JP6175222B2 - Composite yarn fabric - Google Patents

Description

  The present invention relates to a composite yarn fabric suitable as a reinforcing material for a resin composite material molded body. More specifically, it is used as a reinforcing material for resin composite material molded products used for structural parts such as various machines and automobiles, pressure vessels and tubular structures, etc., and when molding the molded products. The present invention relates to a composite yarn fabric in which a molded product having no voids and excellent mechanical properties can be obtained even in a short time molding.

  As one of the intermediate materials for molding the resin composite material, there is a fabric using a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed. Non-woven fabrics, etc., which are knitted or woven with composite yarns alone or with other fibers, laminated randomly, and made by web, and then integrated by thermal fusion using embossing rolls or entanglement using needle punch And used as an intermediate material called a preform. A composite material molded product is obtained by subjecting the preform to compression heating or internal pressure heating to melt and mold the thermoplastic resin fibers. Alternatively, a composite material molded article may be obtained by impregnating a preform with a thermosetting resin and then heating under pressure. When obtaining a preform or a composite material molded product, it is important that the composite yarn is excellent in handleability so that the continuous reinforcing fiber is not easily damaged. In addition, when obtaining composite material molded products, in order to exhibit sufficient mechanical properties by short-time molding, the continuous reinforcing fiber is not damaged in the composite yarn, and the continuous reinforcing fiber and the continuous thermoplastic resin fiber It is very important that is uniformly dispersed and mixed.

  As a method for uniformly dispersing and mixing the continuous reinforcing fiber and the continuous thermoplastic resin fiber, the following Patent Document 1 discloses a method in which gas (air) is collided with the mixed yarn, and the following Patent Document 2 describes a thermoplastic property. A method for imparting crimpability to resin fiber bundles and a method for specifying the amount of sizing agent applied to each fiber bundle are disclosed in Patent Document 3 below. Further, Patent Documents 4 and 5 below disclose a method of opening a fiber bundle in a liquid in order to suppress the occurrence of single fiber breakage, and Patent Document 6 below discloses a method of sucking air flow into a bent fiber bundle. A method of mixing fibers by combining the fiber bundles after having been spread widely by the action of is disclosed, and the following patent document 7 discloses a method of mixing fibers by an electric fiber opening method and an interlace method.

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

  However, in any of the above conventional methods and conditions in which continuous reinforcing fibers and continuous thermoplastic resin fibers are dispersed and mixed, it is difficult to uniformly mix continuous reinforcing fibers and continuous thermoplastic resin fibers. When trying to obtain a fine fiber state or a mixed fiber state, single yarn breakage tends to occur, and there is a problem that the mechanical properties inherent to the reinforcing fiber cannot be obtained. When trying to prevent single yarn breakage, a sufficient mixed fiber state cannot be obtained, the handleability is inferior, and when a composite material molded product is formed in a short time, sufficient mechanical properties are generated. There is a problem that it is necessary to perform molding for a long time of 10 minutes or more in order to obtain sufficient mechanical properties without obtaining the properties.

  For example, in Patent Document 7, it is important that the matrix fiber and the reinforcing fiber are in a mixed state at a single fiber level, and the matrix fiber is uniformly dispersed in the gap between the reinforcing fibers. 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.

  In addition, the method of mixing fibers in a liquid has a problem that an extra step of removing the liquid is required. Further, in the method of mixing fibers by combining widely opened fiber bundles, the spread fiber bundles are combined. However, although a uniform mixed fiber can be obtained at the combined portion, a sufficient mixed state cannot be obtained as a whole.

  The present invention has been made in view of the above problems, and its purpose is to obtain a fabric in which continuous reinforcing fibers and continuous thermoplastic resin fibers are continuously mixed uniformly without damaging the continuous reinforcing fibers. An object of the present invention is to provide a composite yarn fabric using an optimum composite yarn for obtaining a resin composite material molded product which is excellent in handleability and exhibits sufficient mechanical properties even in a short time.

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. It was found that a suitable composite yarn can be obtained, and by using the composite yarn, a composite yarn fabric can be obtained which becomes a composite material molded product having excellent mechanical properties in a short time.
That is, the present invention is as follows.

[1] 50% by weight or more of the fibers constituting the fabric are a mixture of continuous glass fibers and continuous polyamide resin fibers , and the single fiber diameter R (μm) and density D (g / cm) of the continuous glass fibers. ³⁾ the product RD is Ri Do from the composite yarn is 20 ~100μm · g / cm ^3, and the continuous polyamide resin, 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, and these as constituent components A composite yarn fabric, which is a kind selected from the group consisting of copolymerized polyamides .
[2] The fabric is a woven fabric composed of warp and weft, at least 50% by weight of the fibers constituting the warp is the composite yarn, and the fiber-fiber static coefficient of friction between the warp and the weft is 0. The composite yarn fabric according to [1], which is 2 to 3.0.
[3] The composite yarn fabric according to [2], wherein the woven fabric is a plain woven fabric or an oblique woven fabric, and 50% by weight or more of the fibers constituting the weft are the composite yarn.
[4] The above-mentioned [2], wherein the woven fabric is an interwoven fabric, at least 70% by weight or more of the fibers constituting the warp is the composite yarn, and the ratio of warp density / weft density is 2 to 10. Composite yarn fabric.
[5] Using a joint air 110 type air splicer manufactured by Machinetex Co., Ltd., supply air pressure: 0.7 MPa, air injection time: scale 4 of adjusting knob PT150, thread length: scale 4 of regulator PT40 The composite yarn according to any one of [1] to [4], wherein a tensile breaking strength of the spliced yarn connecting the continuous glass fibers is 50 to 100% of a tensile breaking strength of the continuous glass fiber raw yarn. Striped fabric.
[6] The above-mentioned [1] to [5], wherein the interfacial adhesive strength by a microdroplet test measured by attaching the resin constituting the continuous polyamide resin fiber to a single yarn of the continuous glass fiber is 9 MPa or more. The composite yarn fabric as described in any one of Claims.
[7] The composite yarn fabric according to any one of [1] to [6], wherein the continuous glass fiber is substantially untwisted and substantially unentangled.
[8] The above [1] to [7], wherein the ratio (continuous glass fiber / continuous polyamide resin fiber) of the product RD of the continuous glass fibers and the product RD of the continuous polyamide resin fibers is 0.3 to 5. A composite yarn fabric according to any one of the above.
[9] The above [1] to [1], wherein a ratio of a single yarn diameter of the continuous glass fiber to a single yarn diameter of the continuous polyamide resin fiber (continuous glass fiber / continuous polyamide resin fiber) is 0.3 to 2. 8]. The composite yarn fabric according to any one of [8].
[10] The composite yarn fabric according to any one of [1] to [9], wherein the continuous glass fiber and the continuous polyamide resin fiber have a total fineness of 100 to 20,000 dtex.
[11] The composite yarn fabric according to any one of [1] to [10], wherein the continuous polyamide-based resin fiber is substantially untwisted and substantially untangled.
[12] A continuous yarn fiber and a continuous polyamide resin fiber are mixed by a fluid entanglement method, and the composite yarn fabric according to any one of [1] to [11] is manufactured using the obtained composite yarn. how to.
[13] The method according to the above [12], wherein continuous glass fibers and continuous polyamide resin fibers are aligned and supplied to the introduction hole surface of the fluid entanglement nozzle substantially vertically to mix the fibers.

