JP2019181901A - Method for manufacturing molding product - Google Patents

Abstract

To provide a method for manufacturing a molding product capable of efficiently manufacturing a molding product restraining a composite material from slipping during injection filling and having an excellent appearance.SOLUTION: A method for manufacturing a molding product, being a method for manufacturing a molding product formed by laminating a thermoplastic resin B at least on a part of a surface of a resin composite material containing a continuous reinforcing fiber and a thermoplastic resin A, includes: a disposing step for disposing the resin composite material into a cavity of a mold with a melting temperature or less of the thermoplastic resin A; an injection filling step for injection filling the thermoplastic resin B at least on a part of the surface of the resin composite material in a state in which the mold is slightly opened; a joining step for closing the mold, heating a part of the mold up to a melting temperature or more of the thermoplastic resin A, and compression molding the resin composite material and the thermoplastic resin B to join the resin composite material and the thermoplastic rein B together.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a molded article.

  In fields where mechanical properties such as structural parts such as various machines and automobiles, pressure vessels, and tubular structures are required, composite molded bodies including composite materials including reinforcing materials such as glass fibers are used. As such a composite molded body, for example, a composite molded body obtained by joining a composite material containing continuous reinforcing fibers and a thermoplastic resin and a thermoplastic resin composition is known (Patent Document 1).

International Publication No. 2017/073696

The composite molded body described in Patent Document 1 is a composite molded body having excellent bonding strength. In Patent Document 1, as a method of manufacturing a composite molded body, a thermoplastic resin is injected and filled after the mold is closed, and the entire mold is warmed and compression molded to obtain a composite material and a thermoplastic resin composition. A method of joining is described.
However, in the method described in Patent Document 1, since the thermoplastic resin is injected and filled with the mold closed, the pressure loss is large, and if the injection pressure or the injection speed is increased, the composite material is displaced during injection filling. There was a thing. Furthermore, it is necessary to install a heater and a cooling mechanism in the entire mold in order to raise the temperature of the entire mold at the time of joining and then cool it down. It is difficult to install hot runners, eject pins, etc. in the mold. The degree of freedom in designing the mold was low, and there was a need for a device that would further improve production efficiency.

  Accordingly, an object of the present invention is to provide a method for producing a molded product that can efficiently produce a molded product that is less likely to shift the continuous reinforcing fiber orientation of the composite material during injection filling and that has an excellent appearance.

That is, the present invention is as follows.
[1]
A method for producing a molded article in which a thermoplastic resin B is laminated on at least a part of a surface of a resin composite material containing continuous reinforcing fibers and a thermoplastic resin A,
An arrangement step of arranging the resin composite material in a cavity of a mold having a melting point of the thermoplastic resin A or lower;
An injection filling step of injecting and filling the thermoplastic resin B onto at least a part of the surface of the resin composite material in a state where the mold is opened;
The mold is closed, a part of the mold is heated to a temperature equal to or higher than the melting point of the thermoplastic resin A, and the resin composite material and the thermoplastic resin B are compression molded to form the resin composite material and the thermoplastic resin. A joining step for joining B;
The manufacturing method of the molded article characterized by including.

[2]
The method for producing a molded article according to [1], wherein a part of the mold is a mold on the surface side of the resin composite material opposite to the surface on which the thermoplastic resin B is injected and filled.

[3]
The method for producing a molded article according to [1] or [2], wherein, in the injection filling step, the thermoplastic resin B is injected and filled through a hot runner.

[4]
[3] The method for producing a molded article according to [3], wherein after injection filling of the thermoplastic resin B, an injection holding pressure equivalent to the press pressure at the time of compression molding is applied via a hot runner.

[5]
The method for producing a molded article according to any one of [1] to [4], wherein the mold is a mold including an upper mold and a lower mold.

  Since the method for producing a molded product according to the present invention has the above-described configuration, a method for producing a molded product capable of efficiently producing a molded product having an excellent appearance, in which the continuous reinforcing fiber orientation of the composite material is difficult to shift during injection filling. Can be provided.

FIG. 1 is a schematic view showing an example of a method for producing a molded article according to this embodiment. FIG. 2 is a schematic diagram of a bending test in the evaluation of interface strength.

  Hereinafter, an embodiment of the present invention (hereinafter, also referred to as “this embodiment”) will be described in detail, but the present invention is not limited to this embodiment.

The method for producing a molded article of the present invention is a method for producing a molded article in which a thermoplastic resin B is laminated on at least a part of the surface of a resin composite material containing continuous reinforcing fibers and a thermoplastic resin A, Arrangement step of disposing the resin composite material in the cavity of the mold below the melting point of the thermoplastic resin A, with the mold opened, the thermoplastic resin B on at least a part of the surface of the resin composite material Injection filling step of injecting and filling, the mold is closed, a part of the mold is heated to the melting point of the thermoplastic resin A or higher, the resin composite material and the thermoplastic resin B are compression-molded, A hybrid overmolding method including a bonding step of bonding a resin composite material and the thermoplastic resin B.
In this specification, the melting point of the thermoplastic resin A may be referred to as “TmA”, and the melting point of the thermoplastic resin B may be referred to as “TmB”.

