JP2017110322A - Composite yarn, fabric, and continuous reinforced fiber resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite yarn that has excellent handleability and can achieve both strength and yield, a fabric prepared with the composite yarn, and a continuous reinforced fiber resin molding.SOLUTION: A composite yarn has a continuous reinforced fiber, and a thermoplastic resin that coats the continuous reinforced fiber, the composite yarn having a resin thickness uniformity index of its cross section of 2 or less, the index defined by the following formula (1): resin thickness uniformity index=maximum resin thickness/minimum resin thickness.SELECTED DRAWING: None

Description

  The present invention relates to a composite yarn composed of continuous reinforcing fibers and a thermoplastic resin, a fabric using the composite yarn, and a continuous reinforcing fiber resin molded body using the fabric.

Conventionally, a composite molded body in which a reinforcing material such as glass fiber is added to a resin has been used as a material for structural parts such as various machines and automobiles, pressure vessels, and tubular structures.
Such a composite molded body is required to have characteristics capable of following an arbitrary shape in order to achieve both weight reduction and practically sufficient strength.
As a material constituting the composite molded body, conventionally, a composite yarn in which continuous reinforcing fibers and continuous thermoplastic resin fibers are continuously and uniformly mixed, and a woven fabric including the composite yarn have been proposed.
Furthermore, a molded body in which the woven fabric is heated to about 280 ° C. to melt a portion of the thermoplastic resin and then cooled to about 50 ° C. to be solidified has been proposed (for example, see Patent Document 1). .
In addition, in order to reduce the manufacturing process, a composite yarn in which the periphery of the reinforcing fiber is covered with a thermoplastic resin has been proposed (see, for example, Patent Documents 2 and 3).

Japanese Patent Laying-Open No. 2015-101794 Japanese Patent Laid-Open No. 11-20059 JP-A-8-336879

  However, the above-described conventionally known composite yarn has poor handleability in winding, weaving, and the like, and hard and brittle reinforcing fibers are fluffed or the reinforcing fibers are damaged, so that a desired strength cannot be obtained. Or a sufficient yield cannot be obtained.

  Therefore, an object of the present invention is to provide a composite yarn that is excellent in handleability and has both strength and yield, a fabric using the composite yarn, and a continuous fiber reinforced resin molded product.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have obtained a composite yarn in which the periphery of the continuous reinforcing fiber is uniformly coated with a thermoplastic resin, thereby effectively exposing the continuous reinforcing fiber. It has been found that the vibration and amplitude of the yarn during handling of the composite yarn can be reduced, and the damage to the reinforcing fiber can be reduced. It has also been found that by using the composite yarn, a woven fabric capable of achieving both strength and yield and a composite molded body can be obtained, and the present invention has been completed. That is, the present invention is as follows.

[1]
A composite yarn having continuous reinforcing fibers and a thermoplastic resin covering the continuous reinforcing fibers,
A composite yarn having a cross-sectional resin thickness uniformity index defined by the following formula (1) of 2 or less.
Resin thickness uniformity index = maximum resin thickness / minimum resin thickness (1)
[2]
The composite yarn according to [1] above, having a plurality of continuous reinforcing fibers.
[3]
The composite yarn according to [1] or [2], wherein the continuous reinforcing fiber is a multifilament.
[4]
The composite yarn according to any one of [1] to [3], wherein the thermoplastic resin is a polyamide-based resin.
[5]
The composite yarn according to any one of [1] to [4], wherein the continuous reinforcing fiber is any one selected from the group consisting of yarn, cake, and direct winding.
[6]
A woven fabric comprising the composite yarn according to any one of [1] to [5].
[7]
The step of setting the woven fabric according to the above [6] in a mold, pressurizing, holding at a temperature equal to or higher than the melting point of the thermoplastic resin, and melting the thermoplastic resin;
Cooling, and
A process for producing a continuous reinforced fiber resin molded article having
[8]
Continuous pressing as described in [7] above, wherein the fabric described in [6] is pressurized in a mold, and then injection-filled with a thermoplastic resin composition and molded to obtain a hybrid molded body. A method for producing a fiber resin molded body.

  ADVANTAGE OF THE INVENTION According to this invention, the composite yarn which is excellent in handleability and can make a strength and a yield compatible, the textile fabric using the said composite yarn, and a continuous reinforcement fiber resin molded object are obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Composite yarn]
The composite yarn of this embodiment includes continuous reinforcing fibers and a thermoplastic resin that covers the continuous reinforcing fibers.
The periphery of the continuous reinforcing fiber is preferably uniformly coated with a thermoplastic resin, and the resin thickness uniformity index of the cross section is 2 or less, preferably 1.9 or less, and 1.8 or less Is more preferable, and it is still more preferable that it is 1.7 or less, and it is still more preferable that it is 1.6 or less.
The resin thickness uniformity index of the cross section of the composite yarn is an index indicating the uniformity of the resin coating degree.
The measuring method is shown in the examples described later, but is defined by the following equation (1).
Resin thickness uniformity index = maximum resin thickness / minimum resin thickness (1)
The maximum resin thickness represents the maximum value of the length of the portion occupied only by the thermoplastic resin on the line drawn from the center of the continuous reinforcing fiber to the outer periphery of the composite yarn.
On the other hand, the minimum resin thickness similarly represents the length of the minimum portion.
By uniformly covering the thermoplastic resin, the exposed portions of the continuous reinforcing fibers are reduced, and damage to the continuous reinforcing fibers during handling can be reduced. Moreover, the amplitude of the continuous reinforcing fiber when handling the composite yarn of this embodiment can be suppressed by arranging the continuous reinforcing fiber having a larger mass than the coated thermoplastic resin evenly.
The resin thickness uniformity index of the cross-section of the composite yarn is to reduce the shaking of the continuous reinforcing fiber before and after the resin coating apparatus, and the continuous reinforcing fiber and the resin are in contact with each other under a uniform pressure inside the die. By optimizing the shape of the die of the device for coating the resin, it can be controlled to 2 or less.