  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 an optimal composite yarn fabric that becomes a resin composite material molded product that exhibits sufficient mechanical properties even in a short time.

It is a schematic side view which shows an example of the manufacturing apparatus for implementing this invention. It is the schematic which shows an example of the supply state of the alignment thread | yarn to the fluid entanglement nozzle in the apparatus shown in FIG. It is the schematic which shows another example of the supply state of the alignment thread | yarn to the fluid entanglement nozzle in the apparatus shown in FIG. It is the schematic of the measuring apparatus of the static friction coefficient (microsecond) between a warp and a weft.

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.

In the composite yarn fabric of this embodiment, 50% by weight or more of the fibers constituting the fabric are mixed with continuous reinforcing fibers and continuous thermoplastic resin fibers, and the single yarn diameter R ( It is important to be composed of a composite yarn having a product RD of 5 μm to 100 μm · g / cm ³ of μm) and density D (g / cm ³ ). The product RD is preferably 10 to 50, more preferably 15 to 45, and particularly preferably 20 to 45 μm · g / cm ³ .

If the product RD is 5 to 100 μm · g / cm ³ , when both fibers are mixed, the continuous reinforcing fibers are easily damaged without damaging the continuous reinforcing fibers, and both fibers are continuously and uniformly mixed. It is possible. When the product RD is less than 5 μm · g / cm ³ , continuous reinforcing fibers are easily damaged during fiber mixing, and fluff is likely to occur. By receiving, it becomes difficult for the composite material molded product to exhibit sufficient mechanical properties.

When the product RD exceeds 100 μm · g / cm ³ , the continuous reinforcing fibers are difficult to open, and the continuous reinforcing fibers and the continuous thermoplastic resin fibers are difficult to be mixed uniformly and continuously. Therefore, it is difficult to obtain a composite material molded product exhibiting sufficient mechanical characteristics by short-time molding.

  If the product RD is within the above range, the continuous reinforcing fiber can be easily opened without damaging the continuous reinforcing fiber, and the reason why the two fibers can be mixed uniformly and continuously is not necessarily clear. There is no reason, but 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 circumferential 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, so the acceleration generated in the single yarn of the reinforcing fiber during blending is inversely proportional to the product RD of the single yarn diameter and density. Then it is guessed. 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 product RD within the predetermined range, it may be appropriately selected from commercially available continuous reinforcing fibers. That is, when the glass fiber described later is used as the continuous reinforcing fiber, since the density is about 2.5 g / cm ³ , a fiber having a single yarn diameter of 2 to 40 μm may be selected. For example, a single yarn diameter of 9 μm, a fineness of 660 dtex and 400 single yarns, a single yarn diameter of 17 μm, a fineness of 11,500 dtex and a single yarn number of 2,000 can be selected. Moreover, when using carbon fiber, since the density is about 1.8 g / cm ^3, it is sufficient to select one having a single yarn diameter of 2.8 to 55 μm. For example, one having a single yarn diameter of 7 μm, a fineness of 2,000 dtex and a number of single yarns of 3,000 can be selected. When an aramid fiber is used, since the density is about 1.45 g / cm ³ , a fiber having a single yarn diameter of 3.4 to 68 μm may be selected. For example, one having a single yarn diameter of 12 μm, a fineness of 1,670 dtex, and 1,000 single yarns can be selected. In order to make the product RD within a particularly preferable range, for example, a glass fiber having a fineness of 660 dtex and 400 single yarns may be used.