FIG. 1 is a schematic view showing an example of a method for producing a molded article according to this embodiment.
In the arrangement step, the resin in the cavity 5, which is a cavity sandwiched between the upper mold 3 and the lower mold 4, where the temperature of the upper mold 3 and the lower mold 4 is equal to or lower than the melting point of the thermoplastic resin A. The composite material 1 is disposed (FIG. 1A). In this example, a mold comprising a lower mold 4 provided with a heating mechanism and a hot runner 41 and an upper mold 3 provided with a heating mechanism and a cooling mechanism is used.
In the injection filling step, the mold is closed to the opened state (FIG. 1B), and the thermoplastic resin B2 is injection filled onto the surface of the resin composite material 1 (FIG. 1C). In this example, there is a gap 6 that communicates along the parting line between the upper mold 3 and the lower mold 4 in the opened state. Further, the thermoplastic resin B2 is injected and filled onto the lower mold side surface of the resin composite material 1 via the hot runner 41.
In the joining step, the mold is closed (FIG. 1 (d)), the upper mold 3 is heated to the melting point of the thermoplastic resin A or higher (FIG. 1 (e)), the resin composite material 1 and the thermoplastic resin B2 Are compression-molded and joined. Note that the upper mold 3 in FIG. 1 (e) schematically shows a state of being heated.
Thereafter, the heated upper mold is cooled (FIG. 1 (f)), and the mold can be opened to obtain a molded product.
This will be described in detail below.

[Arrangement process]
(Resin composite material)
The resin composite material includes at least continuous reinforcing fibers and a thermoplastic resin A.

-Continuous reinforcing fiber-
The continuous reinforcing fiber is at least one selected from the group consisting of glass fiber, carbon fiber, aramid fiber, ultrahigh strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, and ceramic fiber. Fiber is preferred. Among these, glass fiber, carbon fiber, and aramid fiber are preferable from the viewpoint of mechanical characteristics, thermal characteristics, and versatility, and glass fiber is preferable from the viewpoint of economy. The continuous reinforcing fibers can be used singly or in combination.

  When glass fiber is selected as the continuous reinforcing fiber, a sizing agent may be used. As the sizing agent, a sizing agent containing a silane coupling agent, a lubricant, and a binding agent is preferable, and a sizing agent containing a silane coupling agent, a lubricant, a binding agent, and an emulsifier is more preferable.

--Silane coupling agent--
The silane coupling agent is usually used as a surface treatment agent for glass fibers, and preferably contributes to an improvement in interfacial adhesive strength.
Examples of the silane coupling agent include aminosilanes such as γ-aminopropyltrimethoxysilane and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane; γ-mercaptopropyltrimethoxysilane and γ-mercapto. Mercaptosilanes such as propyltriethoxysilane; epoxy silanes; vinyl silanes; The said silane coupling agent can be used individually by 1 type or in combination of multiple.

--- Lubricant--
It is preferable that the lubricant contributes to an improvement in the opening property of the glass fiber.
As the lubricant, any ordinary liquid or solid lubricating material can be used depending on the purpose. For example, animal or plant or mineral wax such as carnauba wax or lanolin wax; fatty acid amide, fatty acid And surfactants such as esters, fatty acid ethers, aromatic esters, and aromatic ethers. The said lubricant can be used individually by 1 type or in combination of multiple.

--Bundling agent--
It is preferable that the above-mentioned binding agent contributes to the improvement of the binding property and the interfacial adhesive strength of the glass fiber.
As the binding agent, a polymer, a thermoplastic resin, or the like can be used depending on the purpose. The said binding agent can be used individually by 1 type or in combination of multiple.

  Examples of the binder polymer include acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and / or tertiary amines. Can be mentioned. For example, polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and polyester or polyether diols are also suitable. Used for.

  As a copolymerizable monomer constituting a copolymer of acrylic acid and other copolymerizable monomer, for example, among monomers having a hydroxyl group and / or a carboxyl group, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, One or more selected from the group consisting of fumaric acid, itaconic acid, citraconic acid, and mesaconic acid can be mentioned. As a copolymerizable monomer, it is preferable to include one or more ester monomers.

  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. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and standard monodisperse polystyrene.

  Examples of salts with primary, secondary, and tertiary amines include triethylamine salts, triethanolamine salts, and glycine salts. The degree of neutralization is preferably 20 to 90%, and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable. In addition, the said neutralization degree means the value measured by the method based on JISK2501.

  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. From the viewpoint of improving the converging property of the glass fiber, it is preferably 3,000 or more, and preferably 50,000 or less from the viewpoint of improving the properties when formed into a molded product.

Examples of the binder resin include, for example, polyolefin resin, polyamide resin, polyacetal resin, polycarbonate resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, and thermoplastic resin. Examples thereof include polyetherimide, thermoplastic fluororesin, and modified thermoplastic resins obtained by modifying these.
The thermoplastic resin of the binder is the same kind of thermoplastic resin and / or modified thermoplastic resin as the resin (for example, thermoplastic resin A and / or thermoplastic resin B) that covers the periphery of the continuous reinforcing fibers. After forming a molded product, the adhesiveness between the continuous reinforcing fiber such as glass fiber and the thermoplastic resin is improved, which is preferable.

As the binder resin, the adhesive between the continuous reinforcing fiber and the thermoplastic resin coating the continuous reinforcing fiber is further improved, and when the sizing agent is attached to the glass fiber as an aqueous dispersion, the ratio of the emulsifier component is set. A modified thermoplastic resin is preferable from the viewpoint of reducing or eliminating the need for an emulsifier.
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 for the binder include a modified polyolefin resin, a modified polyamide resin, a modified polyester resin, and the like.

  Examples of the modified polyolefin resin for the binder include a copolymer of an olefin monomer such as ethylene and propylene and a monomer copolymerizable with an olefin monomer such as an unsaturated carboxylic acid, and the like. it can. A random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid may be used, or a graft copolymer obtained by grafting an unsaturated carboxylic acid to an olefin may be used.

Examples of the olefin monomer of the modified polyolefin resin include ethylene, propylene, 1-butene and the like. 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, and mesaconic acid. Unsaturated 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 monomer components used for copolymerization is 100% by mass, the olefin monomer is 60 to 95% by mass, and the olefin monomer. It is preferable that it is 5-40 mass% of monomers copolymerizable with olefin-type monomer, and it is more preferable that it is 15-30 mass% of monomers copolymerizable with olefin-type monomer 70-85 mass%.
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-based resin as the 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 alkalis such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine; and the like.
The weight average molecular weight of the modified polyolefin resin of 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.

