JP7650196B2 - Continuous fiber reinforced thermoplastic resin composite material and its manufacturing method - Google Patents

Description

The present invention relates to a continuous fiber reinforced thermoplastic resin composite material and a method for producing the same.

Composite material molded articles in which a reinforcing material such as glass fiber is added to a matrix resin material are used for structural parts of various machines and automobiles, pressure vessels, tubular structures, etc. In particular, from the viewpoint of strength, continuous fiber reinforced resin composite materials in which the reinforcing fiber is continuous fiber are desired.
It is known that voids in a continuous fiber reinforced resin composite material affect the strength, and it is important that the resin is sufficiently impregnated into the fibers. In addition, in order to reduce the fixed cost of producing a continuous fiber reinforced resin composite material, it is essential to impregnate the fibers with the resin in a short process. In order to accelerate the impregnation of the fibers with the resin, a method in which a silane coupling agent or a surfactant is applied to the aramid fiber (see, for example, Patent Document 1), a method in which the resin viscosity is set to a specific range by kneading two types of resin (see, for example, Patent Document 2), and a method in which the surface free energy of the fiber is increased to promote the wetting of the resin (see, for example, Patent Document 3) have been proposed.

International Publication No. 2007/055017 International Publication No. 2019/189820 Patent No. 6356497

However, in all of the above-mentioned conventional continuous fiber-reinforced resin composite materials, the resin does not impregnate the continuous reinforcing fibers (impregnation speed) sufficiently, and further improvement is desired in terms of productivity. In addition, when voids exist between fiber bundles or fiber layers, there is room for improvement in that physical properties such as strength, elastic modulus, and impact are insufficient.

In view of the state of the prior art, the problem that the present invention aims to solve is to provide a method for producing a continuous fiber reinforced thermoplastic resin composite material that has good impregnation of the continuous reinforcing fibers with a thermoplastic resin and is highly productive. Another problem that the present invention aims to solve is to provide a continuous fiber reinforced thermoplastic resin composite material that has excellent impact properties.

The present inventors have intensively studied and conducted repeated experiments to solve such problems, and as a result, have unexpectedly discovered that the above problems can be solved by setting the ratio (ΔW _floc /MFR) of ΔW _floc [mJ/m ² ] calculated from the surface free energy of the thermoplastic resin and the continuous reinforcing fibers to the melt flow rate value MFR [g/10 min] of the thermoplastic resin within a specific range, thereby completing the present invention.

That is, the present invention is as follows.
[1]
The method includes applying an aqueous solution containing a silane coupling agent to the continuous reinforcing fibers, drying the aqueous solution, applying a sizing agent containing a lubricant and a binder, and drying the continuous reinforcing fibers , and impregnating the continuous reinforcing fibers with a thermoplastic resin.
When the dispersion term and polar term of the surface free energy of the thermoplastic resin are γ _pol ^d and γ _pol ^p , respectively, and the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber are γ _fib ^d and γ _fib ^p , respectively, ΔW _floc [mJ/ _m 2 ] is expressed by ΔW _floc = 2 (((γ _pol ^d ) ^1/2 - (γ _fib ^{d ) 1/2} ) ² + ((γ _pol ^p ) ^1/2 - (γ fib p ) ^{1/2 ) 2} ),
The melt flow rate (measured at melting point + 5°C) of the thermoplastic resin is MFR [g / 10 min],
A method for producing a continuous fiber reinforced thermoplastic resin composite material, characterized in that the relationship ΔW _floc /MFR≦0.614 [mJ·10 min /m ² ·g] is satisfied.
[2]
The method for producing a continuous fiber reinforced thermoplastic resin composite material according to [1], wherein the continuous reinforcing fibers are inorganic fibers.
[3]
The method for producing a continuous fiber reinforced thermoplastic resin composite material according to [2], wherein the inorganic fibers are glass fibers and/or carbon fibers.
[4]
The method for producing a continuous fiber reinforced thermoplastic resin composite material according to any one of [1] to [3], wherein the thermoplastic resin is a polyamide-based resin.
[5]
Contains a thermoplastic resin and continuous reinforcing fibers,
When the dispersion term and polar term of the surface free energy of the thermoplastic resin are γ _pol ^d and γ _pol ^p , respectively, and the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber are γ _fib ^d and γ _fib ^p , respectively, ΔW _floc [mJ/ _m 2 ] is expressed by ΔW _floc = 2 (((γ _pol ^d ) ^1/2 - (γ _fib ^{d ) 1/2} ) ² + ((γ _pol ^p ) ^1/2 - (γ fib p ) ^{1/2 ) 2} ),
The melt flow rate (measured at melting point + 5°C) of the thermoplastic resin is MFR [g / 10 min],
A continuous fiber reinforced thermoplastic resin composite material, characterized in that it satisfies the relationship ΔW _floc /MFR≦0.614 [mJ· 10 min/m ² ·g].
[6]
The continuous fiber reinforced thermoplastic resin composite material according to [5], wherein the continuous reinforcing fibers are inorganic fibers.
[7]
The continuous fiber reinforced thermoplastic resin composite material according to [6], wherein the inorganic fibers are glass fibers and / or carbon fibers.
[8]
The continuous fiber reinforced thermoplastic resin composite material according to any one of [5] to [7], wherein the thermoplastic resin is a polyamide-based resin.

According to the present invention, it is possible to provide a method for producing a continuous fiber reinforced thermoplastic resin composite material with good impregnation of the thermoplastic resin into the continuous reinforcing fibers and high productivity. In addition, according to the present invention, it is possible to provide a continuous fiber reinforced thermoplastic resin composite material with excellent impact properties.

1 is a graph showing the measurement results of the impregnation distance of continuous fiber reinforced thermoplastic resin composite materials obtained in Examples , Reference Examples , and Comparative Examples.

The following describes in detail the form for carrying out the present invention (hereinafter, referred to as the "present embodiment"). Note that the present invention is not limited to the following embodiment, and can be carried out in various modifications within the scope of the gist of the present invention.

[Method of manufacturing continuous fiber reinforced thermoplastic resin composite material]
A method for producing a continuous fiber reinforced thermoplastic resin composite material (hereinafter also simply referred to as a "continuous fiber reinforced resin composite material" or "composite material") of this embodiment includes impregnating a continuous reinforcing fiber with a thermoplastic resin, and when the dispersion term and polar term of the surface free energy of the thermoplastic resin are γ _pol ^d and γ _pol ^p , respectively, and the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber are γ _fib ^d and γ _fib ^p , respectively, ΔW floc [mJ/m 2 ] expressed by ΔW _floc = 2(((γ _pol ^d ) ^1/2 _- (γ _fib ^d ) ^1/2 ) ² + ((γ _pol ^p ) ^1/2 _- (γ _fib ^p ) ^1/2 ) ² ) and the value _MFR [g/ ¹⁰ min] of the melt flow rate of the thermoplastic resin (measured at melting point + 5°C) are expressed by: The composition is characterized in that it satisfies the relationship of _floc /MFR≦0.9 [mJ·10 min/m ² ·g].

The method for impregnating continuous reinforcing fibers with a thermoplastic resin to obtain a continuous fiber-reinforced thermoplastic resin composite material is not particularly limited, and various methods can be mentioned, including the following:

In one method, for example, the substrate that constitutes the continuous fiber reinforced resin composite material (e.g., a substrate made of continuous reinforcing fibers, a substrate made of thermoplastic resin) is cut or shaped to fit the desired composite material, and the required number of pieces or layers are stacked in consideration of the thickness of the desired product, and then set in a mold according to the mold shape.

The cutting of the substrate may be performed one by one, or may be performed after stacking a desired number of sheets. From the viewpoint of productivity, it is preferable to cut in a stacked state. The cutting method may be any method, for example, a water jet, a blade press machine, a hot blade press machine, a laser, a plotter, etc. Among them, a hot blade press machine is preferable because it has an excellent cross-sectional shape and further improves handling by welding the end faces when cutting a plurality of sheets stacked together. Although the appropriate cutting shape can be adjusted by repeating trial and error, it is preferable to set it by performing a simulation using CAE (computer aided engineering) according to the shape of the mold.
The substrate may be shaped by any method, for example, into a sheet-like shape.

After the substrate is set in the mold, the mold is closed and compressed. The temperature of the mold is then adjusted to a temperature equal to or higher than the melting point of the thermoplastic resin that constitutes the continuous fiber reinforced resin composite material, and the thermoplastic resin is melted and shaped. There are no particular restrictions on the mold clamping pressure, but it is preferably 1 MPa or higher, and more preferably 3 MPa or higher. The mold may also be clamped once to allow for gas release, etc., and the mold clamping pressure may be released once after compression molding. From the viewpoint of strength expression, the compression molding time is preferably as long as possible within the range in which the thermoplastic resin used is not thermally deteriorated, but from the viewpoint of productivity, it is preferably within 2 minutes, and more preferably within 1 minute.