The composite yarn of this embodiment can be used as a reinforcing fiber to reinforce other materials, can be used as a reinforced fabric to reinforce other materials, and can be used as a reinforcing fabric for processing other materials. It can also be set as a continuous reinforcement fiber resin molding by processing.
As a constitution of the continuous reinforcing fiber resin molded body, the composite yarn of the present embodiment may be used as a reinforcing fiber, and may be combined with various thermoplastic resins and thermosetting resin matrix resins to form a hybrid molded body, or a composite yarn It is good also as matrix resin by melting the thermoplastic resin which comprises.

In the composite yarn of this embodiment, the number of continuous reinforcing fibers may be only one, or a plurality of continuous reinforcing fibers may be used.
By using a plurality of continuous reinforcing fibers, the resin is easily impregnated between the continuous reinforcing fibers at the time of molding, which is preferable from the viewpoint of shortening the molding time and improving the strength.
The larger the number of continuous reinforcing fibers, the better from the viewpoint of molding time and strength. However, if the amount is too large, the productivity tends to deteriorate, so 1 to 50 is preferable, and 2 to 20 is preferable. More preferably, the number is 2 to 10, more preferably 2 to 5.

The composite yarn of this embodiment preferably has a diameter of 0.1 to 5 mm, more preferably 0.15 to 2 mm, and further preferably 0.2 to 1.5 mm from the viewpoint of handleability. preferable.
The volume ratio between the continuous reinforcing fiber and the thermoplastic resin coating the continuous reinforcing fiber is preferably continuous reinforcing fiber: thermoplastic resin = 10: 90 to 80:20, and preferably 20:80 to 70:30. More preferably, it is more preferably 30:70 to 60:40.
When the volume ratio of the continuous reinforcing fiber is 10% or more, a practically sufficient strength can be obtained, and when it is 80% or less, the tension of the composite yarn can be prevented from becoming excessively high, and good handleability can be obtained. can get.

(Continuous reinforcing fiber)
The composite yarn of this embodiment comprises continuous reinforcing fibers.
As the continuous reinforcing fibers, those used for ordinary fiber-reinforced composite molded bodies can be used.
Examples of continuous reinforcing fibers include, but are not limited to, for example, glass fibers, carbon fibers, aramid fibers, ultra-high strength polyethylene fibers, polybenzazole fibers, liquid crystal polyester fibers, polyketone fibers, metal fibers, and ceramics. Examples thereof include fibers.
Glass fibers, carbon fibers, and aramid fibers are preferable from the viewpoint of mechanical characteristics, thermal characteristics, and versatility, and glass fibers are preferable from the viewpoint of productivity.

  When glass fiber is selected as the continuous reinforcing fiber, a sizing agent may be used, and 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.
Examples of the silane coupling agent include, but are not limited to, aminosilanes such as γ-aminopropyltrimethoxysilane and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane; -Mercaptosilanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes and the like.

<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 according to the purpose can be used, and is not limited to the following, but for example, animal and plant systems such as carnauba wax and lanolin wax, or mineral systems And surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

<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 according to the purpose can be used.
Polymers as binders are not limited to the following, but include, for example, acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary of these. Examples include salts with secondary amines. 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 monomer is not limited to the following, but examples thereof include acrylic acid and maleic acid among monomers having a hydroxyl group and / or a carboxyl group. , Methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid (one or more selected from the group consisting of acrylic acid). As a copolymerizable monomer, it is preferable to have one or more ester monomers.
Salts of acrylic acid homopolymers and copolymers with primary, secondary and tertiary amines are not limited to the following, but include, for example, triethylamine salts, triethanolamine salts and glycine salts. Can be mentioned. 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 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 molded body is obtained.
Examples of the thermoplastic resin used as the binder include, but are not limited to, for example, polyolefin resins, polyamide resins, polyacetal resins, polycarbonate resins, polyester resins, polyether ketones, polyether ethers. Examples include ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these. When the thermoplastic resin used as the binder is the same kind of thermoplastic resin and / or modified thermoplastic resin as the resin covering the periphery of the reinforcing fiber, it becomes a composite molded body, and then the glass fiber and the thermoplastic resin. Adhesiveness is improved, which is preferable.

Furthermore, when the adhesion between the continuous reinforcing fiber and the thermoplastic resin coating the continuous reinforcing fiber is improved and the sizing agent is attached to the glass fiber as an aqueous dispersion, the ratio of the emulsifier component can be reduced or no emulsifier can be used. From this viewpoint, the thermoplastic resin used as the binding agent is preferably a modified thermoplastic resin.
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 used as the binding agent is not limited to the following, and examples thereof include a modified polyolefin resin, a modified polyamide resin, and a modified polyester resin.

