JP2022167223A - Continuous fiber-reinforced resin composite material and method for producing the same - Google Patents

Abstract

To provide a fiber-reinforced resin composite material having high vibration fatigue recovery characteristics and strength stability, and a method for producing the same.SOLUTION: A continuous fiber-reinforced resin composite material is a continuous fiber-reinforced resin composite material containing continuous reinforcement fibers and a thermoplastic resin, wherein an interface coating rate variation index represented by the following expression of the continuous fiber-reinforced resin composite material is 0.8 to 1.2. Expression: (interface coating rate variation index)=(interface coating rate of continuous fiber-reinforced resin composite material before destruction test)/(interface coating rate of continuous fiber-reinforced resin composite material after destruction test).SELECTED DRAWING: None

Description

The present invention relates to a continuous fiber reinforced resin composite material and a manufacturing method thereof.

2. Description of the Related Art Composite material molded bodies obtained by adding a reinforcing material such as glass fiber to a matrix resin material are used for structural parts of various machines and automobiles, pressure vessels, tubular structures, and the like. In particular, from the viewpoint of strength, a continuous fiber-reinforced resin composite material in which the reinforcing fibers are continuous fibers is desired. As the continuous fiber reinforced resin composite material, the sizing agent added to the reinforcing fibers is devised (for example, see Patent Document 1 below), and the difference between the melting point and the crystallization temperature is devised (for example, See Patent Document 2 below), add an organic salt to a resin material (see, for example, Patent Document 3 below), and laminate a molding precursor fabric with a thermoplastic resin (for example, Patent Document 4), and those having good adhesive strength, affinity, etc. at the interface between the continuous reinforcing fiber and the resin (for example, see Patent Document 5 below) have been proposed.

Japanese Patent Application Laid-Open No. 2003-238213 Japanese Patent No. 5987335 JP 2017-222859 A Japanese Patent Application Laid-Open No. 2009-19202 WO2019/208586

However, in the continuous fiber reinforced resin composite materials of the prior art, the interface thickness changes before and after the rupture test, so there is room for improvement in that the interface recovery characteristics and strength stability are not sufficient.

In view of the level of such prior art, the problem to be solved by the present invention is to provide a fiber-reinforced resin composite material having high vibration fatigue recovery characteristics and strength stability, and a method for producing the same.

That is, the present invention is as follows.
[1]
A continuous fiber reinforced resin composite material containing continuous reinforced fibers and a thermoplastic resin,
A continuous fiber reinforced resin composite material, wherein the interface coverage change index represented by the following formula of the continuous fiber reinforced resin composite material is 0.8 to 1.2.
(Interfacial coverage change index) = (interfacial coverage of continuous fiber reinforced resin composite material before fracture test) / (interfacial coverage of continuous fiber reinforced resin composite material after fracture test)
[2]
The continuous fiber reinforced resin composite material according to [1], having a reinforcing fiber exposure change index represented by the following formula of 0.8 to 1.2.
(Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material before breaking test) / (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material after breaking test)
[3]
The continuous fiber-reinforced resin composite material according to [1] or [2], wherein the interfacial nitrogen has a relative element change index of 0.8 to 1.2.
[4]
The continuous fiber-reinforced resin composite material according to any one of [1] to [3], wherein the interfacial carbon has a relative element change index of 0.8 to 1.2.
[5]
The continuous fiber-reinforced resin composite material according to any one of [1] to [4], wherein the interface aluminum has a relative element change index of 0.8 to 1.2.
[6]
The continuous fiber-reinforced resin composite material according to any one of [1] to [5], wherein the interfacial silicon has a relative element change index of 0.8 to 1.2.
[7]
The continuous fiber-reinforced resin composite material according to any one of [1] to [6], wherein the interfacial calcium has a relative element change index of 0.8 to 1.2.
[8]
The continuous fiber-reinforced resin composite material according to any one of [1] to [7], wherein the interfacial oxygen has a relative element change index of 0.8 to 1.2.
[9]
A method for producing a continuous fiber reinforced resin composite material according to any one of [1] to [8],
The speed at which the thermoplastic resin impregnates the continuous reinforcing fibers is 0.8 to 1.2 times the speed at which the thermoplastic resin impregnates the coupling continuous reinforcing fibers treated only with the coupling agent,
The bending strength of the continuous coupling fiber reinforced resin composite material comprising the continuous coupling reinforcing fiber and the thermoplastic resin is 0.6 times or more the bending strength of the continuous fiber reinforced resin composite material. A method for producing a continuous fiber reinforced resin composite.

The continuous fiber-reinforced resin composite material according to the present invention has high vibration fatigue recovery characteristics and excellent strength stability.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

[Continuous fiber reinforced resin composite]
The continuous fiber reinforced resin composite material (hereinafter also simply referred to as "composite material") of the present embodiment contains continuous reinforcing fibers and a thermoplastic resin, and the interface coverage change index shown below before and after the fracture test is 0.8 to 1.2.
(Interfacial coverage change index) = (interfacial coverage of continuous fiber reinforced resin composite material before destructive test) / (interfacial coverage of composite material after destructive test)
The interface coverage change index is preferably 0.9 to 1.2, more preferably 0.95 to 1.15.