Examples of the modified polyamide resin of the binder include modified polyamide compounds in which a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component is introduced into the molecular chain, and can be produced by a known method.
Examples of the method for introducing a polyalkylene oxide chain into the molecular chain include a method of copolymerizing a part or all of polyethylene glycol, polypropylene glycol or the like with diamine or dicarboxylic acid. Examples of the method of introducing a tertiary amine component include a method of copolymerizing aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam, and the like.

Examples of the modified polyester resin of the binder include a resin of a polycarboxylic acid or anhydride thereof and a polyol, and a resin having a hydrophilic group in a molecular skeleton including a terminal. Can be manufactured. 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 acid, sulfonate-containing aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, and trifunctional or higher polycarboxylic acid.

Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.
Examples of the sulfonate-containing aromatic dicarboxylic acid include sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoorthophthalate.
Examples of the aliphatic dicarboxylic acid or alicyclic dicarboxylic acid include fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, and succinic anhydride. And maleic anhydride.
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. In addition, 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 and trifunctional or higher functional polyols.
Examples of the diol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Examples thereof include 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 monomer components used for the copolymerization is 100% by mass, and the polycarboxylic acid or its anhydride is 40 to 60 mass. %, Polyol is preferably 40 to 60% by mass, more preferably 45 to 55% by mass of polycarboxylic acid or its anhydride, and 45 to 55% by mass of polyol.
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 the thermoplastic resin used as the binding agent may be used alone or in combination of two or more.
Select from acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary and / or tertiary amines, based on 100% by weight of the binder. It is preferable to use 50% by mass or more, and more preferable to use 60% by mass or more of the 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 is 0.1 to 2% by mass of the silane coupling agent, 0.01 to 1% by mass of the lubricant, and 1 to 25% by mass of the binding agent. It is preferable to contain, 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 0.1 to 2% by mass from the viewpoint of improving the sizing property of the glass fiber, improving the interfacial adhesive strength, and improving the mechanical strength of the molded product. It is preferably 0.1 to 1% by mass, more preferably 0.2 to 0.5% by mass.
The blending amount of the above-mentioned lubricant in the sizing agent for glass fibers is preferably from the viewpoint of giving 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 molded product. It is as follows.
The blending amount of the binding agent in the sizing agent for glass fibers is preferably 1 to 25% by mass, more preferably from the viewpoint of controlling the sizing property of glass fibers and improving the interfacial adhesive strength and improving the mechanical strength of the molded product. It is 3-15 mass%, More preferably, it is 3-10 mass%.

--Usage of sizing agent for glass fiber--
The sizing agent for glass fibers may be adjusted to 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 resin composite material in the method of the present embodiment is obtained by using a known method such as a roller-type applicator in the known glass fiber manufacturing process to convert the sizing agent into a glass fiber. It is obtained continuously by drying the glass fiber produced by applying.
The total mass of the silane coupling agent, lubricant and binder in the sizing agent is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and more preferably 0.2 to 2% by mass with respect to 100% by mass of the glass fiber. Preferably it is 0.2-1 mass%. From the viewpoint of controlling the converging property of glass fibers and improving the interfacial adhesive strength, the total mass is preferably 0.1% by mass or more. Moreover, it is preferable that it is 3 mass% or less from a viewpoint of the tensile breaking strength improvement of the splicing yarn by an air splicer, and the openability improvement in a fiber mixing process.

  When carbon fiber is selected as the continuous reinforcing fiber, the sizing agent preferably includes a lubricant and a binding agent, and more preferably includes only the lubricant and the 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, a material described in JP-A-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.

-Number of single yarns of continuous reinforcing fibers-
The number of single yarns of continuous reinforcing fibers is preferably 30 to 15,000 from the viewpoints of openability at the time of fiber mixing and handleability.

-Thermoplastic resin A-
As the thermoplastic resin A contained in the resin composite material, those usually used for molded articles containing continuous reinforcing fibers can be used. The thermoplastic resin A is preferably a crystalline resin from the viewpoint that it can be processed into a fibrous form.
Examples of the thermoplastic resin A include polyolefin resins such as polyethylene and polypropylene; polyamide resins such as polyamide 6, polyamide 66 and polyamide 46; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate; Polyacetal resins such as oxymethylene; Polycarbonate resins; Polyether ketones; Polyether ether ketones; Polyether sulfones; Polyphenylene sulfides; Thermoplastic polyether imides; Thermoplastic fluororesins such as tetrafluoroethylene-ethylene copolymers; And a modified thermoplastic resin obtained by modifying these, preferably at least one thermoplastic resin selected from the group consisting of continuous fibers obtained by melt spinning the thermoplastic resin. Theft is more preferable.
Among them, polyolefin resin, modified polyolefin resin, polyamide resin, polyester resin, polyether ketone, polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, and thermoplastic fluorine resin are preferable. From the viewpoints of mechanical properties and versatility, polyolefin resins, modified polyolefin resins, polyamide resins, and polyester resins are more preferable. From the viewpoint of thermal properties, polyamide resins and polyester resins are more preferable. Further, from the viewpoint of durability against repeated load loading, a polyamide-based resin is more preferable, and polyamide 66 can be suitably used.
The said thermoplastic resin A can be used individually by 1 type or in combination of multiple.

--- 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 include polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, and the like. A polyester-type resin may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  The polyester resin may be a homopolyester or a copolyester. In the case of a copolyester, a homopolyester suitably copolymerized with a third component is preferred. Examples of the third component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, adipic acid, sebacic acid, Examples thereof include dicarboxylic acid components such as phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid. In addition, polyester resins using raw materials derived from biomass resources can be used, for example, aliphatic polyester resins such as polylactic acid, polybutylene succinate, polybutylene succinate adipate, and polybutylene adipate terephthalate. Aromatic polyester resins and the like can be mentioned.