The modified polyolefin resin as a binder 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.
Although not limited to the following as an olefin type monomer, For example, ethylene, propylene, 1-butene etc. are mentioned. These may 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 may be used individually by 1 type and may be used in combination of 2 or more type.
As a copolymerization ratio of the olefin monomer and the monomer copolymerizable with the olefin monomer, the total mass of the copolymer is 100% by mass, and the olefin monomer is 60 to 95% by mass, and copolymerization with the olefin monomer is possible. The monomer content 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 used as a binder, a modified group such as a carboxyl group introduced by copolymerization may be neutralized with a basic compound. Examples of the basic compound include, but are not limited to, alkalis such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin used as the binder 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 used as a binding agent 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 used as a binder 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, but are not limited to, for example, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride Etc.
Examples of the sulfonate-containing aromatic dicarboxylic acid include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate.
Examples of the aliphatic dicarboxylic acid or alicyclic dicarboxylic acid include, but are not limited to, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1 , 4-cyclohexanedicarboxylic acid, succinic anhydride, maleic anhydride and the like.
Examples of the tri- or higher functional polycarboxylic acid include, but are not limited to, 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 constituting the modified polyester resin include diols, trifunctional or higher functional polyols, and the like.
Examples of the diol include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1, Examples include 6-hexanediol, neopentyl glycol, polytetramethylene 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 the polycarboxylic acid or its anhydride constituting the modified polyester resin and the polyol, the total mass of the copolymer components is 100% by mass, the polycarboxylic acid or its anhydride is 40 to 60% by mass, the polyol 40 It is preferable that it is -60 mass%, and polycarboxylic acid or its anhydride 45-55 mass% and 45-55 mass% of polyol are more preferable.
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 said polymer and thermoplastic resin used as a binder may be used individually by 1 type, and may use 2 or more types together.
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 of sizing agent for glass fiber>
When glass fiber is used as the continuous reinforcing fiber, the glass fiber bundling agent has a silane coupling agent of 0.1 to 2% by mass, a lubricant of 0.01 to 1% by mass, and a binding agent of 1 respectively. It is preferable to contain -25 mass%, It is preferable to dilute these components with water and to adjust the total mass to 100 mass%.
The blending amount of the silane coupling agent in the glass fiber sizing agent is preferably 0.1 to 2% by mass from the viewpoints of improving the glass fiber sizing property, improving the interfacial adhesive strength and improving the mechanical strength of the composite molded article. More preferably, it is 0.1-1 mass%, More preferably, it is 0.2-0.5 mass%.
The blending amount of the lubricant in the sizing agent for glass fibers is preferably 0 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. 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass from the viewpoint of improving the interfacial adhesive strength and improving the mechanical strength of the composite molded body. It is as follows.
The blending amount of the binder in the sizing agent for glass fibers is preferably 1 to 25% by mass, more preferably from the viewpoints of controlling the sizing property of the glass fibers and improving the interfacial adhesive strength and improving the mechanical strength of the composite molded body. It is 3-15 mass%, More preferably, it is 3-10 mass%.

<Use mode of sizing agent for glass fiber>
The sizing agent for glass fibers may be prepared in any form, such as an aqueous solution, a colloidal dispersion form, an emulsion form using an emulsifier, depending on the use mode, but the dispersion stability of the sizing agent is improved. From the viewpoint of improving heat resistance, it is preferably in the form of an aqueous solution.
The glass fiber as the continuous reinforcing fiber constituting the composite yarn and the continuous reinforcing fiber resin molded body of the present embodiment uses the above-described sizing agent using a known method such as a roller-type applicator in a known glass fiber manufacturing process. The glass fiber produced by applying to the glass fiber is continuously obtained by drying.
The sizing agent is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and still more preferably 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. 0.2 to 1% by mass.
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.

When carbon fiber is selected as the continuous reinforcing fiber, the sizing agent is preferably composed of a lubricant and a binding agent. There are no particular limitations on the type of sizing agent, lubricant, and binding agent, and known materials can be used. As a specific material, the material described in the said patent document 1 (Unexamined-Japanese-Patent No. 2015-101794) can be used.
When other continuous reinforcing fibers are used, the type and amount of sizing agent used for glass fibers and carbon fibers may be appropriately selected according to the characteristics of the continuous reinforcing fibers. It is preferable to use the kind and the applied amount.

<Shape of continuous reinforcing fiber>
The continuous reinforcing fibers are preferably multifilaments, and the number of single yarns is preferably 30 to 15,000 from the viewpoints of openability and handling in the blending process.
The single yarn diameter of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, still more preferably 6 to 20 μm, from the viewpoint of strength and handleability. Even more preferably, it is ˜15 μm.
The continuous reinforcing fiber may be in any form, but it is preferable that the continuous reinforcing fiber is wound around a yarn, cake, or DWR (direct winding) because the productivity and production stability in the step of coating the resin are increased. DWR is preferable from the viewpoint of productivity, and yarn is preferable from the viewpoint of production stability.

