent described above to a glass fiber using a known method such as a roller-type applicator in a known glass fiber production process, and drying the produced glass fiber. Can be obtained continuously. The sizing agent is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and still more preferably as a total mass of the silane coupling agent, the lubricant and the binding agent with respect to 100% by mass of the glass fiber. 0.2-1 mass% is provided. From the viewpoint of controlling the sizing property of the glass fiber and improving the interfacial adhesive strength, the amount of sizing agent applied is 0.1% by mass or more as the total mass of the silane coupling agent, the lubricant and the binding agent with respect to 100% by mass of the glass fiber. It is preferable that the amount is 3% by mass or less from the viewpoint of improving the tensile breaking strength of the binding yarn by the air splicer and improving the spreadability in the fiber mixing step.

<Carbon fiber sizing agent>
When carbon fiber is selected as the continuous reinforcing fiber, the sizing agent is preferably composed of a lubricant and a binding agent.

(lubricant)
The lubricant contributes to adjustment of the carbon fiber sizing agent, improvement in damage prevention, and improvement in fiber opening. As the lubricant, any ordinary liquid or solid lubricating material suitable for the purpose can be used, and is not particularly limited. For example, animal or plant or mineral wax such as carnauba wax or lanolin wax; fatty acid amide One or more selected from surfactants such as fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers can be used.

(Binder)
The binding agent contributes to the improvement of the binding property and the interfacial adhesion strength of the carbon fiber. As the binder, a polymer or a thermoplastic resin suitable for the purpose can be used.
Although it does not restrict | limit especially as a polymer, For example, Epoxy resins, such as a bisphenol A type epoxy resin; Phenol resin obtained by making various phenols and formalin react; Urea resin obtained by making urea and formalin react; Melamine and formalin And thermosetting resins such as melamine resins obtained by reacting with. In addition, for example, polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate, and polyester or polyether diols are also preferably used. Is done.

The thermoplastic resin used as the binder is not particularly limited. For example, polyolefin resin, polyamide resin, polyacetal resin, polycarbonate resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone. , Polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these. The same kind of thermoplastic resin and / or modified thermoplastic resin as that of the continuous thermoplastic resin fiber is preferable because the adhesion between the carbon fiber and the thermoplastic resin is improved after the composite material is formed.
Furthermore, in the case of further improving the adhesiveness of both fibers and attaching the sizing agent to the carbon fiber as an aqueous dispersion, from the viewpoint of reducing the ratio of the emulsifier component or eliminating the need for an emulsifier, Modified thermoplastic resins are preferred. Here, the modified thermoplastic resin means that, in addition to the monomer component that can form the main chain of the thermoplastic resin, different monomer components are copolymerized for the purpose of changing the properties of the thermoplastic resin, and hydrophilicity, crystallinity, and the like. Means a modified thermodynamic property.

  The modified thermoplastic resin is not particularly limited, and examples thereof include a modified polyolefin resin, a modified polyamide resin, and a modified polyester resin.

  The modified polyolefin resin is a copolymer of an olefin monomer such as ethylene or propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid, and can be produced by a known method. A random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting an unsaturated carboxylic acid to an olefin may be used.

  Examples of the olefin monomer include ethylene, propylene, 1-butene and the like, and these can be used alone or in combination of two or more. Examples of the monomer copolymerizable with the olefin monomer include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. Saturated carboxylic acid etc. are mentioned, These can also be used individually or in combination of 2 or more types.

  As a copolymerization ratio of the olefin monomer and the monomer copolymerizable with the olefin monomer, the total mass of copolymerization is 100% by mass, the olefin monomer is 60 to 95% by mass, and the monomer copolymerizable with the olefin monomer. The amount is preferably 5 to 40% by mass, more preferably 70 to 85% by mass of the olefin monomer, and 15 to 30% by mass of the monomer copolymerizable with the olefin monomer. If the olefin monomer content is 60% by mass or more, the affinity with the matrix is good, and if the olefin monomer content is 95% by mass or less, the water-dispersibility of the modified polyolefin resin is good. Thus, it is easy to uniformly apply to continuous reinforcing fibers.

In the modified polyolefin resin, a modified group such as a carboxyl group introduced by copolymerization may be neutralized with a basic compound. Examples of the basic compound include alkalis such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine.
Although it does not restrict | limit especially as a weight average molecular weight of modified polyolefin resin, 5,000-200,000 are preferable and 50,000-150,000 are more preferable. 5,000 or more is preferable from the viewpoint of improving the sizing property of the carbon fiber, and 200,000 or less is preferable from the viewpoint of emulsion stability in the case of water dispersibility.

  The modified polyamide resin is a modified polyamide compound in which a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component is introduced into a molecular chain, and can be produced by a known method. In the case of introducing a polyalkylene oxide chain into the molecular chain, for example, it is produced by copolymerizing a part or all of polyethylene glycol, polypropylene glycol or the like modified with diamine or dicarboxylic acid. When a tertiary amine component is introduced, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam and the like are copolymerized.