--- Polyamide resin--
The polyamide-based resin means a polymer compound having a —CO—NH— (amide) bond in the main chain.
Examples of polyamide resins 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. Is mentioned. 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 pyrrolidone, caprolactam, undecane lactam, and dodecalactam.
Examples of ω-aminocarboxylic acid include ω-amino fatty acid which is a ring-opening compound of lactam with water.
The lactam or ω-aminocarboxylic acid may be condensed using two or more monomers in combination.

  Examples of the diamine (monomer) include linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; branched aliphatic diamines such as 2-methylpentanediamine and 2-ethylhexamethylenediamine; p -Aromatic diamines such as phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine;

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

  Examples of polyamide resins include polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecanamide), polyamide 12 (polydodecanamide), and polyamide 46 (polytetramethylene adipamide). ), Polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), and Examples thereof include copolymer polyamides containing these as constituent components.

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

  The thermoplastic resin A may be a fiber. For example, the resin composite material may be composed of a mixed yarn obtained by mixing continuous reinforcing fibers and fibers of the thermoplastic resin A. For example, in a mixed fiber of continuous glass fiber and polyamide fiber, a thermoplastic resin such as polyamide is melted after hot pressing to become a matrix material of a resin composite material. Examples of the fibers of the thermoplastic resin A include polyamide fibers and polyester fibers.

-Form of resin composite material-
The form of the material of the resin composite material is not particularly limited, and a prepreg in which a continuous reinforcing fiber is impregnated with a continuous reinforcing fiber and a fabric including a composite yarn of a fiber of a thermoplastic resin A, a composite yarn, and the like. Shape, sheet shape, film shape, powder shape, granular shape, pellet shape, and the like. From the viewpoint of shape followability in the mold, operability, and shape flexibility, a fabric shape is preferable.

Examples of the form of the fabric include woven fabric, knitted fabric, and non-woven fabric. It does not specifically limit as a method of obtaining a fabric, The well-known method for producing the suitable fabric selected according to the use and the objective can be used.
For example, the woven fabric may use a weaving machine such as a shuttle loom, a rapier loom, an air jet loom, a water jet loom, etc., and may contain a composite yarn at least partially. Among them, it is preferable to obtain the yarn by driving the weft into the warp in which the fibers including the composite yarn are arranged.
The knitted fabric is obtained by knitting a fiber including a composite yarn at least partially using a knitting machine such as a circular knitting machine, a flat knitting machine, a tricot knitting machine, and a raschel knitting machine.
Non-woven fabric is a sheet-like fiber assembly called a web made of fibers containing at least a portion of composite yarn, and then the physical action such as a needle punch machine, stitch bond machine, columnar flow machine, etc. It is obtained by bonding fibers with an adhesive.
About the form of other fabrics, the method of Unexamined-Japanese-Patent No. 2015-101794 can be used suitably.
When a material in the form of a cloth is used as the material for the resin composite material, the material in the form of a cloth has irregularities on the surface of the material in the form of a plate. Unevenness is generated on the joining surface, the joining area between the resin composite material and the thermoplastic resin B is increased, and the anchor effect between the resin composite material and the thermoplastic resin B is manifested, whereby a higher joining strength tends to be obtained. It is in.

  As a material of the cloth-like resin composite material, a cloth using a mixed fiber is preferable, but a cloth using a thread in which a thermoplastic resin A powder is adhered to continuous reinforcing fibers (for example, glass fiber or carbon fiber). Further, a cloth-like continuous reinforcing fiber in which a thermoplastic resin A powder is dispersed or adhered, a film-like thermoplastic resin A and a cloth-like continuous reinforcing fiber or the like may be superposed. .

As a method for producing a blended yarn of continuous reinforcing fibers and fibers of thermoplastic resin A, a known method can be used. For example, continuous reinforcing fibers and / or fibers of thermoplastic resin A can be obtained by electrostatic force or fluid spraying. Examples of the method include a fiber opening and interlacing method in which a fiber is opened by an external force such as pressure, pressure applied to a roller, and the like, and then combined and aligned in a state where the fiber is opened. Among them, the fluid entanglement method (interlace) method is preferable from the viewpoints that the continuous reinforcing fibers can be prevented from being damaged, have excellent spreadability, and can be uniformly mixed. As the fluid entanglement method, two or more vortex turbulence zones with fluids such as air, nitrogen gas, and water vapor are made almost parallel to the yarn axis, and fibers are introduced into the zone to cause loops and crimps. A non-bulky yarn under a certain degree of tension, or a method in which only continuous reinforcing fibers or continuous reinforcing fibers and thermoplastic resin A fibers are opened together and then fluid entangled (fluid entanglement after opening) Law). In particular, it is preferable that the fiber of the thermoplastic resin A is subjected to false twisting in a process including thermal processing alone, and then continuously mixed in the same apparatus and mixed by a fluid entanglement method.
In addition, about the detail of the fiber mixing method, the method described in Unexamined-Japanese-Patent No. 2015-101794 can be used suitably.

  As the resin composite material, a molded material may be used. Examples of the molding method include a method in which a material containing at least the continuous reinforcing fiber and the thermoplastic resin A is set in a mold, the mold is closed and compressed, and molding is performed. The pressure applied to the resin composite material is preferably 1 MPa or more, more preferably 3 MPa or more. Moreover, you may degas etc. in the case of shaping.

  The thickness of the resin composite material is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, from the viewpoint of obtaining a molded article having excellent bonding strength.