(Thermoplastic resin)
The composite yarn of this embodiment includes the above-described continuous reinforcing fiber and a thermoplastic resin that covers the continuous reinforcing fiber.
As the thermoplastic resin, those used for conventionally known composite molded bodies can be used.
The thermoplastic resin is not limited to the following. For example, polyolefin resins such as polyethylene and polypropylene; polyamide resins such as polyamide 6, polyamide 66, and polyamide 46; polyethylene terephthalate, polybutylene terephthalate, polytrimethylene Polyester resin such as terephthalate; Polyacetal resin such as polyoxymethylene; Polycarbonate resin; Polyetherketone; Polyetheretherketone; Polyethersulfone; Polyphenylenesulfide; Thermoplastic polyetherimide; Tetrafluoroethylene-ethylene copolymer And the like, and modified thermoplastic resins obtained by modifying them, and obtained by melt spinning at least one thermoplastic resin selected from them. It is preferable that the connection fibers.
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.
Examples of the polyester resin used as the thermoplastic resin include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene- Examples include 2,6-naphthalenedicarboxylate.
The polyester resin may be a homopolyester or a copolyester.
In the case of a copolyester, a copolymer obtained by suitably copolymerizing a third component with a homopolyester is preferable. Examples of the third component include, but are not limited to, diethylene glycol, neopentyl glycol, polyalkylene glycol, and the like. Diol components, dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid.
In addition, a polyester-based resin using a raw material derived from biomass resources can be used, but is not limited to the following, for example, aliphatic such as polylactic acid, polybutylene succinate, polybutylene succinate adipate Examples thereof include polyester resins and aromatic polyester resins such as polybutylene adipate terephthalate.

<Polyamide resin>
The polyamide-based resin means a polymer compound having a —CO—NH— (amide) bond in the main chain.
The polyamide resin used as the thermoplastic resin is not limited to the following. For example, polyamide obtained by ring-opening polymerization of lactam, polyamide obtained by self-condensation of ω-aminocarboxylic acid, diamine and dicarboxylic acid. Examples thereof include polyamides obtained by condensing acids and copolymers thereof.
A polyamide-type resin may be used individually by 1 type, and may be used as a 2 or more types of mixture.
Examples of the lactam include, but are not limited to, pyrrolidone, caprolactam, undecane lactam, and dodecalactam. Examples of the ω-aminocarboxylic acid include, but are not limited to, 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, but are not limited to, linear aliphatic diamines such as hexamethylene diamine and pentamethylene diamine; 2-methylpentane diamine and 2-ethyl hexamethylene diamine. Branched aliphatic diamines such as: aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine.
Examples of the dicarboxylic acid (monomer) include, but are not limited to, aliphatic dicarboxylic acids such as adipic acid, pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; cyclohexane And alicyclic dicarboxylic acids such as dicarboxylic acids. 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-based resin include, but are not limited to, polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), and polyamide 12 (polydodecanamide). , Polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonanemethylene terephthalamide), and Examples thereof include polyamide 6I (polyhexamethylene isophthalamide) and copolymerized polyamides containing these as constituent components.
Examples of the copolymerized polyamide include, but are not limited to, for example, a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and hexamethylene adipamide. And a copolymer of methylene terephthalamide and 2-methylpentanediamine terephthalamide.

[Production method of composite yarn]
The method for producing a composite yarn according to this embodiment includes a step of coating a continuous reinforcing fiber with a thermoplastic resin.
As a method for coating the continuous reinforcing fiber with the thermoplastic resin, for example, a method as described in Patent Document 3 (Japanese Patent Laid-Open No. 8-336879) can be mentioned.
The composite yarn of this embodiment has a cross-sectional resin thickness uniformity index of 2 or less, and the continuous reinforcing fiber is uniformly coated with a thermoplastic resin.
In order to uniformly coat the thermoplastic resin around the continuous reinforcing fiber, the viscosity of the thermoplastic resin, the specific gravity of the continuous reinforcing fiber, the density, and the affinity between the thermoplastic resin and the continuous reinforcing fiber are important. In contact with the molten thermoplastic resin under pressure, the shape of the die part that is discharged when the continuous reinforcing fiber and the molten thermoplastic resin come into contact, the tension of the continuous reinforcing fiber, the thermoplastic resin It is important to adjust the melting temperature and the line speed, and the die shape is particularly important.
The optimum die shape varies depending on the type, shape, surface treatment agent, and type of resin to be coated, but the pressure of the resin in the part where the molten resin and continuous reinforcing fiber are in contact is uniform. Such a design is preferred. In order to control the pressure uniformly, the diameter of the discharge port discharged in contact with the continuous reinforcing fiber is smaller than the diameter of the inlet that introduces the molten resin into the die, and the continuous reinforcing fiber and the molten resin are in contact with each other. It is preferable to increase the pressure of the portion to be used. It is preferable to keep the pressure at the portion where the continuous reinforcing fiber and the molten resin are in contact with each other by adjusting the pressure at which the molten resin is sent to the die, the viscosity of the resin, and the line speed at which the continuous reinforcing fiber is drawn.

The composite yarn manufacturing apparatus includes a yarn feeding device, a resin melting device, a die, a cooling device, a detector, a winder, and the like, and an extrusion coating device, a dipping coating device, and the like can be used. An extrusion coating apparatus that can easily control the thickness of the resin is preferable.
The melting temperature of the resin may be higher than the melting point of the thermoplastic resin, but from the viewpoint of suppressing thermal degradation, the melting point of the thermoplastic resin is preferably +10 to 100 ° C., and the melting point is +20 to 80 ° C. It is more preferable that the melting point is +30 to 70 ° C. As an apparatus for melting the resin, for example, an extruder may be used. It is preferable to adjust the shape of the screw according to the viscosity of the resin and to feed the molten resin into the die with an appropriate pressure. It is preferable to perform nitrogen purging or venting as necessary.
The cooling may be air cooling, may be performed by immersing in a water bath, or may be performed by wrapping around a cooling roller. Water may be sprayed at the same time as wrapping around the cooling roller. When water is used for cooling, it is preferable to provide a drying mechanism as necessary. Drying may be performed using a fluid such as air, a temperature may be applied, or water may be physically removed with a cloth or the like. The detector can detect the stability of the diameter and the deviation of the center of gravity due to the detection of the yarn deflection width by, for example, an optical method. The winder may be automatically controlled or manually controlled.
The yarn speed is preferably 10 to 2000 m / min, more preferably 50 to 1800 m / min, and preferably 100 to 1500 m / min from the viewpoints of productivity and production stability.