The modified polyester resin is a copolymer of polycarboxylic acid or its anhydride and polyol, and is a resin having a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of hydrophilic groups include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acid, sulfonate-containing aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and trifunctional or higher polycarboxylic acid.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.
Examples of the sulfonate-containing aromatic dicarboxylic acid include sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate.
As aliphatic dicarboxylic acid or alicyclic dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, anhydrous And maleic acid.
Examples of the tri- or higher functional polycarboxylic acid include trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride, and the like.

  Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Moreover, from the viewpoint of emulsion stability when the modified polyester resin is used as an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.

  Examples of the polyol include diols and trifunctional or higher functional polyols. Diols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene Examples include glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof. Examples of the tri- or higher functional polyol include trimethylolpropane, glycerin, pentaerythritol and the like.

  As a copolymerization ratio of polycarboxylic acid or its anhydride and polyol, polycarboxylic acid or its anhydride is 40 to 60% by mass and polyol is 40 to 60% by mass, where the total mass of copolymerization components is 100% by mass. The polycarboxylic acid or its anhydride is preferably 45 to 55% by mass, and the polyol is more preferably 45 to 55% by mass.

  The weight average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. 3,000 or more are preferable from the viewpoint of improving the converging property of the carbon fiber, and 100,000 or less are preferable from the viewpoint of emulsion stability in the case of water dispersibility.

  The polymer and thermoplastic resin used as a binder may be used alone or in combination of two or more.

(composition)
The carbon fiber sizing agent preferably contains 0.01 to 1% by mass of a lubricant and 1 to 25% by mass of a binder as solids, and these components are diluted with water to give a total mass of 100% by mass. Adjust to%.

The blending amount of the lubricant is preferably 0.01% by mass or more from the viewpoint of providing sufficient lubricity, and from the viewpoint of improving the tensile breaking strength of the connecting yarn by the air splicer and improving the opening property in the blending process. The content is preferably 0.02% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less from the viewpoint of improving the interfacial adhesive strength and improving the mechanical strength of the composite material molded body.
The blending amount of the binder is preferably 1 to 25% by mass, more preferably 3 to 15% by mass, from the viewpoints of control of carbon fiber convergence, improvement of interfacial adhesive strength, and improvement of mechanical strength of the composite material molded body. Preferably it is 3-10 mass%.

(how to use)
The carbon fiber sizing agent may be adjusted to any form, such as an aqueous solution, a colloidal dispersion form, or an emulsion form using an emulsifier, depending on the mode of use. From the viewpoint of improvement, an aqueous solution is preferable.

  The carbon fiber used in the present embodiment is obtained by applying the sizing agent described above to a carbon fiber using a known method such as a roller-type applicator in a known carbon fiber production process, and drying the produced carbon fiber. Can be obtained continuously. The sizing agent is preferably 0.1 to 8% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.2 to 3% as the total mass of the lubricant and the binding agent with respect to 100% by mass of the carbon fibers. Mass% is given. From the viewpoint of controlling the sizing properties of carbon fibers and improving the interfacial adhesive strength, the amount of sizing agent applied may be 0.1% by mass or more as the total mass of the lubricant and the binder with respect to 100% by mass of the carbon fibers. Preferably, the amount is 8% by mass or less from the viewpoint of improving the tensile breaking strength of the connecting yarn by the air splicer and improving the spreadability in the fiber mixing process.

<Other sizing agents for continuous reinforcing fibers>
When using fibers other than glass fibers and carbon fibers as continuous reinforcing fibers, depending on the characteristics of the continuous reinforcing fibers, the type and amount of sizing agent according to the sizing agent used for the glass fibers and carbon fibers may be appropriately selected. It is more preferable to set the type and amount of sizing agent according to the sizing agent used for the carbon fiber.

[Continuous thermoplastic resin fiber]
<Type>
As the continuous thermoplastic resin fibers used in the present embodiment, those used for the mixed yarn for composite material molded bodies can be used. For example, polyolefin resins such as polyethylene and polypropylene; polyamide 6, polyamide 66, polyamide Polyamide resin such as 46; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate; Polyacetal resin such as polyoxymethylene; Polycarbonate resin; Polyetherketone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluororesin such as tetrafluoroethylene-ethylene copolymer, and at least selected from modified thermoplastic resins obtained by modifying them It is preferably a continuous fiber obtained by melt spinning the species of the thermoplastic resin. Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether ketones, polyether ether ketones, polyether sulfones, polyphenylene sulfides, thermoplastic polyether imides, and thermoplastic fluorine resins are preferable. Polyolefin resins, modified polyolefin resins, polyamide resins and polyester resins are more preferred from the viewpoints of mechanical properties and versatility, and polyamide resins and polyester resins are more preferred from the viewpoint of thermal properties. In addition, a polyamide-based resin is more preferable from the viewpoint of durability against repeated load application, and polyamide 66 can be suitably used.