[Composition of composite yarn fabric]
In the composite yarn fabric of this embodiment, it is important to use 50% by weight or more of the fibers constituting the composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are mixed. Preferably it is 70 weight% or more, More preferably, it is used 90 weight% or more. By using the above-mentioned composite yarn, the continuous reinforcing fiber and the continuous thermoplastic resin fiber can be continuously and uniformly mixed, and the resulting composite yarn has excellent handleability in a process such as knitting to form a fabric. The strip fabric can be formed into a composite material molded product exhibiting sufficient mechanical properties even in a short time. 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 the composite yarn remains continuous. And / or a nonwoven fabric or the like that is obtained by laminating cut composite yarns alone or together with other fibers, creating a web, and then integrating them by thermal fusion using an embossing roll or entanglement using a needle punch. . 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〕
It is preferable that the woven fabric is composed of warp and weft, and that the composite yarn is used for at least 50% by weight of the fibers constituting the warp. The composite yarn is preferably used in an amount of 70% by weight or more, more preferably 90% by weight or more, and most preferably 100% by weight. From the viewpoint of satisfying mechanical properties such as strength and rigidity at a high level, it is preferable that 50% by weight 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 in which fibers other than the composite yarn are twisted or aligned, (c) strands made of fibers other than the composite yarn of continuous reinforcing fibers and continuous thermoplastic resin fibers, and the like. The strand is a yarn in which a bundle of continuous fibers is untwisted or lightly twisted 100 times / m or less, and it is preferable to use a strand from the viewpoint of increasing the linearity of the fiber, and more preferably the number of twists. It is desirable to use a strand of 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 weight or more, more preferably 70% by weight or more.
The warp may be composed of at least one selected from (a) and (b), or at least one selected from (b) and (b) and at least one selected from (c). In any case, the composite yarn is used in an amount of 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and most preferably 100% by weight 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 weight, and a known fiber can be used according to the use 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-fiber static friction coefficient (hereinafter abbreviated as μs) of warp and weft yarns in a range of 0.2 to 3.0, more preferably 0.25 to 2.5, and particularly preferably 0. .3 to 2.0. If μs is less than 0.2, the linearity of continuous reinforcing fibers in the composite yarn is caused by fluctuations in the tension applied to the warp during weaving, or by slipping of the warp and weft during storage as a fabric after winding or winding. Is impaired, and the mechanical properties of the molded composite material are deteriorated. On the other hand, if μs exceeds 3, it becomes difficult to follow the shape of the molding die due to the shear deformation of the fabric during molding, and it becomes difficult to obtain the shape of the desired composite material molded product. Since μs varies depending on the combination of the fibers constituting the warp, the blending method / condition, the single yarn fineness, the total fineness, etc., these conditions are adjusted so that a desired μs is obtained. In particular, it is important to adjust the type of continuous reinforcing fiber, the type of sizing agent corresponding thereto, and the adhesion rate, which will be described later.

  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 with high equivalence in the warp and weft direction. And plain plain fabrics are particularly preferred. 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.

  In plain woven fabrics and oblique woven fabrics, 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and most preferably 100% by weight of the respective fibers constituting the warp and weft are combined with the composite yarn. It is preferable to improve the mechanical properties of the composite material molded product 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 set to 0.5 to 2.0, preferably 0.7 to 1.5, and the warp and weft are constituted. It is preferable to make the mixing ratio of the composite yarns in the fibers 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 braided fabric has a high warp density, it is possible to obtain a composite material molded product in which the warp direction is reinforced, which is suitable for unidirectional reinforcement. In order to efficiently perform unidirectional reinforcement, it is preferable that at least 70% by weight or more of the fibers constituting the warp is the composite yarn, and the warp density / weft density ratio is 2 to 10. It is desirable that 90% by weight or more, most preferably 100% by weight of the fibers constituting the warp is a composite yarn. The ratio of warp density / weft density is preferably from 3 to 10, particularly preferably from 4 to 8. A ratio of warp density / weft density of 2 to 10 is preferable because 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 thermoplastic resin decomposition product into the composite material molded product.

[Continuous reinforcing fiber]
<Type>
As the continuous reinforcing fiber in the present embodiment, those normally used for fiber reinforced composite materials can be used. For example, glass fiber, carbon fiber, aramid fiber, ultra-high strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester It is preferably at least one selected from fibers, polyketone fibers, metal fibers, and ceramic fibers. Glass fibers, carbon fibers, and aramid fibers are particularly preferable from the viewpoint of mechanical properties, thermal properties, and versatility, and glass fibers are particularly preferable from the viewpoint of price.

<Form>
The continuous reinforcing fiber used in the present embodiment is substantially untwisted and substantially unentangled, which improves the tensile breaking strength of the connecting yarn by an air splicer described later and the spreadability in the blending process. It is preferable from the viewpoint of improvement. Substantially no twist means a state in which there is no twist other than unintentional twist accompanying unraveling and the like, and the number of twists is 10 times / m or less. Substantially non-entangled means a state in which no intentional entanglement by normal entanglement means such as fluid entanglement is present, and the number of entanglement is 5 times / m or less.
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.

<Tensile breaking strength of spliced yarn>
In this embodiment, it is preferable that the tensile breaking strength of the connecting yarn in which continuous reinforcing fibers are connected by an air splicer is 50 to 100% of the tensile breaking strength of the continuous reinforcing fiber yarn. More preferably, it is 60 to 100%, and particularly preferably 65 to 100%. An air splicer is a device that connects yarn ends by opening the yarn ends by air injection and tangling single yarns at the yarn ends. Therefore, if the tensile breaking strength of the splicing yarn by the air splicer is in the above range, it is preferable that the continuous reinforcing fiber can be opened and mixed with air and can be judged to be less damaged.

The connecting yarn is produced using a commercially available air splicer. For example, a joint air type 110 manufactured by Machinetex Co., Ltd. can be used. The chamber and chamber cover of the air splicer are appropriately selected and attached according to the fineness of the continuous reinforcing fiber, and the reinforcing fiber is connected by a predetermined procedure of the air splicer under the following conditions.
Supply air pressure 0.7 MPa
Scale 4 of air injection time adjustment knob PT150
Thread length Length Scale 4 of regulator PT40
The tensile breaking strength of the obtained connecting yarn and continuous reinforcing fiber yarn is measured by the method described in JIS L1013.