Other methods include a method in which the substrate that constitutes the continuous fiber-reinforced resin composite material is continuously supplied using a double belt press or continuous compression molding device, heated above the melting point of the thermoplastic resin, compression molded at a given pressure, and cooled below the crystallization temperature or glass transition temperature of the thermoplastic resin.

In the production of continuous fiber reinforced thermoplastic resin composite materials, whether the thermoplastic resin can sufficiently impregnate the continuous reinforcing fibers in a short time is determined by the affinity between the thermoplastic resin and the continuous reinforcing fibers. The affinity here can be quantified by the closeness of the dispersion term and polar term of the surface free energy of the thermoplastic resin and the continuous reinforcing fibers, and can be expressed by ΔW _floc calculated by the following formula: ΔW _floc = 2 (((γ _pol ^d ) ^1/2 - (γ _fib ^d ) ^1/2 ) ² + ((γ _pol ^p ) ^1/2 - (γ _fib ^p ) ^1/2 ) ² )
γ _pol ^d : dispersion term of surface free energy of thermoplastic resin γ _pol ^p : polar term of surface free energy of thermoplastic resin γ _fib ^d : dispersion term of surface free energy of continuous reinforcing fiber γ _fib ^p : polar term of surface free energy of continuous reinforcing fiber ΔW _floc is considered to indicate the compatibility of resin and fiber. The larger the value of ΔW _floc , the greater the difference between the dispersion term and polar term of the thermoplastic resin and the continuous reinforcing fiber, so the energy required to create the resin-fiber interaction, that is, the energy required for impregnation, becomes larger, and the impregnation distance when measured at the same temperature and the same time becomes shorter (impregnation speed becomes slower). On the other hand, the smaller the value of ΔW _floc , the smaller the energy required for impregnation becomes, and the longer the impregnation distance when measured at the same temperature and the same time (impregnation speed becomes faster). Therefore, the smaller the value of ΔW _floc , the shorter the time it takes to impregnate the thermoplastic resin into the continuous reinforcing fiber, improving the productivity of the composite material.

ΔW _floc can be adjusted by appropriately adjusting the dispersion term and polar term of the surface free energy of the thermoplastic resin and the dispersion term and polar term of the surface free energy of the continuous reinforcing fibers.
In particular, the surface free energy of the continuous reinforcing fiber can be appropriately adjusted by surface treatment of the continuous reinforcing fiber. For example, when the surface treatment of the glass reinforcing fiber is performed using aminosilane as a silane coupling agent, the polar term of the surface free energy of the glass reinforcing fiber tends to be low. Conversely, when the surface treatment of the glass reinforcing fiber is performed using a silane coupling agent other than aminosilane, for example, when the surface treatment of the glass reinforcing fiber is performed using a silane coupling agent having a functional group such as an epoxy group or an acid anhydride, the polar term of the surface free energy of the glass reinforcing fiber tends to be high.
From the viewpoint of the impregnation of the resin into the fibers, ΔW _floc is preferably 10 mJ/m ² or less, more preferably 5 mJ/m ² or less, and further preferably 1 mJ/m ² or less.

In addition, it was found that the impregnation (impregnation speed) of the thermoplastic resin into the continuous reinforcing fiber is greatly affected by the melt flow rate (MFR) of the thermoplastic resin (measured at melting point + 5 ° C). It is considered that MFR indicates the ease with which the thermoplastic resin penetrates into the continuous reinforcing fiber. If the fluidity of the thermoplastic resin is high, the time required to impregnate the continuous reinforcing fiber with the thermoplastic resin is shortened, and the thermoplastic resin is sufficiently impregnated in the minimum necessary time, thereby improving the productivity of the composite material.
The MFR of the thermoplastic resin is preferably 80 g/10 min or less, more preferably 60 g/10 min or less, and even more preferably 40 g/10 min or less from the viewpoints of the strength, rigidity, moldability, and appearance of the obtained continuous fiber reinforced thermoplastic resin composite material. Also, from the viewpoints of fiber impregnation and film formability, it is preferably 5 g/10 min or more, more preferably 10 g/10 min or more, and even more preferably 20 g/10 min or more.

As a result of intensive research by the inventors, it has been found that the impregnation property of a continuous fiber reinforced plastic composite material can be improved by appropriately adjusting the ratio of ΔW _floc to MFR (ΔW _floc /MFR).
The continuous fiber reinforced thermoplastic resin composite material of this embodiment has a ΔW _floc /MFR value of 0.9 [mJ · 10 min / m ² · g] or less, preferably 0.5 [mJ · 10 min / m ² · g] or less, and more preferably 0.1 [mJ · 10 min / m ² · g] or less. When ΔW _floc /MFR is in the above range, the thermoplastic resin sufficiently impregnates the continuous reinforcing fibers in a short time, and the productivity of the continuous fiber reinforced resin composite material is increased.

ΔW _floc is a value that can be calculated by calculating the dispersion term and polarity term of the surface free energy by calculating the contact angle of water and the contact angle of liquid paraffin for each of the thermoplastic resin and the continuous reinforcing fiber, and substituting them into the above-mentioned calculation formula for ΔW _floc . Specifically, it can be calculated by the method described in the examples below.
The MFR is a value measured at melting point + 5° C. in accordance with ISO 1133, and specifically, it can be measured by the method described in the examples below.

In addition, the wettability between the continuous reinforcing fiber and the thermoplastic resin is considered to be good when the wetting angle θ between the continuous reinforcing fiber and the thermoplastic resin is small, and according to the following formula, when the surface free energy of the continuous reinforcing fiber is higher than the surface free energy of the thermoplastic resin, the wetting angle θ becomes small.
2 ((γ _fib ^d γ _pol ^d ) ^1/2 + (γ _fib ^p γ _pol ^p ) ^1/2 ) = (γ _pol ^d + γ _pol ^p ) (1+cos θ)
γ _pol ^d : dispersion term of surface free energy of thermoplastic resin γ _pol ^p : polar term of surface free energy of thermoplastic resin γ _fib ^d : dispersion term of surface free energy of continuous reinforcing fiber γ _fib ^p : polar term of surface free energy of continuous reinforcing fiber On the other hand, ΔW _floc is calculated according to the following formula, as described above, the smaller the difference between the surface free energy values of the thermoplastic resin and the continuous reinforcing fiber, the lower the value.
ΔW _floc = 2 (((γ _pol ^d ) ^1/2 _- (γ _fib ^d ) ^1/2 ) ² + ((γ _pol ^p ) ^1/2 _- (γ _fib ^p ) ^1/2 ) ² )
In this way, the wettability (wetting angle θ) and ΔW _floc are derived from different equations and are different indicators of impregnation.

Surface tension generally refers to the surface free energy of a liquid, and is expressed as the sum of the dispersion term and polar term of the surface free energy. If surface tension is used as an indicator of impregnation, it is not possible to take into account the differences between the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber and the thermoplastic resin, and this lacks precision.

(Continuous reinforcing fiber)
As the continuous reinforcing fibers, those used in ordinary continuous fiber reinforced resin composite materials may be used.
Examples of continuous reinforcing fibers include, but are not limited to, inorganic fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers; and organic fibers such as plant fibers, aramid fibers, ultra-high strength polyethylene fibers, polybenzazole fibers, liquid crystal polyester fibers, and polyketone fibers.
From the viewpoints of mechanical properties, thermal properties, and versatility, glass fibers, carbon fibers, vegetable fibers, and aramid fibers are preferred, and from the viewpoint of productivity, glass fibers are preferred.
The continuous reinforcing fibers may be used alone or in combination of two or more.

The content of the continuous reinforcing fibers relative to 100 parts by mass of the thermoplastic resin is preferably 49 to 84 parts by mass, more preferably 60 to 77 parts by mass, and even more preferably 65 to 73 parts by mass.
The volume fraction Vf (%) of the continuous reinforcing fibers in the continuous fiber reinforced resin composite material is preferably 30 to 70%, more preferably 40 to 60%, and even more preferably 45 to 55%.

-Bundling agent-
When glass fibers are selected as the continuous reinforcing fibers, a sizing agent may be used.
The sizing agent may contain one or more selected from the group consisting of a silane coupling agent, a lubricant, and a binder, and preferably contains at least a binder or a silane coupling agent, and more preferably consists of a silane coupling agent, a lubricant, and a binder. By being a binder that forms a strong bond with the resin that coats the continuous reinforcing fibers, a continuous fiber reinforced resin composite material with low porosity can be obtained.
The sizing agent may be added externally to the material used or may be included internally in the material used, for example, a lubricant may be included in the commercial product of the thermoplastic resin used.