<Polyester resin>
The polyester-based resin means a high molecular compound having a —CO—O— (ester) bond in the main chain. For example, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and the like can be mentioned, but are not limited thereto. . The polyester resin may be a homopolyester or a copolyester. In the case of a copolyester, a homopolyester suitably copolymerized with a third component is preferred. Examples of the third component include diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, adipic acid, sebacic acid, Examples thereof include dicarboxylic acid components such as phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid. Polyester resins using raw materials derived from biomass resources can also be used, for example, aliphatic polyester resins such as polylactic acid, polybutylene succinate, polybutylene succinate adipate, and polybutylene adipate terephthalate. Aromatic polyester resins and the like can be mentioned.

<Polyamide resin>
The polyamide-based resin means a polymer compound having a —CO—NH— (amide) bond in the main chain. Examples thereof include polyamides obtained by ring-opening polymerization of lactam, polyamides obtained by self-condensation of ω-aminocarboxylic acid, polyamides obtained by condensing diamine and dicarboxylic acid, and copolymers thereof. It is not limited to. As the polyamide, one kind may be used alone, or two or more kinds may be used as a mixture.

The lactam is not particularly limited, and examples thereof include pyrrolidone, caprolactam, undecane lactam, and dodecalactam.
Examples of ω-aminocarboxylic acid include ω-amino fatty acid which is a ring-opening compound of lactam with water. Lactam or ω-aminocarboxylic acid may be condensed using two or more monomers in combination.

  Examples of the diamine (monomer) include linear aliphatic diamines such as hexamethylene diamine and pentamethylene diamine; branched aliphatic diamines such as 2-methylpentane diamine and 2-ethyl hexamethylene diamine; p -Aromatic diamines such as phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine.

Examples of the dicarboxylic acid (monomer) include aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Can be mentioned.
Each of the diamine and dicarboxylic acid as the monomer may be condensed alone or in combination of two or more.

  Examples of the polyamide include polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), Polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), and these As a constituent component, there may be mentioned a copolyamide.

  Examples of the copolymerized polyamide include a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and hexamethylene terephthalamide and 2-methylpentanediamine terephthalate. Examples include amide copolymers.

<Form>
The number of single yarns of the continuous thermoplastic resin fibers is preferably 30 to 20,000 from the viewpoints of openability and handling in the fiber mixing process.

[Ratio of product RD of continuous reinforcing fiber and continuous thermoplastic resin fiber]
In this embodiment, the product RD (continuous reinforcing fiber) of the single yarn diameter R (μm) and the density D (g / cm ³ ) of the continuous reinforcing fiber, the single yarn diameter R (μm) and the density D of the continuous thermoplastic resin fiber. The ratio of product RD (continuous thermoplastic resin fiber) of (g / cm ³ ), RD (continuous reinforcing fiber) / RD (continuous thermoplastic resin fiber) is preferably 0.3 to 5, more preferably 0.5. -4, more preferably 0.6-2.
In the fiber mixing step, it is preferable that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are opened and mixed with each other, and for that purpose, the acceleration generated in both fibers by the external force acting at the time of fiber mixing is substantially equal. Is presumed to be preferable. If the ratio of the product RD of the two fibers is within the above range, it is presumed that the acceleration generated in each fiber is substantially equal, and the continuous reinforcing fiber and the continuous thermoplastic resin fiber are easily mixed with each other.

[Ratio of single yarn diameter of continuous reinforcing fiber and continuous thermoplastic resin fiber]
In the present embodiment, the ratio of the single yarn diameter of the continuous reinforcing fiber and the single yarn diameter of the continuous thermoplastic resin fiber is preferably 0.3 to 2, more preferably 0.5 to 1.5, still more preferably 0.00. 5-1.
In the fiber mixing step, it is presumed that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are preferably opened and mixed with each other, and for this purpose, it is preferable that the external force acting at the time of fiber mixing is also substantially equal. If the ratio of the single yarn diameter is in the above range, it is presumed that the external force acting on each fiber is substantially equivalent, and the continuous reinforcing fiber and the continuous thermoplastic resin fiber are easily mixed with each other, which is preferable. Further, if the ratio of the single yarn diameter is within the above range, the single yarn diameter is substantially the same. Therefore, the geometric distribution state of both fibers in the composite yarn is likely to be uniform, and the thermoplastic resin fiber. Is preferably melted by pressurization and heating, so that it becomes easy to impregnate the reinforcing fiber with the thermoplastic resin, and the molding time can be shortened.

In this embodiment, the total fineness of the continuous reinforcing fiber and the continuous thermoplastic resin fiber is preferably 100 to 20,000 dtex, more preferably 200 to 10,000 dtex, still more preferably 500 to 5,000 dtex, and still more preferably 500. ~ 3,000 dtex.
The above range is preferable from the viewpoints of the spreadability and uniform mixing properties of both fibers in the fiber blending process, and the handling properties when obtaining a fabric.

Each content rate of a continuous reinforcement fiber and a continuous thermoplastic resin fiber becomes like this. Preferably it is 30-85 mass% / 70-15 mass%, More preferably, it is 40-70 mass% / 60-30 mass%.
When the content of the continuous reinforcing fiber in the composite yarn is 30% by mass or more, the composite material molded body has high mechanical strength and exhibits a sufficient reinforcing effect. If the content of the continuous reinforcing fiber is 85% by mass or less, the matrix is sufficient, and therefore it is possible to prevent voids from occurring in the composite material molded body.