  In order to set the tensile breaking strength of the continuous reinforcing fiber joining yarn to the above range, the product RD of the single yarn diameter R and the density D is set to an appropriate range, and the sizing agent attached to the bundle surface of the continuous reinforcing fiber is used. Select the type and amount of adhesion as appropriate. The sizing agent prevents the continuous reinforcing fibers from being broken into single yarns, prevents the continuous reinforcing fibers from being damaged during the processing process, and after forming a composite material molded product, It functions to improve adhesion. In this embodiment, the bundling effect that prevents the single yarn from breaking is necessary until the continuous fiber is not damaged until the fiber blending process, but if the bundling effect is excessive, the fiber opening process is performed in the fiber blending process. Since it becomes difficult to mix, it is preferable to appropriately select the type of sizing agent and the amount of adhesion.

<Interfacial adhesive strength>
In addition, since the sizing agent functions to improve the adhesion between the continuous reinforcing fiber and the matrix, the interfacial adhesion by the microdroplet test measured by attaching the resin constituting the continuous thermoplastic resin fiber to the single yarn of the continuous reinforcing fiber. It is preferable to appropriately select the type of sizing agent and the amount of adhesion so that the strength is preferably 9 MPa or more, more preferably 13 MPa or more, and particularly preferably 15 MPa or more. The higher the interfacial adhesive strength, the better. However, if the interfacial adhesive strength becomes too high, problems such as the continuous reinforcing fiber single yarn being cut during the measurement occur. Therefore, the upper limit is preferably 30 MPa.

The interfacial adhesive strength is measured by a microdroplet test using a composite material interfacial property evaluation apparatus HM410 (manufactured by Toei Sangyo Co., Ltd.). A single yarn is taken out from the continuous reinforcing fiber and set in a composite material interface property evaluation apparatus. A drop in which a thermoplastic resin that is a raw material for continuous thermoplastic resin fibers is melted on the apparatus is formed on the continuous reinforcing fiber single yarn, and is sufficiently cooled at room temperature to obtain a sample for measurement. Set the measurement sample in the device again, pinch the drop with the device blade, run the continuous reinforcing fiber single yarn on the device at a speed of 0.06 mm / min, and measure the maximum pulling load f (N) when pulling out the drop Then, the interface adhesive strength τ is calculated by the following formula (2).
Interfacial adhesive strength τ = f / π · R · l (2)
(F: Maximum pulling load (N) R: Continuous reinforcing fiber single yarn diameter (m) l: Particle diameter in the pulling direction of drop (m))

<Glass fiber sizing agent>
The type of sizing agent may be appropriately selected from known sizing agents according to the types of continuous reinforcing fiber and continuous thermoplastic resin fiber.
For example, 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 Mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. It is preferable that it is 1 or more types selected from said enumeration component, Especially, aminosilanes are especially preferable.

(lubricant)
The lubricant contributes to the adjustment of the glass fiber sizing agent and the improvement of the opening property. As the lubricant, any ordinary liquid or solid lubricating material suitable for the purpose can be used. Although not limited to the following, for example, animal and plant or mineral waxes such as carnauba wax and lanolin wax, and surfactants such as fatty acid amides, fatty acid esters or fatty acid ethers, or aromatic esters or 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. Examples of the polymer include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines. Can be mentioned. 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 preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.

  The monomer that forms a copolymer with the acrylic acid constituting a copolymer of acrylic acid and other copolymerizable monomer is not limited to the following, but, for example, among monomers having a hydroxyl group and / or a carboxyl group, acrylic acid , Maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, including at least one type (except for acrylic acid only) ). Of the above monomers, it is preferable to have one or more ester monomers.

  The salt of the acrylic acid homopolymer and / or copolymer with the primary, secondary and tertiary amines is not limited to the following, and examples thereof include triethylamine, triethanolamine and glycine. The neutralization degree is preferably 20 to 90% 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, and is preferably 40 to 60%. It is particularly preferable to do this.

  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 are preferable from the viewpoint of improving the converging property of the glass fiber, and 50,000 or less are preferable from the viewpoint of improving characteristics when a composite material molded product is obtained.

  Examples of the thermoplastic resin used as a binder include, but are not limited to, polyolefin resins, polyamide resins, polycarbonate resins, polyester resins, polyacetal resins, polyether ketones, polyether ether ketones, poly Examples include ether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these, and the same types of thermoplastic resins and / or modified thermoplastics as continuous thermoplastic resin fibers. Resin is preferable because the adhesion between the glass fiber and the matrix is improved. Furthermore, in the case of further improving the adhesion between the two 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 making the emulsifier unnecessary, as the thermoplastic resin, 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.

  Examples of the modified thermoplastic resin include, but are not limited to, modified polyolefin resins, modified polyamide resins, and modified polyester resins.

  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 on 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 above olefin monomer and a monomer copolymerizable with the olefin monomer, the total weight of the copolymerization is 100% by weight, and the olefin monomer can be copolymerized with 60 to 95% by weight. It is preferably 5 to 40% by weight of the monomer, more preferably 70 to 85% by weight of the olefin monomer, and more preferably 15 to 30% by weight of the monomer copolymerizable with the olefin monomer. When the weight percent of the olefin monomer is less than 60 weight percent, the affinity with the matrix may be reduced. When the weight percent of the olefin monomer exceeds 95 weight percent, the water content of the modified polyolefin resin may be reduced. Dispersibility is lowered, and uniform application to continuous reinforcing fibers may be difficult, which is not preferable.

  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 metal salts such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. 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 resin of polycarboxylic acid or anhydride thereof and polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.

  Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.

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.
Aliphatic or alicyclic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, and 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 the copolymerization ratio of the above polycarboxylic acid or its anhydride and polyol, the total weight of copolymerization is 100% by weight, and the polycarboxylic acid or its anhydride is 40 to 60% by weight, and the polyol is 40 to 60% by weight. Preferably, the polycarboxylic acid or its anhydride is 45 to 55% by weight, and the polyol is 45 to 55% by weight.