--Silane coupling agent--
Silane coupling agents are usually used as surface treatment agents for glass fibers, and contribute to improving the 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 γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxy silanes; vinyl silanes, maleic acids, and the like.
When polyamide is used as the thermoplastic resin, it is preferable to select one that is easily bonded to the carboxyl group or amino group that is the terminal group of the polyamide resin, and aminosilanes such as γ-aminopropyltrimethoxysilane, maleic acids, and epoxysilanes are preferred.
The silane coupling agent is an important factor that determines the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber. By treating the surface of the continuous reinforcing fiber with a silane coupling agent and adjusting the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber, ΔW _floc can be appropriately adjusted.

--Lubricant--
The lubricant contributes to improving the opening property of the glass fibers.
As the lubricant, any ordinary liquid or solid lubricating material can be used depending on the purpose, so long as it does not interfere with the silane coupling agent and the binder. Examples of the lubricant include, but are not limited to, animal, vegetable or mineral waxes such as carnauba wax and lanolin wax; surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers.

--Binding agent--
The binder contributes to improving the bundling property of the glass fibers and improving the interfacial adhesive strength.
As the binder, a polymer according to the purpose, or a thermoplastic resin other than the thermoplastic resin as the main material of the continuous fiber reinforced resin composite material can be used.
Examples of the polymer used as the binder include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary, and tertiary amines. In addition, polyurethane resins synthesized from isocyanates such as m-xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate, and polyester or polyether diols, are also preferably used.
The homopolymer of acrylic acid preferably has a weight average molecular weight of 1,000 to 90,000, and more preferably 1,000 to 25,000.
The copolymerizable monomer constituting the copolymer of acrylic acid and other copolymerizable monomers is not limited to the following, but may be, for example, one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, among monomers having a hydroxyl group and/or a carboxyl group (excluding the case where only acrylic acid is used). It is preferable to have one or more ester monomers as the copolymerizable monomer.
Examples of salts of homopolymers and copolymers of acrylic acid with primary, secondary and tertiary amines include, but are not limited to, triethylamine salts, triethanolamine salts, glycine salts, etc. The degree of neutralization is preferably 20 to 90%, more preferably 40 to 60%, from the viewpoints of improving the stability of a mixed solution with other concomitant chemicals (such as a silane coupling agent) and reducing the amine odor.
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 bundling ability of the glass fibers, it is preferably 3,000 or more, and from the viewpoint of improving the properties when made into a composite material, it is preferably 50,000 or less.

Thermoplastic resins used as binders include, but are not limited to, polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, polyether ketones, polyether ether ketones, polyether sulfones, polyphenylene sulfide, thermoplastic polyetherimides, thermoplastic fluorine resins, and modified thermoplastic resins obtained by modifying these resins, etc. If the thermoplastic resin used as the binder is the same type of thermoplastic resin and/or modified thermoplastic resin as the resin that covers the periphery of the continuous reinforcing fibers, the adhesiveness between the glass fibers and the thermoplastic resin is improved after the composite material is formed, which is preferable.
When polyamide is used as the thermoplastic resin, it is preferable to use a resin having good wettability or surface tension similar to that of the polyamide resin as the binder. Specifically, for example, an emulsion of a polyurethane resin, an emulsion of a polyamide resin, or a modified product thereof can be selected.

Furthermore, from the viewpoints of further improving the adhesion between the continuous reinforcing fibers and the thermoplastic resin covering them, and reducing the ratio of the emulsifier component or making the emulsifier unnecessary when the bundling agent is attached to the glass fibers as an aqueous dispersion, a modified thermoplastic resin is preferred as the thermoplastic resin used as the binder.
The modified thermoplastic resin used herein means a thermoplastic resin obtained by copolymerizing a different monomer component other than a monomer component capable of forming the main chain of the thermoplastic resin, for the purpose of changing the properties of the thermoplastic resin, thereby modifying the hydrophilicity, crystallinity, thermodynamic properties, etc.
The modified thermoplastic resin used as the binder is not limited to the following, but examples thereof include modified polyolefin resins, modified polyamide resins, modified polyester resins, and the like.

The modified polyolefin resin used as a binder is a copolymer of an olefin monomer such as ethylene or propylene with a monomer copolymerizable with the olefin monomer, such as an unsaturated carboxylic acid and/or its ester, and can be produced by a known method. It may be a random copolymer in which an olefin monomer is copolymerized with an unsaturated carboxylic acid and/or its ester, or a graft copolymer in which an unsaturated carboxylic acid is grafted onto an olefin.

Examples of olefin monomers include, but are not limited to, ethylene, propylene, 1-butene, etc. These may be used alone or in combination of two or more. Examples of monomers copolymerizable with olefin monomers include unsaturated carboxylic acids such as acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid, and esters of these unsaturated carboxylic acids (methyl esters, ethyl esters, etc.), which may be used alone or in combination of two or more.
The copolymerization ratio of the olefin monomer and the monomer copolymerizable with the olefin monomer is preferably 60 to 95% by mass of the olefin monomer and 5 to 40% by mass of the monomer copolymerizable with the olefin monomer, and 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, with the total mass of the copolymerization components being 100% by mass. If the olefin monomer is 60% by mass or more, the affinity with the matrix is good, and if the mass% of the olefin monomer is 95% by mass or less, the water dispersibility of the modified polyolefin resin is good and it is easy to apply uniformly to the continuous reinforcing fibers.

In the modified polyolefin resin used as a binder, modified groups such as carboxyl groups introduced by copolymerization may be neutralized with a basic compound. Examples of basic compounds include, but are not limited to, alkalis such as sodium hydroxide and potassium hydroxide; ammonia; and amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin used as a binder is not particularly limited, but is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. From the viewpoint of improving the bundling ability of the glass fibers, a molecular weight of 5,000 or more is preferable, and from the viewpoint of emulsion stability when the resin is made water-dispersible, a molecular weight of 200,000 or less is preferable.

The modified polyamide resin used as a binder is a modified polyamide compound having a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component introduced into the molecular chain, and can be produced by a known method.
When a polyalkylene oxide chain is introduced into the molecular chain, for example, polyethylene glycol, polypropylene glycol, etc., partially or entirely modified with a diamine or dicarboxylic acid are copolymerized, and when a tertiary amine component is introduced, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylamino ε-caprolactam, etc. are copolymerized.

The modified polyester resin used as the binder is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and has a hydrophilic group in the molecular skeleton including the terminals, and can be produced by a known method.
Examples of the hydrophilic group include a polyalkylene oxide group, a sulfonate, a carboxyl group, and neutralized salts thereof. Examples of the polycarboxylic acid or anhydride thereof include an aromatic dicarboxylic acid, a sulfonate-containing aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, a trifunctional or higher polycarboxylic acid, and the like.
Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride.
Examples of sulfonate-containing aromatic dicarboxylic acids 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, and maleic anhydride.
Examples of tri- or higher functional polycarboxylic acids include, but are not limited to, trimellitic acid, pyromellitic acid, trimellitic anhydride, and pyromellitic anhydride.
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, and from the viewpoint of emulsion stability when the modified polyester resin is made into 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 tri- or higher functional polyols.
Examples of diols include, but are not limited to, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof, etc. Examples of polyols having three or more functional groups include trimethylolpropane, glycerin, pentaerythritol, etc.

The copolymerization ratio of the polycarboxylic acid or anhydride thereof and the polyol constituting the modified polyester resin is preferably 40 to 60 mass% of the polycarboxylic acid or anhydride thereof and 40 to 60 mass% of the polyol, and more preferably 45 to 55 mass% of the polycarboxylic acid or anhydride thereof and 45 to 55 mass% of the polyol, relative to 100 mass% of the total mass of the copolymerization components.
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. From the viewpoint of improving the bundling ability of the glass fibers, it is preferably 3,000 or more, and from the viewpoint of emulsion stability when it is made water-dispersible, it is preferably 100,000 or less.