[Production method of composite yarn]
In order to manufacture the composite yarn in the present embodiment, a known method can be used as a method of mixing continuous reinforcing fibers and continuous thermoplastic resin fibers. For example, after opening by external force such as electrostatic force, pressure due to fluid spraying, pressure applied to a roller, etc., then opening and closing continuous fibers and continuous thermoplastic resin fibers are opened and then combined and aligned. Method, fluid entanglement (interlace) method. The fluid entanglement method that can suppress damage to continuous reinforcing fibers, has excellent spreadability, and can be mixed uniformly is preferable. Two or more yarns are made almost parallel to the yarn axis, and the fiber is guided to the zone to make a non-bulky yarn under tension that does not cause loops or crimps, or only continuous reinforcing fibers are opened. Examples thereof include a method of fluid entanglement after the continuous or continuous thermoplastic fiber and continuous thermoplastic resin fiber are opened (fluid entanglement method after opening). In particular, it is preferable that the continuous thermoplastic resin fiber is subjected to false twisting in a process including thermal processing alone and then continuously in the same apparatus and mixed by a fluid entanglement method.

  Continuous thermoplastic resin fibers processed in a process that includes thermal processing alone are continuously spun with the same equipment, and continuously or unopened with continuous reinforced fibers that have been opened or not opened. The uniform supply to the fluid entanglement nozzle is preferable because the vortex turbulence caused by the fluid acts on only the continuous reinforcing fibers in a concentrated manner and damage of the continuous reinforcing fibers can be suppressed. Further, supplying the continuous reinforcing fiber alone or the above-described aligned fibers, preferably the aligned fibers substantially perpendicularly to the thread introduction hole surface of the fluid entanglement nozzle, It is preferable because damage to the continuous reinforcing fibers can be suppressed without excessive compression force. In particular, when glass fibers, carbon fibers, and ceramic fibers, which are brittle materials, are used as continuous reinforcing fibers, supplying the aligned fibers substantially perpendicularly to the thread introduction hole surface of the fluid entanglement nozzle has a damage suppressing effect. Is remarkable and preferable. In addition, when using aramid fibers that are susceptible to buckling failure due to compressive force as continuous reinforcing fibers, supplying the aligned fibers substantially vertically to the thread introduction hole surface of the fluid entanglement nozzle will cause buckling failure. It can be suppressed and is preferable. Here, “substantially perpendicular to the yarn introduction hole surface of the fluid entanglement nozzle” means a state where the yarn path can be confirmed to be vertical by visual observation.

In the present embodiment, the specific method for producing the composite yarn is not particularly limited, and for example, a fluid entanglement method using a fluid entanglement device illustrated as a schematic side view in FIG. 1 is exemplified.
In FIG. 1, 11 is a wound body of continuous reinforcing fibers 12a, 21 is a wound body of continuous thermoplastic resin fibers 22a, and 13 is a continuous reinforcing fiber 12a and continuous thermoplastic resin fibers 22a that are pulled out while being combined and aligned. A drive roll, 14 is a fluid entanglement nozzle using compressed air, 16 is a winder for winding the obtained composite yarn 15b, 17 is a heater for heat processing, 18 is a false twisting unit, A nip belt type false twist unit is preferable.

  According to this apparatus, the continuous thermoplastic resin fiber 22a is pulled out while rotating the wound body 21 of the continuous thermoplastic resin fiber, heated to Tg or more by the heat processing heater 17, and then a nip belt type false twisting unit. At 18, false twisting is performed. On the other hand, the continuous reinforcing fiber 12a is pulled out while rotating the wound body 11 of the continuous reinforcing fiber, and the continuous thermoplastic resin fiber subjected to false twisting is combined with the driving roll 13 and aligned, and then driven. Through the roll 13, the aligned yarn 15 a is supplied to the fluid entanglement nozzle 14. From the viewpoint of suppressing damage to the continuous reinforcing fibers, as shown in FIG. 2a, the aligned yarns 15a are supplied so as to be substantially perpendicular (90 degrees) to the yarn introduction hole surface of the fluid entanglement nozzle. preferable. The continuous reinforcing fiber 12a and the continuous thermoplastic resin fiber 22a are pulled out while rotating the respective wound bodies 11 and 21, so that the continuous reinforcing fiber 12a and the continuous thermoplastic resin fiber 22a are not twisted. Because.

The fluid entanglement nozzle 14 can use a well-known thing, for example, KC-AJI-L by Kyocera Corporation, ASM-4522 by Awa Spindle Co., Ltd., etc. are mentioned. For example, compressed air having a pressure of 1 to 3 kg / cm ² is supplied to the fluid entanglement nozzle 14 to create two or more vortex turbulence zones in the nozzle. The yarn 15a aligned in the zone is guided, and the continuous reinforcing fiber 12a and the continuous thermoplastic resin fiber 22a are opened and mixed by the action of the vortex turbulence, so that a non-bulk that does not cause loops or crimps. The composite yarn 15b is used. The obtained composite yarn 15b is wound up by the winder 16 in the direction of arrow A. The processing speed defined by the winding speed may be appropriately determined in consideration of damage suppression to the continuous reinforcing fiber 12a and productivity, and is preferably, for example, 10 to 500 m / min.