  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 the binder may be used alone or in combination of two or more. However, the total amount of the binder is 100% by weight, and the acrylic acid homopolymer, acrylic acid and other co-polymers are used. It is preferable to use 50% by weight or more, particularly 60% by weight or more of at least one polymer selected from a copolymer with a polymerizable monomer and salts of these primary, secondary and tertiary amines.

(composition)
The glass fiber sizing agent preferably contains 0.1 to 2% by weight of a silane coupling agent, 0.01 to 1% by weight of a lubricant, and 1 to 25% by weight of a binder as solids. These ingredients are diluted with water and the total weight is adjusted to 100% by weight.

The blending amount of the silane coupling agent is preferably 0.1 to 2% by weight, and more preferably 0. It is 1-1 weight%, Most preferably, it is 0.2-0.5 weight%.
The blending amount of the lubricant is 0.01% by weight or more, particularly 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 02% by weight or more, and is preferably 1% by weight or less, particularly preferably 0.5% by weight or less, from the viewpoint of improving the interfacial adhesive strength and improving the mechanical strength of the composite material molded product.
The blending amount of the binder is preferably 1 to 25% by weight, more preferably 3 to 15% by weight, from the viewpoint of controlling the glass fiber bundling and improving the interfacial adhesive strength and improving the mechanical strength of the composite material molded product. It is particularly preferably 3 to 10% by weight.

(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 added in an amount of 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, particularly preferably 0.2 to 1% by weight, based on 100% by weight of the glass fiber. %. From the viewpoint of controlling the sizing property of the glass fiber and improving the interfacial adhesive strength, it is preferable that the amount of sizing agent applied is 0.1% by weight or more as a solid content with respect to 100% by weight of the glass fiber. On the other hand, it is preferably 3% by weight or less from the viewpoint of improving the tensile strength at break of the connecting yarn by the air splicer and improving the spreadability in the fiber mixing process.

<Carbon fiber sizing agent>
On the other hand, for example, 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. Although not limited to the following, for example, animal and plant or mineral waxes such as carnauba wax and lanolin wax, and surfactants such as fatty acid amides, fatty acid esters or fatty acid ethers, or aromatic esters or 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. Examples of the polymer include, but are not limited to, epoxy resins such as bisphenol A type epoxy resins, phenol resins obtained by reacting various phenols with formalin, urea resins obtained by reacting urea and formalin, and melamine Examples thereof include thermosetting resins such as melamine resins obtained by reacting formalin. For example, polyurethane resins obtained from isocyanates such as m-xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate and polyester or polyether diols are also preferably used. The

  Examples of the thermoplastic resin used as a binder include, but are not limited to, polyolefin resins, polyamide resins, polycarbonate resins, polyester resins, polyacetal resins, polyether ketones, polyether ether ketones, poly Examples include ether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these, and the same types of thermoplastic resins and / or modified thermoplastics as continuous thermoplastic resin fibers. Resins are preferred because they improve the adhesion between the carbon fibers and the matrix. Furthermore, in the case of further improving the adhesion between the two and attaching the sizing agent to the carbon fiber as an aqueous dispersion, the thermoplastic resin is modified from the viewpoint of reducing the ratio of the emulsifier component or eliminating the need for an emulsifier. 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.

  Examples of the modified thermoplastic resin include, but are not limited to, modified polyolefin resins, modified polyamide resins, and modified polyester resins.

  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 on 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 above olefin monomer and a monomer copolymerizable with the olefin monomer, the total weight of the copolymerization is 100% by weight, and the olefin monomer can be copolymerized with 60 to 95% by weight. It is preferably 5 to 40% by weight of the monomer, more preferably 70 to 85% by weight of the olefin monomer, and more preferably 15 to 30% by weight of the monomer copolymerizable with the olefin monomer. When the weight percent of the olefin monomer is less than 60 weight percent, the affinity with the matrix may be reduced. When the weight percent of the olefin monomer exceeds 95 weight percent, the water content of the modified polyolefin resin may be reduced. Dispersibility is lowered, and uniform application to continuous reinforcing fibers may be difficult, which is not preferable.

  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 metal salts such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. 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 resin of polycarboxylic acid or anhydride thereof and polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. Examples of the hydrophilic group include polyalkylene oxide groups, sulfonates, carboxyl groups, and neutralized salts thereof.
Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.

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.
Aliphatic or alicyclic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, succinic anhydride, and 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 the copolymerization ratio of the above polycarboxylic acid or its anhydride and polyol, the total weight of copolymerization is 100% by weight, and the polycarboxylic acid or its anhydride is 40 to 60% by weight, and the polyol is 40 to 60% by weight. Preferably, the polycarboxylic acid or its anhydride is 45 to 55% by weight, and the polyol is 45 to 55% by weight.

  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 weight of a lubricant and 1 to 25% by weight of a binder as solids, and these components are diluted with water to give a total weight of 100%. Adjust to%.

The blending amount of the lubricant is 0.01% by weight or more, particularly from the viewpoint of providing sufficient lubricity, and from the viewpoint of improving the tensile breaking strength of the binding yarn by the air splicer and improving the opening property in the blending process. The content is preferably 02% by weight or more, and is preferably 1% by weight or less, particularly preferably 0.5% by weight or less, from the viewpoint of improving the interfacial adhesive strength and improving the mechanical strength of the composite material molded product.
The blending amount of the binder is preferably 1 to 25% by weight, more preferably 3 to 15% by weight, from the viewpoints of control of carbon fiber bundling, improvement of interfacial adhesive strength, and improvement of mechanical strength of the composite material molded product. Particularly preferably, it is 3 to 10% by weight.