(Thermoplastic resin B)
As the thermoplastic resin B, a resin generally used in injection molding can be used.
Examples of the thermoplastic resin B include rubber-reinforced styrene resins such as polystyrene, high impact polystyrene, medium impact polystyrene, styrene-acrylonitrile copolymer (SAN resin), acrylonitrile-butyl acrylate rubber-styrene copolymer (AAS). Resin), acrylonitrile-ethylenepropyl rubber-styrene copolymer (AES), acrylonitrile-polyethylene chloride-styrene copolymer (ACS), ABS resin (for example, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene- Styrenic resins such as alpha methyl styrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene copolymer): polymethyl methacrylate (PMMA), etc. Kuryl resin: Polyethylene such as low density polyethylene (LDPE) and high density polyethylene (HDPE), Olefin resin such as polypropylene (PP): Vinyl chloride resin such as polyvinyl chloride and polyvinylidene chloride: Ethylene vinyl vinyl acetate Vinyl chloride resins such as copolymers and ethylene vinyl chloride copolymers: Polyester resins such as polyethylene terephthalate (PETP, PET), polybutylene terephthalate (PBTP, PBT), wholly aromatic polyesters: polycarbonate (PC), modified Polycarbonate resins such as polycarbonate: Polyamide resins such as polyamide 66, polyamide 6 and polyamide 46: Polyacetal (POM) resins such as polyoxymethylene copolymers and polyoxymethylene homopolymers: Other resins Ziniering resin, super engineering resin (for example, polyethersulfone (PES), polyetherimide (PEI), thermoplastic polyimide (TPI), polyetherketone (PEK), polyetheretherketone (PEEK), polyphenylene sulfide (PSU) Etc.); Cellulose derivatives such as cellulose acetate (CA), cellulose acetate butyrate (CAB), ethyl cellulose (EC): liquid crystal polymers such as liquid crystal polymers and liquid crystal aromatic polyesters (LCP): thermoplastic polyurethane elastomers (TPU) , Thermoplastic styrene butadiene elastomer (SBC), Thermoplastic polyolefin elastomer (TPO), Thermoplastic polyester elastomer (TPEE), Thermoplastic vinyl chloride elastomer (TPVC), thermoplastic polyamide elastomer (TPAE), etc., thermoplastic elastomers: polyarylate; polyphenylene ether; modified polyphenylene ether; polysulfone; The thermoplastic resin B can be used alone or in combination.

The thermoplastic resin B is preferably similar to the thermoplastic resin A, and more preferably the same kind of thermoplastic resin, from the viewpoint of further excellent bonding strength with the resin composite material. The melting point (TmB) of the thermoplastic resin B may be higher or lower than the melting point (TmA) of the thermoplastic resin A, but is preferably lower than the melting point (TmA) of the thermoplastic resin A.
Further, from the viewpoint of further improving the bonding strength with the resin composite material, the melting point (TmA) of the thermoplastic resin A and the melting point (TmB) of the thermoplastic resin B are preferably close, and the difference between TmA and TmB is 100. It is more preferable that the temperature is within the range of 45C, and it is further preferable that the temperature is within the range of 45C.
Specifically, when the thermoplastic resin A is polyamide 66, the thermoplastic resin B is preferably a polyamide-based resin, and more preferably polyamide 66.

The thermoplastic resin B may be used by mixing with various fillers.
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, the sizing agent may be used, and the sizing agent preferably contains the silane coupling agent, the lubricant, and the binding agent.

(Mold)
Examples of the mold include a mold composed of two molds, an upper mold and a lower mold, and a mold composed of three or more molds. Among these, a mold composed of two molds, an upper mold and a lower mold, is preferable from the viewpoint of reducing the number of parting lines between the molds and reducing changes in temperature and pressure in the mold cavity.
The mold may be provided with other components, a temperature adjustment mechanism, a thermometer, a pressure gauge, a vent function, and the like.

A steel part having a thermal conductivity of 50 W / m · K or more is preferable for the cavity portion where heating and cooling of the upper mold of the mold is repeated, and a steel material having a thermal conductivity of 100 W / m · K or more is more preferable. . Examples of the steel material include carbon steel, copper alloy, and aluminum alloy.
In addition, in this specification, heat conductivity means the value measured by JISH7801.

The shape of the cavity of the mold, which is an internal space formed when the mold is closed, is not particularly limited, and can be appropriately selected depending on the molded product to be manufactured.
The cavity surface of the mold may have a shape such as a flat surface, an uneven surface, a corrugated surface, or a combination thereof.

  It is preferable that at least one of the molds constituting the mold (for example, an upper mold and a lower mold) is provided with a temperature adjustment mechanism such as a heating mechanism and / or a cooling mechanism. Examples of the heating mechanism include a mechanism that causes a heat medium or the like to flow through a heat medium passage in the mold, a mechanism that incorporates a heater in the mold, and the like. Examples of the cooling mechanism include a mechanism that allows a coolant to flow through the coolant passage in the mold, a mechanism that incorporates a cooling device in the mold, and the like.

In the arrangement step, the number of the resin composite materials arranged in the cavity of the mold is not particularly limited, and may be one or plural. Moreover, you may arrange | position to a part of metal mold | die cavity, and may arrange | position to the whole metal mold cavity.
Only the resin composite material may be disposed in the mold cavity, or may be disposed together with other members. From the viewpoint of joining the thermoplastic resin B to be injected and filled, it is preferable that the resin composite material is at least in contact with the position where the thermoplastic resin B is injected into the mold cavity. For example, in the example of FIG. 1 in which the thermoplastic resin B is injected from the lower mold, the resin composite material is preferably arranged so as to be in contact with at least the cavity surface of the lower mold.

In the arrangement step, the mold temperature is not higher than the melting point (TmA) of the thermoplastic resin A, and preferably not higher than TmA-15 ° C.
Moreover, it is preferable that the temperature of the metal mold | die of an arrangement | positioning process is TmA-80 degreeC or more from a viewpoint that a shaping | molding cycle becomes quick and production efficiency improves further.