The fluid supplied to the fluid entanglement nozzle 14 is not particularly limited as long as it is a safe gas, and examples thereof include air, nitrogen, water vapor, helium, and argon. Air is preferable from the viewpoint of being inexpensive and easy to use. The pressure of the fluid is preferably 1 to ³ kg / cm ² from the viewpoint that the continuous reinforcing fibers 12a are not damaged and the continuous reinforcing fibers 12a and the continuous thermoplastic resin fibers 22a are continuously dispersed and mixed.

[Composite yarn]
In the composite yarn in this embodiment, the continuous reinforcing fiber and the continuous thermoplastic resin fiber are continuously and uniformly mixed, and the continuous thermoplastic resin fiber is continuously and substantially uniformly dispersed in the gap between the continuous reinforcing fibers. Is preferred. Here, continuously and substantially uniformly dispersed means that the number of continuous reinforcing fiber single yarns in contact with the single yarn of continuous thermoplastic resin fibers in any cross section of the composite yarn is A (book). In addition, the total number of single yarns of the continuous reinforcing fiber is B (the number), and the dispersion ratio of the continuous reinforcing fiber calculated by (A / B) × 100 (%) is preferably 30 to 75%, more preferably 40 to 75%.
The dispersion rate is 30 from the viewpoint that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are continuously and uniformly dispersed and mixed, and the composite material molded body obtained by molding in a short time from the composite yarn exhibits excellent mechanical properties. % Or more is preferable. The dispersion rate is preferably 75% or less from the viewpoint of suppressing damage to the continuous reinforcing fibers during blending and preventing the occurrence of fluff.
It is preferable that the continuous reinforcing fiber and the continuous thermoplastic resin fiber do not separate even if the composite yarn in this embodiment is heated. Here, heating refers to exposure to a temperature exceeding the glass transition temperature (Tg) by differential scanning calorimetry (DSC) of continuous thermoplastic resin fibers for 30 seconds or more in a state where no tension is applied. For example, wet heat heating in the dyeing process, dry heating in the drying process, heating with an infrared heater in a preheating process before molding, and the like can be given. The fact that the continuous reinforcing fiber and the continuous thermoplastic resin fiber do not separate means that the dispersion ratio is maintained at 30 to 75% even when heated for dyeing or compression molding. Further, it is also preferable that the dispersion rate does not substantially change before and after heating, in that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are not separated. The continuous reinforcing fiber and the continuous thermoplastic resin fiber are not separated even when heated, but the continuous reinforcing fiber and the continuous thermoplastic resin fiber are continuously and uniformly dispersed and mixed even after the heating, and the composite yarn is molded in a short time. The composite material molded body obtained in (1) is preferable because it exhibits excellent mechanical properties.

  In the composite yarn in this embodiment, it is preferable that the continuous reinforcing fiber is not damaged during the fiber mixing. Here, the fact that the continuous reinforcing fiber is not damaged means that the tensile breaking strength maintenance ratio obtained by dividing the tensile breaking strength of the composite yarn by the tensile breaking strength of the continuous reinforcing fiber is 60% or more. Since the continuous reinforcing fiber is not damaged and the occurrence of fluff is prevented, there is a composite material molded body obtained by knitting, braiding, etc. from the composite yarn to obtain a fabric and a short time molding. From the viewpoint of exhibiting excellent mechanical properties, the tensile fracture strength maintenance rate is preferably 60% or more.

<Fabrication>
The method for obtaining the fabric is not particularly limited, and a known method for producing an appropriate fabric selected according to the use and purpose can be used. For example, the woven fabric may use a weaving machine such as a shuttle loom, a rapier loom, an air jet loom, a water jet loom, etc., and may contain a composite yarn at least partially. Preferably, it may be obtained by driving a weft into a warp in which fibers containing a composite yarn are arranged. The knitted fabric is obtained by knitting a fiber including a composite yarn at least partially using a knitting machine such as a circular knitting machine, a flat knitting machine, a tricot knitting machine, and a raschel knitting machine. Non-woven fabric is a sheet-like fiber assembly called a web made of fibers containing at least a portion of composite yarn, and then the physical action such as a needle punch machine, stitch bond machine, columnar flow machine, etc. It is obtained by bonding fibers with an adhesive.

  EXAMPLES Hereinafter, although an Example and a comparative example of this invention are given and demonstrated concretely, this invention is not limited only to these Examples. In addition, the evaluation method and measurement method performed in the present Example are as follows.

(Boiling water shrinkage rate of continuous reinforcing fiber and continuous thermoplastic resin fiber taken out from the composite yarn)
About 600 mm each of continuous reinforcing fiber and continuous thermoplastic resin fiber are taken out from the composite yarn, and the boiling water shrinkage rate is measured under normal pressure according to JIS L1013 hot water dimensional change rate B method, and the average value of n = 10 Calculated. The difference in boiling water shrinkage was calculated by subtracting the boiling water shrinkage of the continuous reinforcing fiber taken out from the composite yarn from the boiling water shrinkage of the continuous thermoplastic resin fiber taken out from the composite yarn. When it was difficult to separate the continuous reinforcing fiber and the continuous thermoplastic resin fiber, a single yarn was taken out from each fiber in the composite yarn, and the boiling water shrinkage was calculated in the same procedure.