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

When the sizing agent is composed of a silane coupling agent and a binder, the sizing agent is applied and attached in an amount of preferably 0.1 to 3 mass%, more preferably 0.2 to 2 mass%, and even more preferably 0.2 to 1 mass% as the total mass of the silane coupling agent and the binder relative to 100 mass% of the glass fiber. From the viewpoint of controlling the bundling property of the glass fiber and improving the interfacial adhesive strength, the amount of the sizing agent applied is preferably 0.1 mass% or more as the total mass of the silane coupling agent and the binder relative to 100 mass% of the glass fiber, and from the viewpoint of the handleability of the yarn, it is preferably 3 mass% or less.
In addition, when the sizing agent is composed of a silane coupling agent, a lubricant, and a binder, the sizing agent is applied and attached in an amount of preferably 0.1 to 3 mass%, more preferably 0.2 to 2 mass%, and even more preferably 0.2 to 1 mass% as the total mass of the silane coupling agent, lubricant, and binder relative to 100 mass% of the glass fiber. From the viewpoint of controlling the bundling property of the glass fiber and improving the interfacial adhesive strength, the amount of the sizing agent applied is preferably 0.1 mass% or more as the total mass of the silane coupling agent, lubricant, and binder relative to 100 mass% of the glass fiber, and from the viewpoint of the handleability of the yarn, it is preferably 3 mass% or less.

--Composition of glass fiber sizing agent--
When glass fibers are used as the continuous reinforcing fibers, the bundling agent for the glass fibers preferably contains 0.1 to 2 mass % of a silane coupling agent, 0.01 to 1 mass % of a lubricant, and 1 to 25 mass % of a binder, and these components are preferably diluted with water to adjust the total mass to 100 mass %.
The amount of the silane coupling agent in the sizing agent for glass fibers is preferably 0.1 to 2 mass %, more preferably 0.1 to 1 mass %, and even more preferably 0.2 to 0.5 mass %, from the viewpoints of improving the bundling ability of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite material.

The amount of lubricant in the glass fiber sizing agent is preferably 0.01 mass % or more, more preferably 0.02 mass % or more, from the viewpoint of providing sufficient lubricity, and is preferably 1 mass % or less, more preferably 0.5 mass % or less, from the viewpoint of improving the interfacial adhesive strength and the mechanical strength of the composite material.
The blending amount of the binder in the sizing agent for glass fibers is preferably 1 to 25 mass %, more preferably 3 to 15 mass %, and even more preferably 3 to 10 mass %, from the viewpoints of controlling the bundling property of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite material.

--Use of glass fiber sizing agent--
The sizing agent for glass fibers may be prepared in any form, such as an aqueous solution, a colloidal dispersion, or an emulsion using an emulsifier, depending on the mode of use. From the viewpoints of improving the dispersion stability and heat resistance of the sizing agent, however, it is preferable to prepare the sizing agent in the form of an aqueous solution.
The glass fibers as the continuous reinforcing fibers constituting the continuous fiber-reinforced resin composite material of this embodiment can be obtained continuously by applying the above-mentioned sizing agent to glass fibers using a known method such as a roller-type applicator in a known glass fiber production process, and drying the produced glass fibers.

Similarly, when carbon fibers are selected as the continuous reinforcing fibers, a sizing agent may be used, and the sizing agent is preferably composed of a coupling agent, a lubricant, and a binder. The coupling agent may be selected from those having good compatibility with the hydroxyl groups present on the surface of the carbon fibers, the binder may be selected from those having good wettability with the selected thermoplastic resin or having a surface tension similar thereto, and the lubricant may be selected from those not interfering with the coupling agent and the binder.
The type of sizing agent used for the carbon fibers is not particularly limited, and any known sizing agent can be used. Specifically, for example, the one described in JP 2015-101794 A can be used.

When using other continuous reinforcing fibers, the type and amount of sizing agent that can be used with glass fibers and carbon fibers can be appropriately selected depending on the characteristics of the continuous reinforcing fibers, and it is preferable to use a type and amount of sizing agent similar to that used with carbon fibers.

- Shape of continuous reinforcing fibers -
The continuous reinforcing fiber is a multifilament consisting of a plurality of filaments, and the number of single yarns is preferably 30 to 15,000 from the viewpoint of handleability. The single yarn diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, even more preferably 6 to 20 μm, and most preferably 8 to 18 μm from the viewpoint of strength and handleability.
The product RD of the single fiber diameter R (μm) and density D (g/cm3) of the continuous reinforcing fiber is preferably 5 to 100 μm g/cm3, more preferably 10 to 50 μm g/cm3, even more preferably 15 to 45 μm g/cm3, and still more preferably 20 to 45 μm g/cm3, from the viewpoints of the handleability of the continuous reinforcing fiber and the strength of the composite material.

により算出することができる。また、単糸径Ｒ（μｍ）は例えば、連続強化繊維単糸のＳＥＭ観察によって求めることができる。 The density D can be measured by a specific gravity meter. On the other hand, the single yarn diameter R (μm) can be calculated from the density D (g/cm3), the fineness (dtex), and the number of single yarns (pieces) by the following formula:

The single fiber diameter R (μm) can be determined, for example, by SEM observation of the continuous reinforcing fiber single fiber.

To set the product RD of the continuous reinforcing fiber within a specified range, the fineness (dtex) and number of single threads (pieces) of commercially available continuous reinforcing fibers can be appropriately selected according to the density of the continuous reinforcing fiber. For example, when glass fiber is used as the continuous reinforcing fiber, the density is about 2.5 g/cm3, so a single thread diameter of 2 to 40 μm can be selected. Specifically, when the single thread diameter of the glass fiber is 9 μm, the product RD is 23 by selecting a glass fiber with a fineness of 660 dtex and 400 single threads. When the single thread diameter of the glass fiber is 17 μm, the product RD is 43 by selecting a glass fiber with a fineness of 11,500 dtex and 2,000 single threads. When carbon fiber is used as the continuous reinforcing fiber, the density is about 1.8 g/cm3, so a single thread diameter of 2.8 to 55 μm can be selected. Specifically, if the carbon fiber has a single filament diameter of 7 μm, the product RD will be 13 by selecting carbon fiber with a fineness of 2,000 dtex and 3,000 single filaments. If aramid fiber is used as the continuous reinforcing fiber, the density is approximately 1.45 g/cm3, so a single filament diameter of 3.4 to 68 μm should be selected. Specifically, if the aramid fiber has a single filament diameter of 12 μm, the product RD will be 17 by selecting aramid fiber with a fineness of 1,670 dtex and 1,000 single filaments.

Continuous reinforcing fibers, for example glass fibers, are manufactured by weighing and mixing raw glass, molten glass in a melting furnace, spinning this into glass filaments, applying a bundling agent, and passing through a spinning machine into a wound form such as direct wound roving (DWR), cake, or twisted yarn. The continuous reinforcing fibers can be in any form, but being wound into yarn, cake, or DWR is preferable because it increases productivity and production stability in the resin coating process. From the viewpoint of productivity, DWR is the most preferable.

The form of the continuous reinforcing fiber is not particularly limited, and various forms can be mentioned, such as woven fabric, knitted fabric, braided cord, pipe-shaped material, non-crimp fabric, unidirectional material, etc. Among them, woven fabric, non-crimp fabric, and unidirectional material are preferably used.

(Thermoplastic resin)
The thermoplastic resin used in the production of the continuous fiber reinforced thermoplastic resin composite material of this embodiment may be used alone or in combination of two or more, but it is preferable to use two or more types. By appropriately combining two or more types of thermoplastic resins, the physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, appearance, etc.) of the continuous fiber reinforced resin composite material can be adjusted.
In addition, the two or more types of thermoplastic resins are preferably compatible with each other. When the two or more types of thermoplastic resins contained in the continuous fiber reinforced resin composite material are compatible with each other, the physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, appearance, etc.) tend to be improved.
The state in which the thermoplastic resins are compatible with each other means a state in which no domains are formed by a plurality of thermoplastic resins when the thermoplastic resin is electronically stained and observed with a scanning electron microscope (SEM) in a cross section perpendicular to the longitudinal direction of the continuous reinforcing fibers contained in the continuous fiber reinforced resin composite material. Specifically, the observation can be performed by the method described in the examples below.

From the viewpoint of high temperature properties and water absorption properties, the resin with the largest mass proportion among two or more types of thermoplastic resins preferably has a mass proportion of 5 times or less, more preferably 4 times or less, and even more preferably 3 times or less, of the resin with the second largest mass proportion. When the mass proportion of the thermoplastic resin is within the above range, the physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, appearance, etc.) tend to be improved.

Thermoplastic resins include, but are not limited to, polyolefin resins such as polyethylene and polypropylene; polyamide resins such as polyamide 6, polyamide 66, polyamide 46, polyamide 612, and polyamide 6I; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate; polyacetal resins such as polyoxymethylene; polycarbonate resins; polyether resins such as polyether ketone, polyether ether ketone, polyether glycol, polypropylene glycol, and polytetramethylene ether glycol; polyether sulfone; polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluorine resins such as tetrafluoroethylene-ethylene copolymer; polyurethane resins; acrylic resins, and modified thermoplastic resins obtained by modifying these.

Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyethersulfone, polyphenylene sulfide, thermoplastic polyetherimide, and thermoplastic fluorine resins are preferred, and polyolefin resins, modified polyolefin resins, polyamide resins, polyester resins, polyurethane resins, and acrylic resins are more preferred from the viewpoint of mechanical properties and versatility, and polyamide resins and polyester resins are even more preferred from the viewpoint of thermal properties. Furthermore, polyamide resins are even more preferred from the viewpoint of durability against repeated loads.

- Polyester resin -
The polyester resin refers to a polymer compound having --CO--O-- (ester) bonds in the main chain.
Examples of polyester resins include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate.
The polyester resin may be a homopolyester or a copolymer polyester.
In the case of a copolymer polyester, a homopolyester copolymerized with an appropriate third component is preferred. Examples of the third component include, but are not limited to, diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid.
In addition, polyester-based resins using raw materials derived from biomass resources can also be used, and examples thereof include, but are not limited to, aliphatic polyester-based resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and aromatic polyester-based resins such as polybutylene adipate terephthalate.

- Polyamide resin -
The polyamide resin refers to a polymer compound having an --CO--NH-- (amide) bond in the main chain, and examples thereof include aliphatic polyamides, aromatic polyamides, and wholly aromatic polyamides.

Examples of polyamide-based resins include, but are not limited to, polyamides obtained by ring-opening polymerization of lactams, polyamides obtained by self-condensation of ω-aminocarboxylic acids, polyamides obtained by condensing diamines and dicarboxylic acids, and copolymers thereof.
The polyamide resin may be used alone or in combination of two or more kinds.
Examples of lactams include, but are not limited to, pyrrolidone, caprolactam, undecanelactam, and dodecalactam.
Examples of ω-amino carboxylic acids include, but are not limited to, ω-amino fatty acids, which are ring-opened compounds of lactams with water. Two or more kinds of lactams or ω-amino carboxylic acids may be condensed in combination.
Examples of diamines (monomers) include, but are not limited to, linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; branched aliphatic diamines such as 2-methylpentanediamine and 2-ethylhexamethylenediamine; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; and alicyclic diamines such as cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine.
Examples of dicarboxylic acids (monomers) 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, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The diamines and dicarboxylic acids as monomers may each be condensed alone or in combination of two or more.

Examples of polyamide-based resins include, but are not limited to, aliphatic polyamides such as polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecane amide), polyamide 12 (polydodecane amide), polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, and polyamide 612; semi-aromatic polyamides such as polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide); and copolymer polyamides containing these as constituent components.
Examples of copolymerized polyamides include, but are not limited to, copolymers of hexamethylene adipamide and hexamethylene terephthalamide, copolymers of hexamethylene adipamide and hexamethylene isophthalamide, and copolymers of hexamethylene terephthalamide and 2-methylpentanediamine terephthalamide.

In the case where a polyamide resin is used, it is preferable that the thermoplastic resin contains (A) 50 to 99 parts by mass of an aliphatic polyamide, and (B) 1 to 50 parts by mass of a semi-aromatic polyamide containing dicarboxylic acid units containing at least 75 mol % of isophthalic acid units and diamine units containing at least 50 mol % of diamine units having 4 to 10 carbon atoms.
When the thermoplastic resin contains the aliphatic polyamide (A) and the semi-aromatic polyamide (B) within the above range, the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, appearance, etc.) of the continuous fiber reinforced resin composite material tend to be improved compared to a case in which the polyamide contains only the aliphatic polyamide (A).
The total content of the aliphatic polyamide (A) and the semi-aromatic polyamide (B) is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, and even more preferably 90 to 100 mass%, based on 100 mass% of the thermoplastic resin.

The weight average molecular weight (Mw) of the thermoplastic resin containing the aliphatic polyamide (A) and the semi-aromatic polyamide (B) is preferably 15000 to 35000, more preferably 17000 to 35000, even more preferably 20000 to 35000, still more preferably 22000 to 34000, particularly preferably 24000 to 33000, and most preferably 25000 to 32000. When the weight average molecular weight (Mw) of the thermoplastic resin is within the above range, strength and rigidity tend to be improved.
In the thermoplastic resin, the weight average molecular weight MwA of the aliphatic polyamide (A) is preferably 1.5 times or more, more preferably 2 times or more, of the weight average molecular weight MwB of the semi-aromatic polyamide (B). When MwA is 1.5 times or more of MwB, strength and rigidity tend to be improved.
The weight average molecular weight (Mw) of the thermoplastic resin, the aliphatic polyamide (A), and the semi-aromatic polyamide (B) can be measured by gel permeation chromatography (GPC), and specifically, can be observed by the method described in the examples below.

Examples of the aliphatic polyamide (A) include, but are not limited to, polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, and polyamide 612.
The content of the aliphatic polyamide (A) in 100% by mass of the polyamide in the thermoplastic resin is preferably 50 to 99% by mass, more preferably 60 to 90% by mass, and further preferably 70 to 80% by mass.

Examples of the semi-aromatic polyamide (B) include, but are not limited to, polyamide 6I, polyamide 9I, polyamide 10I, and the like.
The total amount of the isophthalic acid units and the diamine units having 4 to 10 carbon atoms is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%, relative to 100 mol% of all structural units of the semi-aromatic polyamide (B).
The proportion of the monomer units constituting the semi-aromatic polyamide (B) can be measured, for example, by ¹³ C nuclear magnetic resonance spectroscopy (NMR).

(B) In the semi-aromatic polyamide, the proportion of isophthalic acid units in the dicarboxylic acid units is at least 75 mol%, preferably 85 mol% or more, and more preferably 90 mol% or more. When the proportion of isophthalic acid units in the dicarboxylic acid units is within the above range, the high temperature properties and water absorption properties tend to be improved.

(B) In the semi-aromatic polyamide, the proportion of diamine units having 4 to 10 carbon atoms in the diamine units is at least 50 mol%, preferably 60 mol% or more, and more preferably 70 mol% or more. When the proportion of diamine units having 4 to 10 carbon atoms in the diamine units is within the above range, the high temperature properties and water absorption properties tend to be improved.

The content of (B) semi-aromatic polyamide in 100% by mass of polyamide in the thermoplastic resin is preferably 1 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 20 to 30% by mass.

The above (A) aliphatic polyamide and (B) semi-aromatic polyamide may be end-capped with a known end-capping agent, and the total amount of the blocked ends of the (A) aliphatic polyamide and (B) semi-aromatic polyamide expressed as an equivalent per 1 g of polyamide including the (A) aliphatic polyamide and the (B) semi-aromatic polyamide is preferably 5 to 180 μ equivalents/g, more preferably 10 to 170 μ equivalents/g, even more preferably 20 to 160 μ equivalents/g, particularly preferably 30 to 140 μ equivalents/g, and most preferably 40 to 140 μ equivalents/g. When the amount of blocked ends is within the above range, physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, appearance, etc.) tend to be improved.
The amount of blocked ends is the total amount of amino ends and carboxyl ends blocked with a blocking agent. The amount of blocked ends can be measured by ^1H -NMR, specifically, by the method described in the Examples below.

The terminal group concentration of the aliphatic polyamide (A) is preferably 1/2 or less, more preferably 2/5 or less, of the terminal group concentration of the semi-aromatic polyamide (B). When the terminal group concentration of the aliphatic polyamide (A) is 1/2 or less of the terminal group concentration of the semi-aromatic polyamide (B), the physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, appearance, etc.) tend to be improved.
The end group concentrations of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide can be measured using ¹ H-NMR, specifically, by the method described in the examples below.

The difference in tan δ peak temperature between the aliphatic polyamide (A) and the semi-aromatic polyamide (B) is preferably 45 to 100° C., more preferably 50 to 90° C., and even more preferably 60 to 90° C. When the difference in tan δ peak temperature between the aliphatic polyamide (A) and the semi-aromatic polyamide (B) is within the above range, high temperature properties and water absorption properties tend to be improved.
The peak temperatures of tan δ of the aliphatic polyamide (A) and the semi-aromatic polyamide (B) can be measured, for example, using a viscoelasticity measuring analyzer, and specifically, can be measured by the method described in the examples below.

From the viewpoints of strength, rigidity, moldability and appearance, the difference in viscosity between the aliphatic polyamide (A) and the semi-aromatic polyamide (B) is preferably 3 times or more, and more preferably 4 times or more.
The viscosity of the thermoplastic resin can be determined by MFR measurement (in accordance with ISO 1133), and specifically, can be observed by the method described in the examples below.