(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 added in an amount of 0.1 to 8% by weight, more preferably 0.2 to 5% by weight, particularly preferably 0.2 to 3% by weight, based on 100% by weight of carbon fiber. It is to be. From the viewpoint of controlling the sizing property of carbon fibers and improving the interfacial adhesive strength, it is preferable that the amount of sizing agent applied is 0.1% by weight or more as a solid content with respect to 100% by weight of carbon fibers. On the other hand, it is preferably 8% by weight 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>
Moreover, when using fibers other than glass fiber and carbon fiber as the continuous reinforcing fiber, it is 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 fiber used in the present embodiment, those used for the mixed yarn for composite material molded products 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, polyether ketone, polyether ether ketone, polyether sulfone, At least selected from thermoplastic fluororesins such as polyphenylene sulfide, thermoplastic polyetherimide, tetrafluoroethylene-ethylene copolymer, and modified thermoplastic resins obtained by modifying these It is preferably a continuous fiber obtained by melt spinning the species of the thermoplastic resin. Among these, polyolefin-based resins, modified polyolefin-based resins, polyamide-based resins, and polyester-based resins are more preferable from the viewpoints of mechanical properties and general versatility, and polyamide-based resins and polyester-based resins are more preferable from the viewpoint of thermal properties. Particularly preferred. Further, from the viewpoint of durability against repeated load application, a polyamide-based resin is particularly preferable, and polyamide 66 is most preferable.

<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 limited to the following, and examples thereof include pyrrolidone, caprolactam, undecane lactam, and dodecalactam.
On the other hand, examples of the ω-aminocarboxylic acid include ω-amino fatty acid which is a ring-opening compound of the above lactam with water. The lactam or the ω-aminocarboxylic acid may be condensed using two or more monomers.

  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; Aromatic diamines such as p-phenylenediamine and m-phenylenediamine; cycloaliphatic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine are listed.

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. Is 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 obtained as described above include polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), and polyamide 46 (polytetramethylene azide). Pamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide) ), And copolymerized polyamides containing these as constituents.

  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. Examples include terephthalamide copolymers.

<Form>
The continuous thermoplastic fiber used in the present embodiment is substantially untwisted and substantially unentangled from the viewpoint of improving the spreadability in the fiber blending process. Substantially no twist means a state in which there is no twist other than unintentional twist accompanying unraveling and the like, and the number of twists is 10 times / m or less. Substantially non-entangled means a state where the intentional entanglement by normal entanglement means such as fluid entanglement is the minimum number of times to maintain the handleability, and the number of entanglement is 5 times / m or less.
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.

[Combination of continuous reinforcing fiber and continuous thermoplastic resin fiber]
In this embodiment, the product RD (reinforced 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. g / cm ³ ) product RD (thermoplastic resin fiber) ratio, RD (reinforced fiber) / RD (thermoplastic resin fiber) is preferably 0.3-5, more preferably 0.5-4. Especially preferably, it is 0.6-2. In the fiber blending process, it is preferable that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are opened and mixed with each other. For this purpose, the acceleration generated in each fiber is approximately equal due to the external force acting during the fiber blending. Is presumed to be preferable. If the ratio of the product RD of both fibers is within the above range, it is presumed that the acceleration generated in each fiber is substantially the same, and the continuous reinforcing fiber and the continuous thermoplastic resin fiber are easily mixed with each other, which is preferable.

  In this 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, particularly preferably. 0.5 to 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 during the fiber mixing is also substantially equal. If the ratio of the single yarn diameter is within the above range, it is presumed that the external forces acting on each fiber are substantially equal, 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, particularly preferably 500 to 5,000 dtex, most preferably. Is 500 to 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.

  The content of each of the continuous reinforcing fiber and the continuous thermoplastic resin fiber in the composite yarn is preferably 30 to 85% by weight / 70 to 15% by weight, more preferably 40 to 70% by weight / 60 to 30% by weight. It is to do. If the content of the continuous reinforcing fiber in the composite yarn is less than 30% by weight, the mechanical strength of the composite material molded product is relatively low, and it is difficult to exert a sufficient reinforcing effect, and the content of the continuous reinforcing fiber is 85. When the weight percentage is exceeded, voids due to insufficient matrix may easily occur in the composite material molded product.

[Production method of composite yarn]
<Mixed fiber>
In order to produce the composite yarn of this 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. Two or more eddy current turbulent zones by fluids such as air, nitrogen gas and water vapor are formed almost in parallel with the yarn axis, and fibers are guided to the zone so as not to cause loops and crimps. So-called fluid entanglement (interlace) method with bulky yarns, fluid entanglement method after fluid entanglement in which only continuous reinforcing fibers are opened, or after both continuous reinforcing fibers and continuous thermoplastic resin fibers are opened, etc. Is mentioned. Fluid entanglement methods such as a fluid entanglement method and a fluid entanglement method that are excellent in spreadability, can be mixed uniformly, and can be uniformly mixed are preferable.

  Supplying to the fluid entanglement nozzle with continuous thermoplastic resin fibers that have been opened or not opened, or after opening or without opening the continuous reinforcing fibers, is possible only for continuous reinforcing fibers. It is preferable because vortex turbulence caused by fluid acts intensively and damage of continuous reinforcing fibers can be suppressed. Furthermore, supplying the aligned fibers substantially perpendicularly to the thread introduction hole surface of the fluid entanglement nozzle allows continuous reinforcing fibers to be applied without excessive elongation and compression force due to bending acting on the continuous reinforcing fibers. This is preferable because it can suppress damage. 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.

Although the specific manufacturing method of the composite yarn of this embodiment is not restrict | limited below, For example, the fluid entanglement method using the fluid entanglement apparatus illustrated in FIG. 1 is illustrated.
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 for the above, 14 is a fluid entanglement nozzle using compressed air, and 16 is a winder for winding the obtained composite yarn 15b.