(Crimping rate of continuous reinforcing fiber and continuous thermoplastic resin fiber taken out from the composite yarn)
About 300 mm of continuous reinforcing fiber and continuous thermoplastic resin fiber were each taken out from the composite yarn, the crimp rate was measured according to JIS L1013 stretch A method, and calculated by the average value of n = 20. The difference in the crimp rate was calculated by subtracting the crimp rate of the continuous reinforcing fiber taken out from the composite yarn from the crimp rate of the continuous thermoplastic resin fiber taken out from the composite yarn. When it was difficult to separate the continuous reinforcing fiber and the continuous thermoplastic resin fiber, a single yarn was taken out from each fiber in the composite yarn, and the crimp rate was calculated in the same procedure.

(Single yarn diameter of continuous reinforcing fiber and continuous thermoplastic resin fiber)
The single yarn diameter R (μm) of the continuous reinforcing fiber and the continuous thermoplastic resin fiber is represented by the following formula (1) using the density D (g / cm ³ ), the fineness T (dtex), and the number of single yarns F (number) of the catalog value. ).
R = 20 × (T / π · F · D) ^0.5 (1)
In general, a continuous reinforcing fiber has a sizing agent attached thereto, and the density D as a catalog value is a sizing agent unless otherwise specified in the catalog, for example, that the density does not include a sizing agent. Means the density as a continuous reinforcing fiber in a state where is attached. That is, if the catalog value is used as it is as the density D and is described as the density of the continuous reinforcing fiber in a state not containing the sizing agent, the value is set as the density D and the continuous reinforcing fiber in the state containing the sizing agent. The density is described as density D.
Moreover, in a present Example, about the evaluation method and measurement method regarding a continuous reinforcing fiber, the value in the state to which the sizing agent was adhered may be sufficient.

(Dispersion rate of continuous reinforcing fiber)
Three points of 20 cm in length are sampled every 20 m in the longitudinal direction of the composite yarn, and the cross section (perpendicular to the yarn axis) is cut with a sharp blade for each sample collected. Take a photo. From the photograph, the number of continuous reinforcing fibers that would come into contact with a single yarn of continuous thermoplastic resin fiber or contact with a single yarn of continuous thermoplastic resin fiber was shifted by 10% of the single yarn diameter. This is A (book). The number of single yarns of continuous reinforcing fibers existing in the entire cross section of the composite yarn photographed in the photograph is measured, and this is designated as B (book). From the measured A and B, the average value (n = 3) of the dispersion rate% of the continuous reinforcing fibers was calculated by the formula (3).
Dispersion rate = (A / B) × 100% (3)

(Tensile rupture strength maintenance rate of composite yarn)
The tensile breaking strength of the composite yarn and continuous reinforcing fiber was measured according to JIS L1013 with Tensilon manufactured by Orientec Co., Ltd., with a grip interval of 20 cm, a pulling speed of 20 cm / min, and n = 10. The value was obtained, the ratio of both arithmetic mean values was calculated, and the tensile breaking strength maintenance ratio of the composite yarn was determined.

(Tensile properties of molded composite materials)
After attaching the fabric to a metal frame having a length of 30 cm and a width of 5 cm so that the fabric has a width of 2.5 cm, by hand, the composite material is molded to a thickness of 1 mm, and then using a vacuum dryer, 100 Vacuum-dried at 24 ° C. for 24 hours. After drying, the fabric was transferred together with the metal frame to a mold for flat plate molding that was preheated to the melting point of the thermoplastic resin fiber + 20 ° C. Transfer the mold to a desktop press equipped with a hot plate heated to the melting point of the thermoplastic resin fiber + 20 ° C, pressurize 0.5MPa for 1 minute, and then provide a cooler plate cooled with water to 25 ° C And pressurized at 0.5 MPa, and cooled until the mold temperature reached below the glass transition point of the thermoplastic resin fiber. After cooling, the pressure was released and the composite material molded body was taken out of the mold. The tensile properties (tensile breaking strength, tensile initial elastic modulus) were measured in accordance with JIS K7054 with the axial direction of the reinforcing fiber in the obtained composite material molded body as the tensile direction of the test piece.

(Coefficient of static friction between warp and weft μs)
Measurement is performed using the apparatus shown in FIG. A weft 100 having a length of about 690 m is wound around the cylinder 200 with a tension of about 0.2 cN / dtex at a twill angle of 15 °. Further, a warp yarn 300 having a length of 30.5 cm is hung on the cylinder. At this time, the warp 300 is on the cylinder 200 and is parallel to the winding direction of the cylinder. A weight 400 having a load of 0.1 cN / dtex (counter warp) is connected to one end of the warp 300 applied to the cylinder 200, and a strain gauge 500 is connected to the other end. Next, the cylinder 200 is rotated at a peripheral speed of 1 mm / min, and the tension is measured with the strain gauge 500. From the tension thus measured, μs is obtained from the following equation.
μs = (1 / π) × Ln (T2 / T1)
In the formula, T1 represents the weight of the weight 400 applied to the warp, T2 represents the tension measured with a strain gauge, Ln represents the natural logarithm, and π represents the circumference.