[Additives]
Additives may be added to the continuous fiber reinforced thermoplastic resin composite material of the present embodiment as necessary. Examples of additives include colorants, antiaging agents, antioxidants, weathering agents, metal deactivators, light stabilizers, heat stabilizers, ultraviolet absorbers, antibacterial and antifungal agents, deodorizers, electrical conductivity imparting agents, dispersants, softeners, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanization assistants, foaming agents, foaming assistants, flame retardants, vibration dampers, nucleating agents, neutralizing agents, lubricants, antiblocking agents, dispersants, flow improvers, and mold release agents.
The amount of the additive may be 3% by mass or less relative to 100% by mass of the composite material.

(Coloring Agent)
Examples of colorants include carbon black, nigrosine, aluminum pigments, titanium dioxide, ultramarine, cyanine blue, cyanine green, quinacridone, diatomaceous earth, monoazo salts, perylene, disazo, condensed azo, isoindoline, red iron oxide, nickel titanium yellow, diketone pyrrolopyrrole, metal salts, perylene red, metal oxides, bismuth vanadate, cobalt green, cobalt blue, anthraquinone, phthalocyanine green, phthalocyanine blue, etc. Among these, black colorants are preferred, and carbon black and nigrosine are more preferred.

[Continuous fiber reinforced thermoplastic resin composite material]
The continuous fiber reinforced thermoplastic resin composite material of the present embodiment includes continuous reinforcing fibers and a thermoplastic resin, and when the dispersion term and polar term of the surface free energy of the thermoplastic resin are γ _pol ^d and γ _pol ^p , respectively, and the dispersion term and polar term of the surface free energy of the continuous reinforcing fibers are γ _fib ^d and γ _fib ^p , respectively, ΔW _floc [mJ/m ² ] expressed by ΔW floc = 2(((γ _pol ^d ) ^1/2 _- (γ _fib ^d ) ^1/2 ) ² + ((γ _pol ^p ) ^1/2 _- (γ _fib ^p ) ^1/2 ) ² ), and the melt flow rate (measured at melting point + 5°C) value MFR [g/10 min] of the thermoplastic resin satisfy ΔW _floc /MFR≦0.9 [ _mJ ·10 min/m ² ·g] is satisfied.
The continuous fiber reinforced thermoplastic resin composite material of this embodiment can be produced, for example, by the above-mentioned method for producing a continuous fiber reinforced thermoplastic resin composite material.

The continuous fiber reinforced thermoplastic resin composite material of this embodiment has a ΔW _floc /MFR value of 0.9 [mJ · 10 min / m ² · g] or less, preferably 0.5 [mJ · 10 min / m ² · g] or less, and more preferably 0.1 [mJ · 10 min / m ² · g] or less. When the ΔW _floc /MFR is in the above range, the continuous fiber reinforced thermoplastic resin composite material has excellent impact properties.
Moreover, from the viewpoint of the impregnation of the resin into the fibers, the ΔW _floc is preferably 10 mJ/m ² or less, more preferably 5 mJ/m ² or less, and further preferably 1 mJ/m ² or less.
From the viewpoints of strength, rigidity, moldability, and appearance of the continuous fiber reinforced thermoplastic resin composite material, the MFR is preferably 80 g/10 min or less, more preferably 60 g/10 min or less, and even more preferably 40 g/10 min or less. From the viewpoints of fiber impregnation and film formability, the MFR is preferably 5 g/10 min or more, more preferably 10 g/10 min or more, and even more preferably 20 g/10 min or more.

ΔW _floc is a value that can be calculated by calculating the dispersion term and polarity term of the surface free energy by calculating the contact angle of water and the contact angle of liquid paraffin for each of the thermoplastic resin and the continuous reinforcing fiber, and substituting them into the above-mentioned calculation formula for ΔW _floc . Specifically, it can be calculated by the method described in the examples below.
The MFR is a value measured at melting point + 5° C. in accordance with ISO 1133, and specifically, it can be measured by the method described in the examples below.

The types of continuous reinforcing fibers and thermoplastic resin constituting the continuous fiber reinforced thermoplastic resin composite material of this embodiment may be as described above.

[Mold of continuous fiber reinforced thermoplastic resin composite material]
The form of the continuous fiber reinforced thermoplastic resin composite material is not particularly limited, and may be any of the following various forms: a form in which a woven fabric, knitted fabric, braided cord, or pipe-shaped continuous reinforcing fiber is combined with a thermoplastic resin, a form in which continuous reinforcing fibers aligned in one direction are combined with a thermoplastic resin, a form in which a thread made of continuous reinforcing fibers and a thermoplastic resin is aligned in one direction and shaped, and a form in which a thread made of continuous reinforcing fibers and a thermoplastic resin is shaped into a woven fabric, knitted fabric, braided cord, or pipe.
The continuous fiber reinforced thermoplastic resin composite material of the present embodiment may be a flat plate, or may be a laminate including a layer of continuous reinforcing fibers and a layer of thermoplastic resin. For example, the length direction of the continuous reinforcing fibers may be arranged approximately parallel to the surface of the flat plate. The continuous reinforcing fiber layer may be a layer including continuous reinforcing fibers (for example, a continuous reinforcing fiber substrate) and may be a layer in which the thermoplastic resin is impregnated into the interior of the continuous reinforcing fibers.
The form of the intermediate material before shaping of the continuous fiber reinforced thermoplastic resin composite material is not particularly limited, and examples thereof include a mixed fiber yarn of continuous reinforcing fibers and resin fibers, a coated yarn in which a bundle of continuous reinforcing fibers is covered with resin, continuous reinforcing fibers impregnated with resin in advance and formed into a tape-like shape, continuous reinforcing fibers sandwiched between resin films, continuous reinforcing fibers with resin powder attached thereto, a bundle of continuous reinforcing fibers as a core material and braided with resin fibers around it, reinforcing fibers pre-impregnated with resin, and a form in which continuous reinforcing fibers are in contact with molten resin.

[Molding of continuous fiber reinforced thermoplastic resin composite material]
The continuous fiber reinforced thermoplastic resin composite material of the present embodiment can be further molded. For example, the continuous fiber reinforced thermoplastic resin composite material of the present embodiment can be cut into a predetermined size, heated with an infrared heater, and heated and compressed with a press molding machine.

The present invention will be specifically described below with reference to examples , reference examples , and comparative examples. However, the present invention is not limited to these examples, and it goes without saying that the present invention can be practiced with various modifications within the scope of the gist of the present invention.

First, the measurement methods used in the Examples , Reference Examples , and Comparative Examples will be described.

(Contact angle measurement)
Measurement of contact angle of thermoplastic resin: Water and liquid paraffin were dropped onto the flat surface of a resin molded product produced by injection molding, and the droplets formed 3 seconds after the dropping were observed from the side (in a direction parallel to the flat surface), and the contact angles between the resin molded product and each droplet were measured by the θ/2 method.
Measurement of contact angle of reinforcing fiber: Double-sided tape was applied onto a flat preparation, and finely chopped reinforcing fiber was sprinkled on it sufficiently so that the fiber length was 1 mm or less, so that the reinforcing fiber was adhered to the double-sided tape, and the unadhered reinforcing fiber was removed to obtain a sample. Water and liquid paraffin were dropped onto the sample, and the contact angle of the reinforcing fiber was measured by the θ/2 method in the same manner as the above resin molded product.
The contact angle was measured using a contact angle measuring device (CA-X150 contact angle meter manufactured by Kyowa Interface Science Co., Ltd., Japan).

(Calculation of surface free energy)
The surface free energy of the solid samples, thermoplastic resin and reinforcing fiber, was calculated by substituting the results of the above (contact angle measurement) using two liquids with known compositions, water and liquid paraffin, into the following equation.
2 ((γ _S ^d γ _L ^d ) ^1/2 + (γ _S ^p γ _L ^p ) ^1/2 ) = (γ _L ^d + γ _L ^p ) (1+cos θ)
γ _L ^d : dispersion term of the surface free energy of the liquid γ _L ^p : polar term of the surface free energy of the liquid γ _S ^d : dispersion term of the surface free energy of the solid sample γ _S ^p : polar term of the surface free energy of the solid sample The dispersion term of the surface free energy of water is 21.8 [mJ/m ² ],
The polar term of the surface free energy of water is 51.0 [mJ/m ² ].
The dispersion term of the surface free energy of liquid paraffin is 38.1 [mJ/m ² ].
The polar term of the surface free energy of liquid paraffin is set to 0 [mJ/m ² ].
It was calculated as:
By substituting the value of θ measured by water contact angle measurement and the surface free energies of water γ _L ^d (21.8 mJ/m ² ) and γ _L ^p (51.0 mJ/m ² ) into the above equation, a relational equation consisting of two unknowns, the dispersion term γ _S ^d and the polar term γ _S ^p of the surface free energy of the solid sample, was obtained.
In addition, by substituting the value of θ measured by measuring the contact angle of liquid paraffin and the surface free energies γ _L ^d (38.1 mJ/m ² ) and γ _L ^p (0 mJ/m ² ) of liquid paraffin into the above equation, a relational equation consisting of two unknowns, the dispersion term γ _S ^d and the polar term γ _S ^p of the surface free energy of the solid sample, was obtained.
By combining the above two equations consisting of two unknowns obtained from the results for water and liquid paraffin, the dispersion term γ _S ^d and the polar term γ _S ^p of the surface free energy of the thermoplastic resin and the reinforcing fiber were calculated, respectively.