  It is preferable that the yarn feeding device, the die in which the continuous reinforcing fiber contacts the molten resin, and the cooling device are arranged in a straight line. It is preferable to pass a guide slightly larger than the diameter of the yarn as necessary before and after each device to control the position of the yarn before and after the die.

[Intermediate materials such as textiles]
The method for producing a continuous reinforcing fiber resin molded body using the composite yarn of the present embodiment is not particularly limited, but an intermediate material is produced according to the shape of the intended continuous reinforcing fiber resin molded body, and the intermediate material is used. It is preferable to produce the intended continuous reinforced fiber resin molding.
The intermediate material is not particularly limited, and examples thereof include a unidirectional reinforcing material in which composite yarns are aligned in a specific direction, woven fabrics, knitted fabrics, laces, felts, non-woven fabrics, films and plate-like bodies using composite yarns.
As an intermediate material, a flexible unidirectional reinforcing material, a woven fabric, a knitted fabric, a lace, a felt, and a non-woven fabric are preferable from the viewpoint of shape followability in a mold when producing continuous reinforcing fiber resin moldability. The unidirectional reinforcing material and the woven fabric shape are more preferable because the continuous reinforcing fiber is less bent and the strength is easily obtained, and the woven fabric shape is more preferable from the viewpoint of form stability.
The weaving method of the woven fabric is not particularly limited, and examples thereof include plain weave, twill weave, satin weave, weave weave, and reed.
From the viewpoint of the strength of the continuous reinforcing fiber resin molding of the present embodiment, a twill weave in which the crimp rate of the continuous reinforcing fibers is low is more preferable.
The method for obtaining these intermediate materials is not particularly limited, and can be selected according to the application and purpose.
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. For example, a preferable method is a method obtained by driving a weft into a warp in which fibers containing composite yarns 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.
For other intermediate materials, the method described in Patent Document 1 (Japanese Patent Laid-Open No. 2015-101794) can be used as appropriate.

[Continuous Reinforced Fiber Resin Molded Body and Method for Producing the Same]
The continuous reinforcing fiber resin molded body of the present embodiment contains the above-described composite yarn or intermediate material as a constituent material.
In addition, the manufacturing method of the continuous reinforcement fiber resin molding of this embodiment is not limited to the following, A various method is applicable.
For example, a base material constituting a continuous reinforcing fiber resin molded body, preferably a fabric-shaped base material, is cut in accordance with a desired molded body, and a necessary number of layers are laminated in consideration of the desired product thickness. Set according to the shape. At this time, by using the above-mentioned intermediate material, it is possible to increase the degree of freedom with respect to the mold as compared with a conventional composite plate in which a resin is impregnated with a general reinforcing fiber. Even when there is a difference, it is possible to mold with a high degree of shape freedom. After setting the substrate in the mold, the mold is closed and compressed. Then, the mold is heated to a temperature equal to or higher than the melting point of the thermoplastic resin constituting the continuous reinforcing fiber resin molded body, and the thermoplastic resin is melted and shaped. The clamping pressure is not particularly specified, but is preferably 1 MPa or more, more preferably 3 MPa or more. Alternatively, one-end clamping may be performed for degassing and the like, and after the compression molding, the clamping pressure of the one-end mold may be released.

In the production process of a continuous reinforcing fiber resin molded body, an intermediate material is set in a mold, the mold is closed and pressurized, and after a predetermined time, a predetermined thermoplastic resin composition is further injected and filled. The continuous reinforced fiber resin molded body that is a hybrid molded body may be manufactured by bonding the thermoplastic resin and the predetermined thermoplastic resin composition.
The timing at which the predetermined thermoplastic resin composition is injected and filled greatly affects the interface strength between the two thermoplastic resins.
The mold temperature when injection-filling the predetermined thermoplastic resin composition is preferably equal to or higher than the melting point or glass transition temperature of the thermoplastic resin constituting the continuous reinforcing fiber resin molded body. More preferably, the melting point of the thermoplastic resin constituting the continuous reinforced fiber resin molded body is + 10 ° C. or higher or the glass transition temperature + 10 ° C. or higher, more preferably the melting point + 20 ° C. or higher or the glass transition temperature + 20 ° C. or higher. Is melting point + 30 ° C. or higher or glass transition temperature + 30 ° C. or higher.
In addition, the timing of injection filling the predetermined thermoplastic resin composition is such that the mold temperature is raised above the melting point and glass transition point of the thermoplastic resin after the intermediate material is set in the mold and the mold is closed. Then, within 30 seconds is preferable.
In the hybrid molded body, it is preferable that the joining portion of the thermoplastic resin constituting the continuous reinforcing fiber resin molded body and the thermoplastic resin composition formed by injection molding has a concavo-convex structure mixed with each other.
It is effective to increase the interfacial strength by setting the mold temperature to be equal to or higher than the melting point of the thermoplastic resin composition to be injected and to increase the resin holding pressure during injection molding, for example, 1 MPa or higher. In order to increase the interfacial strength, the holding pressure is preferably 5 MPa or more, and more preferably 10 MPa or more.
Holding the pressure holding time long, for example, 5 seconds or more, preferably 10 seconds or more, more preferably the time until the mold temperature is equal to or lower than the melting point of the thermoplastic resin composition is from the viewpoint of increasing the interfacial strength. preferable.