[Examples 1 to 4]
A glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) having a fineness of 660 dtex to which 1.0% by mass of the following sizing agent A was adhered was used as a continuous reinforcing fiber.
Composition of sizing agent A:
Silane coupling agent: 0.6% by mass of γ-aminopropyltriethoxysilane [trade name: KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
・ Lubricant: 0.1% by weight of wax [Brand name: Carnauba wax (manufactured by Hiroyuki Kato)]
・ Binder: 5% by mass of acrylic acid / maleic acid copolymer salt [trade name: Aqualic TL (manufactured by Nippon Shokubai Co., Ltd.)]
Table 1 shows the results of measuring the tensile breaking strength and the interfacial adhesive strength of the connecting yarns of this glass fiber.
Polyamide 66 fiber (trade name: Leona (registered trademark) 470 / 136BAP (manufactured by Asahi Kasei Fibers Co., Ltd.)), fineness 470 dtex, number of single yarn 136] was used.
The fibers were subjected to the following condition thermal processing and false twisting using IVF338 manufactured by Ishikawa Seisakusho.
False twist number 0T / m (pass through the spindle as it is) or 1050T / m
Heater temperature 240 ° C or 200 ° C
Yarn speed 100m / min or 40m / min
After the two fibers were combined and drawn, they were supplied substantially vertically to the fluid entanglement nozzle as shown in FIG. 2a and fluid entangled under the following conditions to obtain a composite yarn.
-Fluid entanglement nozzle KC-AJI-L (1.5 mm diameter, propulsion type) manufactured by Kyocera Corporation
・ Air pressure 2.5kg / cm ²
・ Processing speed: 100m / min or 40m / min
The evaluation results of the obtained composite yarn are shown in Table 1. Incidentally, the boiling water shrinkage rate and crimp rate of the glass fiber were both 0%.
This composite yarn is used as warp and weft, a plain weave (Example 1) and 2/2 twill weave (Example 1) having a warp density of 30 / 2.54 cm, a weft density of 30 / 2.54 cm, and a width of 1000 mm. 2) A 3/3 twill fabric (Example 3) and a 2 × 2 basket fabric (Example 4) were woven. In all cases, no fluff or fibrils were generated during weaving, and no lint or fluff was observed on the loom, and the weaving was good.
Table 1 also shows the results of molding composite material molded bodies using these woven fabrics and measuring the tensile properties. In the molding, the heating temperature was 280 ° C., and the mold temperature when taking out after cooling was 50 ° C.

Example 5
A warp density of 22 yarns / 2.54 cm and a warp yarn density of 14 yarns / 2.54 cm are used as warp yarns. A plain woven fabric having a width of 1000 mm was woven. In both cases, no fluff or fibrils were generated during weaving, and no lint or fluff was observed on the loom, and the weaving was good. Next, similarly, composite materials molded using these woven fabrics and the tensile properties measured are shown in Table 1. In the molding, the heating temperature was 300 ° C., and the mold temperature when taking out after cooling was 50 ° C.

Example 6
A fabric and a composite material molded body were obtained in the same manner as in Example 1 except that the number of single yarns of polyamide 66 fibers was 72. The evaluation results are shown in Table 1.

[Examples 7 to 8, Comparative Example 1]
Using a false twister, a composite yarn obtained under the conditions of a twist of 1050 T / m, a heater temperature of 240 ° C. (Example 7), 180 ° C. (Example 8), and unused (Comparative Example 1) is warp and weft 3/3 twill fabric with a warp density of 30 / 2.54 cm, a weft density of 30 / 2.54 cm, and a width of 1000 mm was woven. There was no generation of fluff or fibrils during weaving, and no lint or fluff was observed on the loom, and weaving was good.
Table 1 also shows the results of molding composite material molded bodies using these woven fabrics and measuring the tensile properties. In the molding, the heating temperature was 280 ° C., and the mold temperature when taking out after cooling was 50 ° C.

[Comparative Example 2]
A fabric and a composite material molded body were obtained in the same manner as in Example 1 except that the number of false twists was 1450 T / m and the heater temperature was 250 ° C. Yarn breakage and fluffing occurred in the fiber mixing process, and similarly, fluffing occurred during weaving, resulting in poor processability.
The evaluation results are shown in Table 1.

Example 9
A fabric and a composite material molded body were obtained in the same manner as in Example 2 except that the number of single fibers of the glass fiber was 100.
The evaluation results are shown in Table 1.

Example 10
A fabric and a composite material molded body were obtained in the same manner as in Example 2 except that polyethylene terephthalate fiber having a boiling water shrinkage of 6% (Type 556 manufactured by Hyousung, fineness 470 dtex, 96 single yarns) was used as the continuous thermoplastic resin fiber. It was.
The evaluation results are shown in Table 1.