(Calculation of ΔW _floc )
ΔW _floc is calculated by substituting the dispersion term and polar term of the surface free energy of the thermoplastic resin obtained in the above (calculation of surface free energy) and the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber into the following formula.
ΔW _floc = 2 (((γ _pol ^d ) ^1/2 _- (γ _fib ^d ) ^1/2 ) ² + ((γ _pol ^p ) ^1/2 _- (γ _fib ^p ) ^1/2 ) ² )
γ _pol ^d : Dispersion term of surface free energy of thermoplastic resin γ _pol ^p : Polar term of surface free energy of thermoplastic resin γ _fib ^d : Dispersion term of surface free energy of continuous reinforcing fiber γ _fib ^p : Polar term of surface free energy of continuous reinforcing fiber

(Melt point measurement)
Using a differential scanning calorimeter (DSC: DSC8500 manufactured by PERKINELMER), the melting point [°C] was determined as the peak top temperature of the endothermic peak that appeared when the temperature was raised from 23°C at a heating rate of 10°C/min. When two or more endothermic peaks appeared, the peak top temperature of the endothermic peak on the highest temperature side was determined as the melting point.

(Measurement of MFR)
In accordance with JIS K7210:1999 (ISO 1133:1997), the MFR [g/10 min] was measured at a temperature 5° C. higher than the melting point of each thermoplastic resin using a Semi-Auto Melt Indexer 2A manufactured by Toyo Seiki Seisakusho Co., Ltd. under a load of 2.16 kg. The average of three measurement results was taken as the measured MFR value.

(Measurement of impregnation distance)
The glass cloth and the thermoplastic resin film were impregnated with resin as follows.
A hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons was used as the press machine. Two thermoplastic resin films (40 mm x 40 mm) were placed on a glass cloth (80 mm x 80 mm), and then the glass cloth and the thermoplastic resin film were sandwiched between two Kapton film sheets (manufactured by Toray DuPont Co., Ltd., 100 mm x 100 mm) to obtain a laminate. The laminate was further sandwiched between two iron plates (300 mm x 300 mm x 5 mmt).
The temperature of the press was preheated to 270°C, and the laminate sandwiched between the iron plates was pressed at a pressure of 5 MPa for 30 seconds to impregnate the glass reinforcing fibers with the thermoplastic resin, and then the laminate was pressed at 5 MPa in a press cooled to room temperature with water until the temperature reached 30°C or below.
A test piece of 10 mm x 10 mm was cut out from the center of the sample prepared in the above process, and the cross section was polished. The polished cross section was observed with a high-resolution scanning electron microscope (SEM) (Hitachi, Ltd. FESEM/EDX S-4700) to measure the impregnation distance. In the above cross section, the average distance between the line constituted by the surface of the thermoplastic resin side of the glass cloth and the line constituted by the impregnated tip of the impregnated thermoplastic resin was calculated by observing a range of at least 3 mm wide, and the impregnation distance was calculated. This was carried out three times under the same conditions, and the average was taken, which was used as the impregnation distance [μm] for each Example , Reference Example , and Comparative Example.

(Measurement of impact properties)
The continuous fiber reinforced resin composite materials obtained in Comparative Example 6, Examples 10, and 11 were cut into samples having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm, and the impact energy and ductility index of the composite materials at the time of impact were measured using a drop weight impact tester (manufactured by INSTRON Corp.) The total weight of the weight was 10.2 kg, the height of the weight was 1.12 m, and the impact energy was 112 J.
The impact energy [J] was obtained by integrating the force [N] at the time of impact measured by a load cell with the time at the time of impact. The ductility index at the time of impact is the ratio of the "impact energy up to the peak top [J]", which is the value obtained by integrating the impact force measured by the load cell with time up to the peak top, to the "impact energy after the peak top [J]", which is the value obtained by integrating the impact force measured by the load cell with time after the peak top, and was calculated by the following formula.
Ductility index during impact = (impact energy up to the peak top) ÷ (impact energy after the peak top)

The materials used in the examples , reference examples , and comparative examples are as follows.

(glass reinforced fiber)
・GF-1
Glass fibers having a fineness of 11,500 dtex and 2,000 single fibers were produced. The winding form was DWR, and the average single fiber diameter was 17 μm.
The sample was used as it was without applying any bundling agent.
GF-2
Glass fibers having a fineness of 11,500 dtex and 2,000 single fibers were produced. The winding form was DWR, and the average single fiber diameter was 17 μm.
An aqueous solution containing 2 mass% polyurethane resin Y65-55 (manufactured by ADEKA Corporation) was applied to the glass fibers so that the adhesion amount was 0.15 mass%, and then dried. After that, a sizing agent prepared with deionized water so that the adhesion amount was 0.30 mass%, was applied and dried. The sizing agent was 1 mass% carnauba wax and 3 mass% copolymer compound (a copolymer compound having a weight average molecular weight of 20,000, obtained by copolymerizing 80 mass% maleic anhydride, 10 mass% methyl acrylate, and 10 mass% methyl methacrylate).
GF-3
Glass fibers having a fineness of 11,500 dtex and 2,000 single fibers were produced. The winding form was DWR, and the average single fiber diameter was 17 μm.
An aqueous solution containing 0.5 mass% γ-aminopropyltriethoxysilane (hereinafter simply referred to as "aminosilane") KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2 mass% polyurethane resin Y65-55 (manufactured by ADEKA Corporation) was applied to the glass fibers so that the adhesion amount was 0.15 mass%, and then dried. After that, a sizing agent prepared with deionized water so that the adhesion amount was 0.30 mass%, was applied and dried. The sizing agent was 1 mass% carnauba wax and 3 mass% copolymer compound (a copolymer compound having a weight average molecular weight of 20,000, obtained by copolymerizing 80 mass% maleic anhydride, 10 mass% methyl acrylate, and 10 mass% methyl methacrylate).
GF-4
Glass fibers having a fineness of 11,500 dtex and 2,000 single fibers were produced. The winding form was DWR, and the average single fiber diameter was 17 μm.
An aqueous solution containing 0.5% by mass of aminosilane was applied to the glass fibers so that the adhesion amount was 0.15% by mass, and then dried. Then, a sizing agent prepared with deionized water so that the adhesion amount was 0.30% by mass was applied and dried. The sizing agent was 2% by mass of polyurethane resin Y65-55 (manufactured by ADEKA Corporation), 1% by mass of carnauba wax, and 3% by mass of a copolymer compound (a copolymer compound having a weight average molecular weight of 20,000, obtained by copolymerizing 40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate).
GF-5
Glass fibers having a fineness of 11,500 dtex and 2,000 single fibers were produced. The winding form was DWR, and the average single fiber diameter was 17 μm.
An aqueous solution containing 0.5 mass % aminosilane and 2 mass % polyurethane resin Y65-55 (manufactured by ADEKA Corporation) was applied to the glass fibers so that the adhesion amount was 0.15 mass % and dried, and then a sizing agent prepared with deionized water so that the adhesion amount was 0.30 mass % (a copolymer compound having a weight average molecular weight of 20,000, obtained by copolymerizing 20 mass % maleic anhydride, 50 mass % methyl acrylate, and 30 mass % methyl methacrylate) was applied to the glass fibers so that the adhesion amount was 0.30 mass % and dried.
GF-6
Glass fibers having a fineness of 11,500 dtex and 2,000 single fibers were produced. The winding form was DWR, and the average single fiber diameter was 17 μm.
An aqueous solution containing 0.5% by mass of aminosilane was applied to the glass fibers so that the adhesion amount was 0.15% by mass, and then dried. Then, a sizing agent prepared with deionized water so that the adhesion amount was 0.30% by mass was applied and dried, and the sizing agent was 2% by mass of polyurethane resin Y65-55 (manufactured by ADEKA Corporation), 1% by mass of carnauba wax, and 3% by mass of a copolymer compound (a copolymer compound having a weight average molecular weight of 20,000, obtained by copolymerizing 50% by mass of methyl acrylate and 50% by mass of methyl methacrylate).
The measurement results for each glass reinforcing fiber are shown in Table 1.