(Resin for injection molding)
The thermoplastic resin composition for injection molding used for producing the hybrid molded body is not particularly limited as long as it is a thermoplastic resin composition used for general injection molding.
The thermoplastic resin composition is not limited to the following, for example, polyethylene, polypropylene, polyvinyl chloride, acrylic resin, styrene resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyphenylene ether, modified A resin composition in which one or two or more of polyphenylene ether resin, wholly aromatic polyester, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide resin, polysulfone, polyetheretherketone, polyetherketone, etc. are mixed Can be mentioned.
Moreover, various fillers may be mix | blended with these thermoplastic resin compositions.
Examples of the various fillers include short fibers and long fiber materials that are discontinuous reinforcing materials of the same type as the continuous reinforcing fibers.
When short glass fibers or long fibers are used as the discontinuous reinforcing material, a sizing agent may be used in the same manner as the continuous reinforcing fibers included in the composite yarn of this embodiment.
Bundling agents are silane coupling agents and lubricants. And a binding agent. Regarding the types of the silane coupling agent, the lubricant, and the binding agent, the same sizing agent as the above-mentioned continuous reinforcing fiber sizing agent can be used.
The thermoplastic resin composition used for injection molding is similar to the thermoplastic resin constituting the continuous reinforced fiber resin molded body from the viewpoint of the interfacial strength between the continuous reinforced fiber resin molded body part and the injection molded thermoplastic resin composition part. Are preferable, and the same type is more preferable. Specifically, when polyamide 66 fiber is used as the thermoplastic resin constituting the continuous reinforcing fiber resin molded body, the resin material of the thermoplastic resin composition for injection molding is preferably polyamide 66.

[Applications for continuous reinforcing fiber resin moldings]
The continuous reinforcing fiber resin molded body of the present embodiment can be suitably used for structural material applications such as aircraft, vehicles, and construction materials.
In a car application, although not limited to the following, for example, it can be used for a chassis / frame, a suspension, a drive system component, an interior component, an exterior component, a functional component, and other components.
Specifically, steering shaft, mount, sunroof, step, soof trim, door trim, trunk, boot lid, bonnet, seat frame, seat back, retractor, retractor support bracket, clutch, gear, pulley, cam, AG, elastic beam , Buffing, lamp, reflector, glazing, front end module, back door inner, brake pedal, handle, electrical component, sound absorbing material, door exterior, interior panel, instrument panel, rear gate, ceiling tension, seat, seat frame, wiper support, EPS, small motor, heat sink, ECU box, ECU housing, steering gear box housing, plastic housing, EV motor housing, wire harness, in-vehicle meter, combination Switch, small motor, spring, damper, wheel, wheel cover, frame, subframe, side frame, two-wheel frame, fuel tank, oil pan, intake manifold, propeller shaft, drive motor, monocoque, hydrogen tank, fuel cell electrode, Panel, floor panel, outer panel, door, cabin, roof, hood, valve, EGR valve, variable valve timing unit, connecting rod, cylinder bore, member (engine mounting, front floor cross, footwell cross, seat cross, inner side , Rear cross, suspension, pillar lean force, front side, front panel, upper, dash panel cross, steering), tunnel, fastening insert, crash , Crash rail, corrugated, roof rail, upper body, side rail, braiding, door surround assembly, airbag components, body pillar, dash-up pillar gusset, suspension tower, bumper, body pillar lower, front body pillar, rain force Instrument panel, rail, roof, front body pillar, roof rail, roof side rail, rocker, door belt line, front floor under, front body pillar upper, front body pillar lower, center pillar, center pillar hinge, door outside panel, ), Side outer panel, front door window frame, NICS bulk, torque box, radiator support, radiator Fan, water pump, fuel pump, electronic control throttle body, engine control ECU, starter, alternator, manifold, transmission, clutch, dash panel, dash panel insulator pad, door side impact protection beam, bumper beam, door beam, bulkhead, outer pad , Inner pad, rear seat rod, door panel, door trim bod SUB-ASSY, energy absorber (bumper, shock absorption), shock absorber, shock absorption garnish, pillar garnish, roof side inner garnish, resin rib, side rail front spacer, side rail Rear spacer, seat belt pretensioner, airbag sensor, arm (suspension, lower Hood hinge), suspension link, shock absorbing bracket, fender bracket, inverter bracket, inverter module, hood inner panel, hood panel, cowl louver, cowl top outer front panel, cowl top outer panel, floor silencer, dump seat, hood insulator, Fender side panel protector, cowl insulator, cowl top ventilator looper, cylinder head cover, tire deflector, fender support, strut tower bar, mission center tunnel, floor tunnel, radio core support, luggage panel, luggage floor, etc. be able to.

  Hereinafter, the present embodiment will be described with reference to examples and comparative examples, but the present embodiment is not limited to the following examples.