Example 11
Glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) has a fineness and the number of single yarns of 11,500 dtex and 2,000, and 10 continuous polyamide 66 fibers (manufactured by Asahi Kasei Fibers Co., Ltd.) are aligned. In the same manner as in Example 17 except that the fabric and composite material molded body were obtained.
The evaluation results are shown in Table 1.

Example 12
The continuous reinforcing fiber is an aramid fiber (trade name: Kevlar (registered trademark) 29 (manufactured by Toray DuPont Co., Ltd.), fineness 1670 dtex, number of single yarns 1000), and polyamide 66 fiber (Asahi Kasei Fiber ( Fabrics and composite material molded bodies were obtained in the same manner as in Example 1 except that 4 products manufactured by the same company) were used.
The evaluation results are shown in Table 1.

Example 13
A fabric and a composite material molded body were obtained in the same manner as in Example 1 except that glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was twisted 50 times / m.
The evaluation results are shown in Table 1.

  From Table 1 above, not only mere yarns / alignment, but also mixed fibers by the fluid entanglement method, etc., the composite yarn has a high dispersion rate and is evenly mixed, and the tensile fracture strength maintenance rate is equivalent. As described above, it was confirmed that the processability in weaving was excellent and the generation of fluff was suppressed, and therefore the mechanical properties in the case of a composite material molded body were excellent.

  The fabric of the present invention is useful as a material for resin composite material moldings that require high-level mechanical properties, such as structural parts of various machines and automobiles, pressure vessels, and tubular structures.

DESCRIPTION OF SYMBOLS 11 Continuous reinforcing fiber wound body 12a Continuous reinforcing fiber 21 Continuous thermoplastic resin fiber wound body 22a Continuous thermoplastic resin fiber 13 Drive roll 14 Fluid entanglement nozzle 15a Alignment yarn 15b Composite yarn 16 Winding roll 17 Heat Heater for processing 18 False twist unit 100 Weft 200 Measuring cylinder 300 Warp 400 Weight 500 Strain gauge

Claims (17)

A fabric comprising a composite yarn,
The composite yarn is a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed,
The difference in boiling water shrinkage between the continuous reinforcing fiber and the continuous thermoplastic resin fiber taken out from the composite yarn is 0 to 10%, and the continuous reinforcing fiber and the continuous thermoplastic resin fiber taken out from the composite yarn A fabric in which the difference in crimping ratio is 0.5 to 20%.   The fabric according to claim 1, wherein the composite yarn is 50% by mass or more of the fibers constituting the fabric.   The fabric according to claim 1 or 2, wherein the fabric is a woven fabric composed of warps and wefts.   The fabric according to claim 3, wherein the composite yarn is 50 mass% or more of the fibers constituting the warp.   The fabric according to claim 3 or 4, wherein a coefficient of static friction between fibers of the warp and the weft is 0.2 to 3.0.   The fabric according to any one of claims 3 to 5, which is a plain fabric or an oblique fabric.   The fabric according to any one of claims 3 to 6, wherein the composite yarn is 50 mass% or more of fibers constituting the weft.   The fabric according to any one of claims 3 to 5, which is a bamboo woven fabric.   The fabric according to claim 8, wherein the composite yarn is 70 mass% or more of the fibers constituting the warp.   The fabric according to claim 8 or 9, wherein a ratio of warp density / weft density is 2 to 20.   The fabric according to any one of claims 1 to 10, wherein a difference in boiling water shrinkage between the continuous reinforcing fiber taken out from the composite yarn and the continuous thermoplastic resin fiber is 0 to 2.5%.   The boiling water shrinkage rate of the continuous thermoplastic resin fiber taken out from the composite yarn is 0 to 10%, and the crimp rate of the continuous thermoplastic resin fiber taken out from the composite yarn is 0.5 to 20%. The fabric according to any one of claims 1 to 11, which is%.   The continuous reinforcing fiber is at least one selected from the group consisting of glass fiber, carbon fiber, aramid fiber, ultrahigh strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber. The fabric according to any one of claims 1 to 12.   The continuous thermoplastic resin fiber is a group consisting of polyolefin resin, polyamide resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, and thermoplastic fluorine resin. The fabric according to any one of claims 1 to 13, which is a continuous fiber obtained by melt spinning at least one thermoplastic resin selected from the group consisting of:   The fabric according to any one of claims 1 to 14, wherein the composite yarn is a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed by a fluid entanglement method. Alone is communicated Zokunetsu thermoplastic resin fibers, after being processed by processes including thermal processing, successively with the same equipment, pulling continuous reinforcing fibers and continuous thermoplastic resin fibers that are processed by a process comprising hot working Align is continuous thermoplastic resin fibers and continuous reinforcing fibers are supplied to the fluid entangling nozzle is commingled with, method for producing a fabric according to claim 15. Continuous reinforcing fibers alone or continuous reinforcing fibers and continuous thermoplastic resin fibers that are processed by a process comprising thermal processing is aligned drawn, continuous reinforcing fibers are substantially vertically supplied to the introducing hole surface of the fluid entangling nozzle that the continuous thermoplastic resin fibers are commingled production method of a fabric of claim 15.