[Injection filling process]
In the manufacturing method of the present embodiment, after the resin composite material is disposed, the mold is opened.
The open state means a state where there is a slight gap connecting the outside and the inside of the mold cavity, and a state where there is a gap connecting the outside of the mold and the inside of the cavity is preferable, along the parting line More preferably, there is a communicating gap. Examples of the slight gap that connects the outside and the inside of the mold cavity include, for example, a state where at least part of the parting line between the molds constituting the mold is not adhered, the outside and the inside of the cavity communicated, and steam Further, there may be a state where there is a pipe for supplying carbon dioxide or the like into the cavity. Note that when the pressure does not escape from the inside of the cavity to the outside through the gap, it is not included in the state where the mold is opened.
When injection molding is performed with the mold closed, the pressure loss is large, and the fiber direction of the continuous reinforcing fibers in the continuous composite material may shift. By performing injection molding in the open state, it is possible to obtain a molded product having a small appearance with a low pressure loss, a small deviation of continuous reinforcing fibers, and a low anisotropy of the thermoplastic resin B to be injected.

As the above-mentioned state of opening, the size of opening (the volume of the gap formed between the projection surface of the resin composite material put into the mold and the molding surface) is at least twice the injection volume of the thermoplastic resin B. It is preferable that
There may be one gap or a plurality of gaps.

  During the injection filling process, the size of the opening may be changed. For example, the opening gap may be gradually reduced.

In the injection filling process, the thermoplastic resin B is one of the resin composite materials in the vertical mold molding machine from the viewpoint of cost reduction due to the reduction of discarded materials, the improvement of the bondability between the resin composite material and the thermoplastic resin B, and the like. From the viewpoint of easily laminating the thermoplastic resin B on one side of the portion and from the viewpoint of applying injection holding pressure into the cavity until the thermoplastic resin A is solidified, it is preferable to perform injection filling via a hot runner.
In the injection filling step, the temperature of the thermoplastic resin B to be filled is preferably TmB + 10 to TmB + 60 ° C., more preferably TmB + 25 to TmB + 50 ° C. from the viewpoint of the bondability between the resin composite material and the thermoplastic resin B. is there.

In the injection filling step, it is preferable that the thermoplastic resin B is injection-filled on at least a part of the surface of the resin composite material, and is injection-filled on at least a part of one surface of the resin composite material. More preferably, injection filling is performed on one entire surface.
In addition, injection filling may be performed at a plurality of locations on the surface of the resin composite material.

[Jointing process]
In the method for manufacturing a molded product according to this embodiment, the mold is closed after the injection filling of the thermoplastic resin B is completed.
The mold may be closed simultaneously with the end of injection filling, or the mold may be closed with an interval (for example, an interval within 5 seconds). Among these, from the viewpoint of obtaining a molded article with even better adhesive strength, it is preferable to close the mold simultaneously with the end of injection filling, and the process of closing the mold, heating a part of the mold, and compression molding is continued. More preferably.

Closing the mold means that the pressure does not escape from the inside of the cavity. For example, the mold is tightened, the tube that connects the outside and the cavity is closed, and the outside and the cavity are in communication. Examples of the method include applying pressure to the tube with a medium such as steam or carbon dioxide.
The joining step is preferably performed with the mold closed.

In the joining step, the temperature of a part of the mold is raised rather than raising the temperature of the entire mold.
A part of the mold is preferably a mold on the surface side of the resin composite material opposite to the surface on which the thermoplastic resin B is injected and filled. The mold is preferably provided with a heating mechanism and a cooling mechanism.
The mold on the surface side where the thermoplastic resin B is injection-filled is preferably not provided with a cooling mechanism, and is preferably provided with a hot runner, an ejector pin, and the like.

For example, when a thermoplastic resin B is injected and filled through a hot runner in a lower mold in a mold composed of an upper mold and a lower mold as shown in FIG. 1, a part of the mold is An upper mold is preferred.
Usually, from the viewpoint of production efficiency, an injection mold includes a heater and a cooler for heating and cooling the mold. In particular, since raising and lowering the temperature greatly affects production efficiency, a heater and a cooler are incorporated in the entire mold. For this reason, hot runners, eject pins, etc. cannot be provided in the mold, and there is a limit to the degree of freedom in designing products and molds. In the method for producing a molded product of the present invention, since a part of the mold is heated, it is not necessary to provide a cooler other than the part to be heated, so that a product or a mold can be designed freely.

In the joining step, the part of the mold is preferably heated to the melting point of the thermoplastic resin A or more, more preferably TmA + 10 ° C. or more, from the viewpoint of the joining property between the resin composite material and the thermoplastic resin B. More preferably, it is TmA + 30 degreeC or more.
Also. From the viewpoint of suppressing deterioration of the resin, TmA + 50 ° C. or lower is preferable.

In the joining step, the resin composite material and the thermoplastic resin B can be joined by compression molding the resin composite material and the thermoplastic resin B after heating a part of the mold.
In the method for producing a molded product according to the present invention, the mold on the resin composite material side is heated (FIG. 1 (e)), so that the thermoplastic resin A in the resin composite material is melted and bonded to the thermoplastic resin B. By doing so, a molded product having excellent bonding strength can be obtained.

  The pressure applied to the resin composite material during the compression molding is appropriately selected depending on the shape of the molded product, and may be, for example, 1 to 30 MPa.

When holes such as a hole that connects the hot runner and the outside and the cavity are on the cavity surface, after injection filling of the thermoplastic resin, the pressure on the holes of the hot runner (for example, equivalent to the press pressure during vapor compression molding) It is preferable to apply an injection holding pressure. Further, the hole may be closed with a lid or the like.
Here, when the press pressure is larger than the injection holding pressure, the thermoplastic resin A in the resin composite material flows out, and a non-reinforced resin portion containing no reinforcing fiber is formed. It tends to be vulnerable. On the other hand, when the injection holding pressure is larger than the pressing pressure, the orientation of the continuous reinforcing fibers is lost due to the injection holding pressure, and the appearance of the molded product tends to be disturbed.
In addition, it is not necessary that the pressures are the same, and includes a case where there is a pressure difference of ± 10 MPa, preferably ± 5 MPa. Here, the injection holding pressure is a holding pressure at the time of injection molding.