  According to this apparatus, the continuous reinforcing fiber 12a is pulled out while rotating the continuous reinforcing fiber wound body 11, and similarly, the continuous thermoplastic resin fiber 22a is rotated while rotating the continuous thermoplastic resin fiber wound body 21. After pulling out and aligning and aligning just before the drive roll 13, the aligned yarn 15 a is supplied to the fluid entanglement nozzle 14 through the drive roll 13. As shown in FIG. 2B, the aligned yarn 15a is supplied obliquely (45 degrees) to the yarn introduction hole surface of the fluid entanglement nozzle, as shown in FIG. It is preferable to supply the fluid entanglement nozzle so as to be substantially perpendicular (90 degrees) to the thread introduction hole surface. 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 illustrated. For example, compressed air having a pressure of 1 to 3 kg / cm ² is supplied to the fluid entanglement nozzle 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 examples thereof include 10 to 500 m / min.

The fluid supplied to the fluid entanglement nozzle 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 and uniformly mixed.

  The composite yarn obtained by the above blending is preferably in a state in which continuous reinforcing fibers and continuous thermoplastic resin fibers are uniformly mixed, and the continuous thermoplastic resin fibers are substantially uniformly dispersed in the gaps between the continuous reinforcing fibers. Here, 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 an arbitrary cross section of the composite yarn is A (main), and The total number of single yarns of continuous reinforcing fibers is B (number), and the dispersion rate of continuous reinforcing fibers calculated by (A / B) × 100 (%) is 30 to 75%, preferably 40 to 75%. . The dispersion rate is 30% from the viewpoint that the continuous reinforcing fiber and the continuous thermoplastic resin fiber are uniformly mixed, and the composite material molded product obtained by molding in a short time from the fabric using the composite yarn exhibits excellent mechanical properties. The above 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.

  Furthermore, it is preferable that the continuous yarn is not damaged when the composite yarn is mixed. 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 yarn is 60% or more. Since the continuous reinforcing fibers are not damaged and the occurrence of fluff is prevented, the handling properties for obtaining a fabric from a composite yarn by knitting and the composite material molded product obtained by short-time molding have excellent mechanical properties From the viewpoint of exhibiting the above, 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, a woven fabric can be obtained by using a weaving machine such as a shuttle loom, a rapier loom, an air jet loom, a water jet loom, or the like, by driving wefts into warps in which fibers containing composite yarns are arranged at least partially. . 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.

〔Evaluation method〕
Hereinafter, evaluation methods performed in Examples and Comparative Examples will be described.
(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 expressed 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)

(Tensile rupture strength of continuous reinforcing fiber connecting yarns)
Select and install the air splicer chamber and chamber cover according to the fineness of the continuous reinforcing fiber using the joint air type 110 manufactured by Machinetex Co., Ltd. Obtained.
Supply air pressure 0.7 MPa
Scale 4 of air injection time adjustment knob PT150
Thread length Length Scale 4 of regulator PT40
The tensile strength at break of the obtained splicing yarn and continuous reinforcing fiber yarn was measured with a Tensilon manufactured by Orientec Co., Ltd. according to JIS L1013 at a gripping interval of 20 cm and a pulling speed of 20 cm / min, and the ratio of the two measured values was calculated. did.

(Interfacial adhesive strength)
The interfacial adhesive strength was measured by a microdroplet test using a composite material interfacial property evaluation apparatus HM410 (manufactured by Toei Sangyo Co., Ltd.). A single yarn was taken out from the continuous reinforcing fiber and set in a composite material interface property evaluation apparatus. A drop in which a thermoplastic resin as a raw material for continuous thermoplastic resin fibers was melted on the apparatus was formed on a continuous reinforcing fiber single yarn and cooled sufficiently at room temperature to obtain a sample for measurement. Set the measurement sample in the device again, pinch the drop with the device blade, run the continuous reinforcing fiber single yarn on the device at a speed of 0.06 mm / min, and measure the maximum pulling load f (N) when pulling out the drop The interfacial bond strength τ was calculated from the following formula (2).
Interfacial adhesive strength τ = f / π · R · l (2)
(F: Maximum pulling load (N) R: Continuous reinforcing fiber single yarn diameter (m) l: Particle diameter in the pulling direction of drop (m))

(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 the continuous reinforcing fiber yarn is measured with a tensilon manufactured by Orientec Co., Ltd. according to JIS L1013, with a grip interval of 20 cm, a pulling speed of 20 cm / min, and n = 10. The value was obtained, and the ratio of both arithmetic mean values was calculated as the maintenance rate.

(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.

(Tensile properties of molded composite materials)
After attaching the composite yarn cloth to a metal frame having a length of 30 cm and a width of 5 cm so as to have a width of 2.5 cm by a hand so as to be 1 mm thick when formed into a composite material molded body, a vacuum dryer And vacuum dried at 100 ° C. for 24 hours. After drying, the composite yarn fabric together with the metal frame was transferred 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.

Examples 1 and 2
Glass fibers having a fineness of 660 dtex to which the following sizing agent A was attached at a weight of 660 dtex and 400 single yarns were used as continuous reinforcing fibers.
Composition of sizing agent A (solid content conversion):
Silane coupling agent: 0.6% by weight 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 weight 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 fibers (trade name: Leona (registered trademark) 470/144 BAU (manufactured by Asahi Kasei Fibers Co., Ltd.), fineness 470 dtex, number of single yarns 144) not subjected to entanglement treatment were used as continuous thermoplastic resin fibers.
After the two fibers were combined and drawn, they were supplied substantially vertically to the fluid entanglement nozzle as shown in FIG. 2-a and fluid entangled under the following conditions to obtain a composite yarn.
-Fluid entanglement nozzle: Kyocera KC-AJI-L (1.5 mm diameter, propulsion type)
Air pressure: 2 kg / cm ² (Example 1), 4 kg / cm ² (Example 2)
Processing speed: 30 m / min Table 1 shows the results of measuring the dispersion rate and tensile breaking strength maintenance rate of the continuous reinforcing fibers of the obtained composite yarn. Furthermore, using the composite yarn as warp and weft, a weave fabric having a warp density of 40 / 5cm, a weft density of 8 / 5cm, and a width of 200mm 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. Further, this woven fabric was stable without warping even when cut to a width of 25 mm, and the handleability was good. Table 1 also shows the result of measuring the tensile properties of the composite material molded body using the interwoven fabric. In the molding, the heating temperature was 280 ° C., and the mold temperature when taking out after cooling was 50 ° C.