(Preparation of glass cloth)
A glass cloth was produced by weaving the glass reinforced fibers as warp and weft yarns using a rapier loom (weaving width 2 m). The weaving form of the obtained glass cloth was plain weave, the weaving density was 6.5 threads/25 mm, and the basis weight was 600 g/ ^m2 .

(Thermoplastic resin)
Polyamide (PA) 66: Leona 1300S (Asahi Kasei Corporation, melting point 265°C)
Polyamide (PA) 6I: Leona R16024 (Asahi Kasei Corporation, glass transition temperature 130° C.)
Polypropylene (PP): Novatec MA3 (Japan Polypropylene Corporation, melting point 168°C)
・PA-1
Only PA66 was used as it was. The MFR value was 27.1 g/10 min.
・PA-2
PA66 and PA6I were compounded at a ratio of 70% by mass and 30% by mass, respectively. The melting point of PA-2 was 262° C. The MFR value was 43.2 g/10 min.
PP: Novatec MA3 alone was used. The MFR value was 11.0 g/10 min.
The measurement results for each thermoplastic resin are shown in Table 2.

(Preparation of Thermoplastic Resin Film)
The above thermoplastic resin was molded using a T-die extrusion molding machine (manufactured by Soken Co., Ltd.) to obtain a thermoplastic resin film. The extrusion temperatures were 260°C, 285°C, 290°C, and 260°C in the case of PA1 and PA2, in order from just below the hopper, and 165°C, 180°C, 185°C, and 165°C in the case of PP, in order from just below the hopper. The thickness of the obtained film was 180 μm.

[ Reference Example 1, Examples 2 to 9, Comparative Examples 1 to 5]
In each of the Examples and Comparative Examples, the glass reinforcing fibers and thermoplastic resins shown in Table 3 were used.
The measurement results of each physical property are shown in Table 3. The measurement results of the impregnation distance are shown in Figure 1.

Regarding the impregnation distance, the results of Comparative Example 1 , Reference Example 1 , and Examples 2 to 5 show that the impregnation distance improved as the ΔW _floc value decreased. In particular, impregnation proceeded well when ΔW _floc /MFR was 0.5 mJ·10 min/m ² ·g or less, and even better when it was 0.1 mJ·10 min/m ² ·g or less.
In addition, as a result of comparing Example 4 with Example 6 and Example 5 with Example 7, when ΔW _floc was the same, impregnation proceeded well when PA-2 having a high MFR value was used.
When the results of Comparative Examples 2 to 5 and Examples 8 and 9 were compared with the results of Comparative Example 1 , Reference Example 1 , and Examples 2 to 7, a similar tendency was confirmed between ΔW _floc /MFR and impregnation distance for PP having no polar functional group as for PA.

[Comparative Example 6]
The GF-1 glass cloth and the PA-1 resin film were molded as follows to obtain a continuous fiber reinforced thermoplastic resin composite material.
As a molding machine, a hydraulic molding machine (manufactured by Shoji Co., Ltd.) with a maximum clamping force of 50 tons and a die with a spigot structure for obtaining a flat-plate type continuous fiber reinforced resin composite material (length 200 mm, width 100 mm, thickness 2 mm) were prepared. Five sheets of the above GF-1 glass cloth and six sheets of PA-1 resin film were prepared and cut to fit the shape of the die, and then the sheets were alternately stacked so that the PA-1 resin film was on the surface and placed in the die. The mass of the resin and the mass of the glass reinforced fiber were adjusted so that the glass reinforced fiber was 230 parts by mass per 100 parts by mass of resin.
The temperature inside the molding machine was heated to 330° C., and then the mold was clamped with a clamping force of 5 MPa to perform compression molding. The molding time was set to 1 minute after the temperature reached 265° C., which is the melting point of polyamide 66. The mold was rapidly cooled to 25° C. and then opened, and the continuous fiber reinforced thermoplastic resin composite material was taken out.
The measurement results of each physical property of the obtained continuous fiber reinforced thermoplastic resin composite material are shown in Table 4.

[Examples 10 and 11]
A continuous fiber reinforced thermoplastic resin composite material was obtained in the same manner as in Comparative Example 6, except that the glass cloth and thermoplastic resin film were changed as shown in Table 4.
The measurement results of each physical property of the obtained continuous fiber reinforced thermoplastic resin composite material are shown in Table 4.

Regarding the impact energy of the composite material, the results of Comparative Example 6 and Examples 10 and 11 showed that the impact energy of the composite material increased as ΔW _floc /MFR decreased, and Examples 10 and 11 showed good impact properties.
Regarding the ductility index of the composite material upon impact, the results of Comparative Example 6 and Examples 10 and 11 showed that as ΔW _floc /MFR decreased, the ductility index of the composite material upon impact increased, and Examples 10 and 11 showed good ductility index upon impact.
For example, when the composite material is used as a structural member of a vehicle, the composite material is capable of absorbing the impact energy, thereby ensuring the safety of passengers. Therefore, it is desirable that the impact energy of the composite material is high.
In addition, when a material breaks, it is desirable for the break to be ductile rather than brittle in order to absorb large amounts of energy for as long as possible. By using a composite material with a good ductility index during impact, it is possible to change the break to something closer to ductile fracture rather than brittle fracture.

The manufacturing method of the continuous fiber reinforced resin composite material of this embodiment allows for the manufacture of the continuous fiber reinforced resin composite material with high productivity. In addition, the continuous fiber reinforced resin composite material of this embodiment has industrial applicability as a material for structural parts, pressure vessels, tubular structures, and the like, of various machines and automobiles that require high levels of mechanical properties.

Claims (8)

The method includes applying an aqueous solution containing a silane coupling agent to the continuous reinforcing fibers, drying the aqueous solution, applying a sizing agent containing a lubricant and a binder, and drying the continuous reinforcing fibers , and impregnating the continuous reinforcing fibers with a thermoplastic resin.
When the dispersion term and polar term of the surface free energy of the thermoplastic resin are γ _pol ^d and γ _pol ^p , respectively, and the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber are γ _fib ^d and γ _fib ^p , respectively, ΔW _floc [mJ/ _m 2 ] is expressed by ΔW _floc = 2 (((γ _pol ^d ) ^1/2 - (γ _fib ^{d ) 1/2} ) ² + ((γ _pol ^p ) ^1/2 - (γ fib p ) ^{1/2 ) 2} ),
The melt flow rate (measured at melting point + 5°C) of the thermoplastic resin is MFR [g / 10 min],
A method for producing a continuous fiber reinforced thermoplastic resin composite material, characterized in that the relationship ΔW _floc /MFR≦0.614 [mJ·10 min /m ² ·g] is satisfied. The method for producing a continuous fiber reinforced thermoplastic resin composite material according to claim 1, wherein the continuous reinforcing fibers are inorganic fibers. The method for producing a continuous fiber-reinforced thermoplastic resin composite material according to claim 2, wherein the inorganic fibers are glass fibers and/or carbon fibers. The method for producing a continuous fiber-reinforced thermoplastic resin composite material according to any one of claims 1 to 3, wherein the thermoplastic resin is a polyamide-based resin. Contains a thermoplastic resin and continuous reinforcing fibers,
When the dispersion term and polar term of the surface free energy of the thermoplastic resin are γ _pol ^d and γ _pol ^p , respectively, and the dispersion term and polar term of the surface free energy of the continuous reinforcing fiber are γ _fib ^d and γ _fib ^p , respectively, ΔW _floc [mJ/ _m 2 ] is expressed by ΔW _floc = 2 (((γ _pol ^d ) ^1/2 - (γ _fib ^{d ) 1/2} ) ² + ((γ _pol ^p ) ^1/2 - (γ fib p ) ^{1/2 ) 2} ),
The melt flow rate (measured at melting point + 5°C) of the thermoplastic resin is MFR [g / 10 min],
A continuous fiber reinforced thermoplastic resin composite material, characterized in that it satisfies the relationship ΔW _floc /MFR≦0.614 [mJ· 10 min/m ² ·g]. The continuous fiber reinforced thermoplastic resin composite material according to claim 5, wherein the continuous reinforcing fibers are inorganic fibers. The continuous fiber reinforced thermoplastic resin composite material according to claim 6, wherein the inorganic fibers are glass fibers and/or carbon fibers. The continuous fiber reinforced thermoplastic resin composite material according to any one of claims 5 to 7, wherein the thermoplastic resin is a polyamide resin.

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