  After the joining step, the mold is cooled and the molded product is taken out, whereby the molded product of the present embodiment can be obtained. By cooling only some of the heated molds, the energy cost can be reduced.

  The molded product obtained by the method of the present embodiment can be suitably used for structural material applications such as aircraft, vehicles, and construction materials. As a vehicle application, 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.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
"Production method of resin composite material"
Glass fibers having a fineness of 685 dtex and 400 single yarns were used as continuous reinforcing fibers.
As the thermoplastic resin A, polyamide 66 fibers having a fineness of 144 dtex and 144 single yarns not subjected to the entanglement treatment were used. The melting point of the thermoplastic resin A was 265 ° C.
Two bundles of the above glass fibers and two bundles of the above PA66 fibers were combined and aligned, and then supplied substantially vertically to the fluid entanglement nozzle and fluid entangled to obtain a composite yarn.
Using the obtained composite yarn as warp and weft, a woven fabric (fabric: material of resin composite material) was woven.

Next, using the woven fabric, a flat molded product (length 250 mm, width 250 mm, wall thickness 2.0 mm) was produced according to the following procedure. The molded product is composed of a compression molded part (1.4 mm) made of a resin composite material and an injection molded part (0.6 mm) made of a thermoplastic resin B, and 1.4 mm on one side is a resin composite material. It is configured. 1A to 1F show a manufacturing process of a molded product including injection filling, joining, and compression molding processes.
As the molding machine, a vertical injection compression molding machine (S100V-8A manufactured by Toshiba Machine) was used. Moreover, the metal mold | die consisting of the upper metal mold | die provided with the heating mechanism and the cooling mechanism, and the lower metal mold | die provided with the heating mechanism, the hot runner, and the ejector pin was used.

“Cloth cutting step”: The woven fabric (fabric) produced as described above was cut into a width of 250 mm and a length of 250 mm.
“Arrangement process”: Open the mold heated to 200 ° C., set the above five fabrics at a predetermined position in the mold (FIG. 1A), and then mold the upper mold from the top of the fabric. The upper mold was brought closer to the lower mold until the surface was 5 mm away (opened state) (FIG. 1B). The PL surface (parting line surface) between the upper mold and the lower mold was separated by 5 mm, and the cross-sectional area of the gap connecting the outside and the inside of the cavity was 313 cm ² .
“Jointing step”: After the above opening, a resin composition of polyamide 66 resin [trade name: Leona (registered trademark) 14G33] containing 33% of short fibers GF, a cylinder set temperature of 290 ° C., an injection pressure of 20 MPa, an injection speed of 50 mm / In seconds, injection filling is performed through a hot runner set at a temperature of 290 ° C. (FIG. 1C), and the mold is clamped with a clamping force of 65 t immediately before the completion of injection filling (FIG. 1D). An injection holding pressure of 10 MPa was applied through the runner. Next, after the temperature of the upper mold was raised to 300 ° C., which is equal to or higher than the melting point of the thermoplastic resin (A) (FIG. 1 (e)), compression molding was performed by holding for 3 minutes.
“Cooling step”: Next, the upper mold was cooled to 200 ° C. and cooled and solidified (FIG. 1 (f)). The injection holding pressure was maintained at 10 MPa up to 200 ° C., which is not higher than the solidification temperature of the thermoplastic resin (A).
“Mold release step”: The mold was opened, and a flat molded product was taken out using an ejector pin.

  As a result of observation, a sample with a beautiful appearance without meandering or opening of continuous reinforcing fibers was obtained. As a result of the bending test, only the back side where the bending indenter, which is the portion with the largest elongation, was in contact with the test piece was broken and the test was completed.

(Example 2)
In Example 2, the mold used in Example 1 was used. However, assuming that the mold had no hot runner, the temperature of the hot runner was set to 200 ° C., the same as the lower mold in which the hot runner was incorporated. .
“Cloth cutting step”: The woven fabric (fabric) produced as described above was cut into a width of 250 mm and a length of 250 mm.
“Arrangement process”: The upper and lower molds are opened while being heated to 200 ° C., the five fabrics are set at predetermined positions in the mold, and then the PL surfaces (parties) of the upper mold and the lower mold are arranged. The upper mold was brought close to the lower mold up to a position 5 mm away from the grinding line). The cross-sectional area of the gap communicating with the outside and the inside of the cavity was 313 cm ² .
“Jointing step”: After the above opening, a resin composition of polyamide 66 resin [trade name: Leona (registered trademark) 14G33] containing 33% of short fibers GF, a cylinder set temperature of 290 ° C., an injection pressure of 20 MPa, an injection speed of 50 mm / Injection filling was performed in seconds, injection filling was performed via a hot runner set at a temperature of 200 ° C., and the mold was clamped with a clamping force of 65 t immediately before the completion of injection filling, and an injection holding pressure of 10 MPa was applied for 10 seconds.
While the nozzle of the injection molding machine was still touching the mold, the mold temperature was raised to 300 ° C., which is higher than the melting point of the thermoplastic resin A, and then held for 3 minutes to perform compression molding.
“Cooling step”: Next, the mold was cooled to 200 ° C. and cooled and solidified.
“Mold release step”: The mold was opened, and a flat molded product was taken out using an ejector pin.

  As a result of observation, a sample with a beautiful appearance without meandering or opening of continuous reinforcing fibers was obtained. Further, as a result of the bending test, the test piece was terminated by breaking the most stretched portion, and when the interface was confirmed after the test was completed, only a very small part of the interface was broken.