[Comparative Example 1]
A composite yarn fabric and a composite material molded body were obtained in the same manner as in Example 1 except that only glass fiber and polyamide 66 fiber were combined and drawn, and no special fiber mixing was performed. When only the fibers were aligned, fluff was generated during weaving, and the processability was poor.
The evaluation results are shown in Table 1.

Example 3
A composite yarn fabric and a composite material molded body were obtained in the same manner as in Example 1 except that the number of single fibers of the glass fiber was 100.
The evaluation results are shown in Table 1.

Example 4
A composite yarn fabric and a composite material molded body were obtained in the same manner as in Example 1 except that the number of single fibers of the glass fiber was 60.
The evaluation results are shown in Table 1.

[ Reference Example 5]
Other than using the stainless steel fiber [trade name: Naslon (registered trademark) (manufactured by Nippon Seisen Co., Ltd.), fineness 470 dtex, number of single yarns 72] to which the sizing agent A is attached as 1.0% by weight as continuous reinforcing fiber Produced a composite yarn fabric and a composite material molded body in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Comparative Example 2]
A composite yarn fabric and a composite material molded body were obtained in the same manner as in Example 5 except that the number of single yarns of the stainless steel fiber was 36.
The evaluation results are shown in Table 1.

From Table 1 above, when Example 1 and Comparative Example 1 are compared, not only simple yarn / drawing, but also mixed yarn by the fluid entanglement method etc., the composite yarn has a high dispersion rate and is uniform. It has been mixed, the tensile fracture strength maintenance ratio is equal or better, the processability in weaving is excellent, the generation of fluff is suppressed, and therefore it is confirmed that it has excellent mechanical properties when made into a composite material molded product did.
In Examples 3-4, Reference Example 5, when compared with Comparative Example 2, if the product RD single filament diameter of the continuous reinforcing fiber (R) and the density (D) is a specific range, the continuous reinforcing fibers Machine with high splicing strength, excellent spreadability and blending properties, high dispersion of continuous reinforcing fibers in composite yarns, and uniform mixing. It was confirmed that the physical properties were excellent.

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

DESCRIPTION OF SYMBOLS 11 Continuous reinforced 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 100 Weft 200 Measuring cylinder 300 Warp 400 Weight 500 Strain gauge

Claims (13)

50% by weight or more of the fibers constituting the fabric are a mixture of continuous glass fibers and continuous polyamide resin fibers , and the continuous glass fibers have a single yarn diameter R (μm) and a density D (g / cm ³ ). product RD Ri is Do from the composite yarn is 20 ~100μm · g / cm ^3, and the continuous polyamide resin, polyamide 4 (poly α--pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (poly Undecanamide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, and copolymerized polyamide containing these as constituent components A composite yarn fabric, which is a kind selected from the group consisting of:   The fabric is a woven fabric composed of warp and weft, at least 50% by weight or more of the fibers constituting the warp is the composite yarn, and the fiber-fiber static coefficient of friction between the warp and the weft is 0.2-3. The composite yarn fabric according to claim 1, which is 0.0.   The composite yarn fabric according to claim 2, wherein the woven fabric is a plain woven fabric or an oblique woven fabric, and 50% by weight or more of fibers constituting the weft are the composite yarn.   The composite yarn according to claim 2, wherein the woven fabric is an interwoven fabric, at least 70% by weight or more of the fibers constituting the warp is the composite yarn, and the ratio of warp density / weft density is 2 to 10. Fabric.   Using a joint air 110 type air splicer manufactured by Machinetex Co., Ltd., supply air pressure: 0.7 MPa, air injection time: scale 4 of adjustment knob PT150, thread length: scale 4 of regulator PT40 The composite yarn fabric according to any one of claims 1 to 4, wherein the tensile breaking strength of the splicing yarn connected with glass fibers is 50 to 100% of the tensile breaking strength of the continuous glass fiber yarn.   The interface adhesive strength by the microdroplet test measured by making the resin which comprises the said continuous polyamide-type resin fiber adhere to the single yarn of the said continuous glass fiber is 9 Mpa or more, It is any one of Claims 1-5. Composite yarn fabric.   The composite yarn fabric according to any one of claims 1 to 6, wherein the continuous glass fiber is substantially untwisted and substantially unentangled.   The ratio of the product RD of the continuous glass fibers and the product RD of the continuous polyamide resin fibers (continuous glass fibers / continuous polyamide resin fibers) is 0.3 to 5, according to any one of claims 1 to 7. The composite yarn fabric described.   The ratio of the single yarn diameter of the continuous glass fiber to the single yarn diameter of the continuous polyamide resin fiber (continuous glass fiber / continuous polyamide resin fiber) is 0.3-2. The composite yarn fabric described in the item.   The composite yarn fabric according to any one of claims 1 to 9, wherein a total fineness of the continuous glass fiber and the continuous polyamide-based resin fiber is 100 to 20,000 dtex.   The composite yarn fabric according to any one of claims 1 to 10, wherein the continuous polyamide-based resin fiber is substantially untwisted and substantially unentangled.   The method for producing a composite yarn fabric according to any one of claims 1 to 11, wherein continuous glass fibers and continuous polyamide resin fibers are mixed by a fluid entanglement method, and the obtained composite yarn is used.   The method according to claim 12, wherein the continuous glass fibers and the continuous polyamide resin fibers are aligned and supplied to the introduction hole surface of the fluid entanglement nozzle substantially perpendicularly to mix the fibers.

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