The composite yarn manufactured by the Example and comparative example which are mentioned later, and the evaluation method of the characteristic of a continuous reinforcement fiber resin molding are shown.
[Tensile test method for composite yarn]
Based on JIS L1013, it was measured at a gripping interval of 20 cm and a tensile speed of 20 cm / min with Tensilon manufactured by Orientec Corporation.
When performing a tensile test on a composite yarn, two types of breakage points are observed: continuous reinforcing fiber break points and resin break points. Of particular importance is the breaking strength of the continuous reinforcing fiber observed first, and this strength also depends on the thickness of the continuous reinforcing fiber. For this reason, the value which converted into the stress value which remove | divided the intensity | strength observed by the tension test by the cross-sectional area of the continuous reinforcement fiber was used as tensile strength.
The cross-sectional area of the continuous reinforcing fiber was obtained by image analysis after embedding, cleaving, and polishing the composite yarn.

[Tensile test method for continuous reinforced fiber resin moldings]
Using an Instron 100kN universal testing machine, strip-shaped test pieces with a length of 70 mm, a width of 10 mm, and a wall thickness of 3 mm are chucked at intervals of 30 mm in the longitudinal direction, at a speed of 5 mm / min, in an environment of 23 ° C. and 50% RH. The tensile strength was measured at

[Measurement method of resin thickness uniformity index of cross section of composite yarn]
30 arbitrary points of the composite yarn were cut at a cross section perpendicular to the yarn direction, observed with a microscope, and a resin thickness uniformity index was measured by image processing.
When the yarn bundle was loosened or difficult to observe, the yarn bundle was wrapped with a shrink tube and observed.
Alternatively, the cross-section was observed by embedding with an embedding material such as epoxy.
The microscope was observed in the reflection mode of an optical microscope.
SEM was used for the samples that are difficult to contrast.
The resin thickness uniformity index of the composite yarn was calculated by the following formula.
Resin thickness uniformity index = maximum resin thickness / minimum resin thickness The maximum resin thickness is the length of the portion occupied only by the thermoplastic resin on the line drawn from the center of the continuous reinforcing fiber to the outer periphery of the composite yarn. Represents the maximum value.
On the other hand, the minimum resin thickness similarly represents the length of the minimum portion.

[Evaluation of workability and durability of composite yarn]
As a method for evaluating the workability and durability of the composite yarn, the workability and strength maintenance property when passed through a fluid entanglement nozzle were measured.
Using the fluid entanglement nozzle shown below, supplying the composite yarn substantially perpendicularly to the nozzle, flowing the fluid under the following conditions, and winding up the composite yarn were repeated 10 times.
-Fluid entanglement nozzle: Kyocera KC-AJI-L (1.5 mm diameter, propulsion type)
・ Air pressure: 4kg / cm ²
-Machining speed: 30 m / min The condition of the composite yarn was confirmed by visual observation and used as a guide for workability.
In addition, the composite yarn was subjected to a tensile test before and after processing, and the case where 90% or more of the strength of the composite yarn before processing was maintained was ○, and the strength was less than 90% of the strength of the composite yarn before processing. The case is represented by x.

The raw materials of the composite yarn produced in the examples and comparative examples described later are shown below.
[Resin for coating]
The following resins were prepared as thermoplastic resins for coating the continuous reinforcing fibers.
・ PA66 (Asahi Kasei Chemicals 1402S-011)
The PA66 has a relative viscosity of 45 and a water content of 0.09%, with 99.29 parts by mass of PA66, 0.03 parts by mass of copper acetate (monohydrate), and 0.1% of potassium iodide. 50 parts by mass, 0.01 parts by mass of manganese (II) lactate, 0.12 parts by mass of AlSt, and 0.06 parts by mass of PEG400 were added.

[Continuous reinforcing fiber]
A glass fiber having a fineness of 685 dtex and 400 single yarns, to which 1.0% by mass of the following sizing agent a was attached, was used as the continuous reinforcing fiber (A). The winding form was yarn, and the average single yarn diameter was 9 μm.
A glass fiber having a fineness of 1350 dtex and 800 single yarns to which 1.0% by mass of the following sizing agent a was adhered was used as the continuous reinforcing fiber (B). The winding form was a cake, and the average single yarn diameter was 9 μm.
(Composition of sizing agent a (in terms of solid content)):
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.)]

[Composite yarn manufacturing apparatus and composite yarn manufacturing method]
A coating machine manufactured by AIKI was used. When the yarn was used, the roll was fixed as it was when the yarn was used, and the yarn was fed as it was. When the cake was used, the yarn was rolled off. From yarn feeding to die, cooling and winding, arrange the yarn so that it is straight, just before the die, just after touching the cooling water, just after leaving the cooler, just before the winder Was installed. The extruder was installed at a 90 degree angle to the yarn. For cooling, a water bath was used, and after cooling, water was blown off by air. The yarn speed was 200 m / min and was controlled by a winder. Extrusion was performed at 280-295 ° C. Use a die that has been squeezed so that the contact portion with the continuous reinforcing fiber is smaller than the resin introduction portion so that the resin melted inside the die and the continuous reinforcing fiber come into contact with each other in a slightly pressurized state. The extrusion speed of the extruder was finely adjusted.
The composite yarn manufacturing apparatus and the composite yarn manufacturing method described above were applied to the following [Examples 1 and 2].

[Production method of woven fabric]
A rapier weaving machine (DORNIER RAPIER WEAVING MACHINE P1 manufactured by DORNIER) was used to weave a composite yarn using warps and wefts, a warp density of 6/5 mm, a weft density of 6/5 mm, and a twill weave.
In addition, the manufacturing method of the textile fabric mentioned above was applied to the following [Examples 1 and 2, Comparative Examples 1 and 2].