(Comparative Example 1)
In Comparative Example 1, the parting surfaces of the upper mold and the lower mold were bonded in the woven fabric (fabric) placement process, and the mold was clamped with a clamping force of 65 t until the mold release process. Moreover, since pressure loss is large when injection is performed with the mold completely closed, the resin composition was injection filled at an injection pressure of 50 MPa and an injection speed of 50 mm / sec. Except that, molding was performed under the same conditions as in Example 1.

  As a result of the observation, a sample in which the continuous reinforcing fibers of the fabric meandered greatly due to the injection pressure of the injection resin, and the appearance was not good with a mesh opening was obtained. Further, as a result of the bending test, the test was terminated by breaking from the interface.

(Comparative Example 2)
In Comparative Example 2, a mold was used in which both sides of the mold could be heated, but the layout of the eject pins and hot runners could not be performed by the heater and cooling water pipe embedded in the entire mold.
“Cloth cutting step”: The woven fabric (fabric) produced as described above was cut into a width of 250 mm and a height of 250 mm.
“Arrangement step”: The upper and lower molds were opened in a state of being heated to 200 ° C., five of the fabrics were set at predetermined positions in the mold, and the mold was clamped with a mold clamping force of 100 t.
“Jointing step”: After mold clamping, a resin composition of polyamide 66 resin [trade name: Leona (registered trademark) 14G33] containing 33% short fibers GF, a cylinder set temperature of 290 ° C., an injection pressure of 50 MPa, and an injection speed of 100 mm / sec. Then, the lower side of the resin composite material was injected and filled, and an injection holding pressure of 10 MPa was applied for 10 seconds. With the nozzle of the injection molding machine still touching the mold, the temperature of both the upper and lower molds was raised to 300 ° C., which is equal to or higher than the melting point of the thermoplastic resin A, and held for 3 minutes to perform compression molding. .
“Cooling step”: Next, the mold was cooled to 200 ° C. and cooled and solidified.
“Mold release step”: The mold was opened, and a flat composite molded product was manually taken out.

  As a result of the observation, a sample in which the continuous reinforcing fibers of the fabric meandered greatly due to the injection pressure of the injection resin, and the appearance was not good with a mesh opening was obtained. As a result of the bending test, the interface was completely broken and the test was completed.

[Evaluation]
The molded article obtained in the examples and comparative examples was subjected to the following measurements.
(Slip of resin composite material)
The deviation of the resin composite material was confirmed to have the following two points.
1. 1. Continuous reinforcing fiber meandering Opening of continuous reinforcing fiber When either of the above two points occurred in the molded product, it was evaluated as “x” (defect), and when none occurred, it was evaluated as “◯” (good).

(Production efficiency)
Production efficiency was judged based on whether ejector pins and hot runners could be incorporated into the mold. If an ejector pin can be incorporated, the mold release speed will be improved and the production efficiency will be improved. In addition, if a hot runner can be incorporated, the runner will be eliminated, eliminating the process of cutting the molded runner, leading to improved production efficiency.
When both ejector pins and hot runners are used with either mold, "◎" (best), when either ejector pins or hot runners are used, "○" (good), neither is used The case was evaluated as “x” (defect).

(Interface strength)
The interfacial strength was evaluated under the following conditions according to ISO 178 except for the shape of the test piece.
The molded product was cut into a rectangular shape with a length of 100 mm and a width of 10 mm, and a bending test was performed under the following conditions.
・ Test environment: 23 ° C, 50RH%
・ Test speed: 1 mm / min
-Between spans: 32mm
-Equipment used: Instron 50kN (Instron)
FIG. 2 shows an outline of this bending strength test. In FIG. 2, reference numeral 7 denotes the above-described test piece. A bending test was performed by applying a load in the direction of the arrow from the thermoplastic resin material B side of the test piece 7 through the bending indenter 8.
In the bending test, when the applied load is reduced by 20%, the test ends, and the interface formed by the resin composite material and the thermoplastic resin B after the test ends is observed with a microscope (trade name “VHX1000”). It was evaluated.
In the table, “◎” (excellent) indicates that there was no destruction at the interface at the end of the test, “◯” (good) indicates that there was partial destruction at the interface, and “x” (defect). Indicates that the interface is completely destroyed.

1 Resin composite material 2 Thermoplastic resin B
3 Upper mold 4 Lower mold 41 Hot runner 5 Cavity 6 Gap 7 Test piece 8 Bending indenter 9 Support rod

Claims (5)

A method for producing a molded article in which a thermoplastic resin B is laminated on at least a part of a surface of a resin composite material containing continuous reinforcing fibers and a thermoplastic resin A,
An arranging step of arranging the resin composite material in a cavity of a mold having a melting point or less of the thermoplastic resin A;
An injection filling step of injecting and filling the thermoplastic resin B onto at least a part of the surface of the resin composite material in a state where the mold is opened;
The mold is closed, a part of the mold is heated to the melting point or higher of the thermoplastic resin A, and the resin composite material and the thermoplastic resin B are compression molded to form the resin composite material and the thermoplastic resin. A joining step for joining B;
The manufacturing method of the molded article characterized by including.   The method for producing a molded product according to claim 1, wherein a part of the mold is a mold on the surface side of the resin composite material opposite to the surface on which the thermoplastic resin B is injected and filled.   The manufacturing method of the molded product of Claim 1 or 2 with which the said thermoplastic resin B is injection-filled via a hot runner in the said injection filling process.   The manufacturing method of the molded article of Claim 3 which applies the injection holding pressure equivalent to the press pressure at the time of the said compression molding through the hot runner after the injection filling of the said thermoplastic resin B.   The manufacturing method of the molded product of any one of Claims 1-4 whose said metal mold | die is a metal mold | die which consists of an upper metal mold | die and a lower metal mold | die.

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