[Production method of continuous reinforcing fiber resin molding]
(Textile compression molding process)
The molding machine used was Toshiba Machine (S100V-8A) with a maximum clamping force of 300 tons.
A mold for obtaining a box-shaped continuous reinforcing fiber resin molded body (length 200 mm, width 200 mm, height 120 mm, wall thickness 3 mm) was prepared.
Eight woven fabrics cut into a shape matched to the mold were prepared.
A mold heated in advance to 300 ° C. was opened, the woven fabric was set at a predetermined position of the mold, and then clamped with a clamping force of 240 MPa to perform compression molding.
(Injection molding process)
Ten seconds after the clamping, the polyamide 66 resin [trade name: Leona (registered trademark) 14G33] containing 33% short fibers GF is maintained in a state where the temperature of the mold is maintained at a temperature equal to or higher than the melting point of the thermoplastic resin. The resin composition is injected and filled at an injection pressure of 50 MPa and an injection speed of 30 mm / sec, a holding pressure of 10 MPa is applied, the mold temperature is cooled to 150 ° C., cooling and solidification is performed, and the fabric portion and the resin composition are joined. went.
The cylinder set temperature of the injection molding machine was 280 ° C.
(Release process)
The mold was opened, and a continuous reinforcing fiber resin molded body which was a box-shaped hybrid molded body was taken out.
In addition, the manufacturing method of the continuous reinforcement fiber resin molding mentioned above was applied to the following [Examples 1, 2 and Comparative Examples 1 and 2].

[Example 1]
A composite yarn was produced using the continuous reinforcing fiber (B).
The extrusion speed of the resin was manually changed, and the operation was performed so that the volume ratio of the continuous reinforcing fiber to the resin was 40:60.
Using the composite yarn, a woven fabric and a continuous reinforcing fiber resin molded body were produced by the method described above.

[Example 2]
A composite yarn was produced in the same manner as in Example 1 except that two continuous reinforcing fibers (A) were used.
Using the composite yarn, a woven fabric and a continuous reinforcing fiber resin molded body were produced by the method described above.

[Comparative Example 1]
Two polyamide 66 fibers [trade name: Leona (registered trademark) 470 / 144BAU (manufactured by Asahi Kasei Fibers Co., Ltd.), fineness: 470 dtex, number of single yarns: 144], and two continuous reinforcing fibers (A) Using this, both were combined and drawn, then supplied substantially vertically to the fluid entanglement nozzle, 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: 2kg / cm ²
-Processing speed: 30 m / min Using the said composite yarn, the textile fabric and the continuous reinforcement fiber resin molding were produced by the method mentioned above.

[Comparative Example 2]
With reference to Example 1 of JP-A-8-336879, a composite yarn was produced with two continuous reinforcing fibers (A), a die temperature of 290 ° C., and a cylinder temperature of 250 ° C. The discharge amount was adjusted so that the volume ratio of the continuous reinforcing fiber to the resin was 40:60.
Using the composite yarn, a woven fabric and a continuous reinforcing fiber resin molded body were produced by the method described above.

The evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in [Table 1] below.
In Table 1 below, “−” means that the coating amount (denominator) of the continuous reinforcing fiber with the resin is 0, and thus cannot be calculated.

In Examples 1 and 2, the continuous reinforcing fibers are completely covered with the resin, and the continuous reinforcing fibers are not damaged in the manufacturing process of the composite yarn, and the processability is excellent. For this reason, the molded object which pressure-molded the textile also showed the high intensity | strength.
It was found that Example 2 using two continuous reinforcing fibers had higher impregnation properties and higher strength of the molded body.
Since Comparative Example 1 was coated non-uniformly, it was found that there was damage to the continuous reinforcing fibers during the production of the composite yarn and during the textile processing, and the strength of the pressure-molded molded body was also reduced.
In Comparative Example 2, it was found that the strength of the composite yarn was low because the continuous reinforcing fiber was exposed.

  The composite yarn, woven fabric, and continuous reinforcing fiber resin molded body of the present invention have industrial applicability as a reinforcing material for materials that require high-level mechanical properties such as structural parts of various machines and automobiles. Have.

Claims (8)

A composite yarn having continuous reinforcing fibers and a thermoplastic resin covering the continuous reinforcing fibers,
A composite yarn having a cross-sectional resin thickness uniformity index defined by the following formula (1) of 2 or less.
Resin thickness uniformity index = maximum resin thickness / minimum resin thickness (1)   The composite yarn according to claim 1, comprising a plurality of continuous reinforcing fibers.   The composite yarn according to claim 1 or 2, wherein the continuous reinforcing fibers are multifilaments.   The composite yarn according to any one of claims 1 to 3, wherein the thermoplastic resin is a polyamide-based resin.   The composite yarn according to any one of claims 1 to 4, wherein the continuous reinforcing fiber is any one selected from the group consisting of yarn, cake, and direct winding.   A woven fabric comprising the composite yarn according to any one of claims 1 to 5. The step of setting the woven fabric according to claim 6 in a mold, pressurizing, holding at a temperature equal to or higher than the melting point of the thermoplastic resin, and melting the thermoplastic resin;
Cooling, and
A process for producing a continuous reinforced fiber resin molded article having   The continuous reinforced fiber resin according to claim 7, further comprising a step of injection-filling and molding the thermoplastic resin composition after pressurizing the woven fabric according to claim 6 in a mold to obtain a hybrid molded body. Manufacturing method of a molded object.