In this specification, the interfacial coverage (%) of the continuous fiber-reinforced resin composite material means that continuous reinforcing fibers after dissolving the thermoplastic resin from the continuous fiber-reinforced resin composite material in a solvent are measured by X-ray photoelectron spectroscopy (XPS). ) in the total of the relative element concentrations of the component elements derived from the thermoplastic resin remaining on the continuous reinforcing fiber surface and the relative element concentrations of the component elements derived from the continuous reinforcing fiber when measured by It can be determined from the ratio of the relative element concentrations of the component elements derived from the thermoplastic resin.
The interfacial coverage (interfacial coverage of the composite material before the fracture test) of the continuous fiber-reinforced resin composite material of the present embodiment is preferably 3 to 44%, more preferably 10 to 40%, and still more preferably 20%. ~37%.

In the continuous fiber-reinforced resin composite material of the present embodiment, the coverage of the thermoplastic resin remaining on the surface of the continuous reinforcing fibers after dissolving the thermoplastic resin in a solvent (interfacial coverage of the continuous reinforcing fiber resin composite material) is , for example, can be measured by the following method.
A continuous fiber reinforced resin composite material is immersed in a solvent, and the thermoplastic resin contained in the composite material is dissolved in the solvent. After removing the solvent, the remaining composite material is washed again with the fresh solvent to remove the thermoplastic resin on the surface of the continuous reinforcing fibers. At this time, the thermoplastic resin that strongly binds to the sizing agent (preferably the coupling agent) on the surface of the continuous reinforcing fibers remains on the surface of the continuous reinforcing fibers, and only the thermoplastic resin that is not bound to the sizing agent is removed by the solvent. be. Relative element concentrations of component elements derived from the thermoplastic resin remaining on the surface of the continuous reinforcing fiber and relative element elements derived from the continuous reinforcing fiber when the composite material was measured by X-ray photoelectron spectroscopy (XPS) after drying The interfacial coverage (%) of the continuous fiber reinforced resin composite material can be obtained from the ratio of the relative element concentration of the component elements derived from the thermoplastic resin remaining on the surface of the continuous reinforcing fiber to the total element concentration.

For example, when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, the following treatment methods may be used.
(a) The continuous fiber reinforced resin composite material is cut into thin pieces.
(b) 100 mg of the continuous fiber-reinforced resin composite material and 20 mL of hexafluoroisopropanol (HFIP) as a solvent are placed in a mix rotor and stirred at 23° C. for 5 hours.
(c) Remove the solvent by suction filtration, sprinkle 40 mL of fresh HFIP on the filter to wash the composite material, and then air dry.
(d) The composite material obtained in (c) and 20 mL of fresh HFIP are placed in a mix rotor and stirred at 23° C. for 2 hours.
(e) Remove the solvent by suction filtration, sprinkle 40 mL of fresh HFIP on the filter to wash the composite material, and then dry with a nitrogen blow at 23°C.
(f) The continuous reinforcing fibers obtained in (e) and 20 mL of fresh HFIP are placed in a mix rotor and stirred at 23°C for 2 hours.
(g) Remove the solvent by suction filtration, sprinkle 40 mL of fresh HFIP on the filter to wash the composite material, and air dry.
(h) Dry overnight in a vacuum oven set at 23°C.
The interfacial coverage is
(Interface coverage) (%) = [N] / ([N] + [Si]) x 100
can be found at Here, [N] is the relative elemental concentration of nitrogen and [Si] is the relative elemental concentration of silicon determined by XPS measurement.

For example, when the thermoplastic resin is polyamide and the continuous reinforcing fibers are carbon fibers, HFIP is used as a solvent, and a sample is prepared in the same manner as when the thermoplastic resin is polyamide and the continuous reinforcing fibers are glass fibers, The interfacial coverage is
(Interface coverage) (%) = [N] / ([N] + [O]) x 100
can be found at Here, [O] is the relative elemental concentration of oxygen determined by XPS measurement.

For example, when the thermoplastic resin is polypropylene and the continuous reinforcing fiber is glass fiber, the sample is prepared using xylene as the solvent. At this time, the temperature when stirring the composite material and solvent was 90 ° C., the temperature when drying and the temperature of nitrogen blow was 120 ° C., and the temperature of vacuum drying was 120 ° C., except that the thermoplastic resin was polyamide. , Prepare the sample in the same manner as when the continuous reinforcing fiber is glass fiber. The interfacial coverage is
(Interface coverage) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100
can be found at [C] is the relative elemental concentration of carbon determined by XPS measurement. For [C0], a composite material and a sample are prepared in the same manner using continuous reinforcing fibers from which a surface treatment agent such as a sizing agent has been removed by incineration or the like from continuous reinforcing fibers, and the surface treatment agent has not been treated, and XPS measurement is performed. It is the relative elemental concentration of carbon required when In the case of a combination of polypropylene and glass fiber, the interface coverage is a carbon element detected even when a sample that is considered to contain no carbon is measured by XPS, so the surface treatment agent It is calculated using the relative element concentration of carbon after treatment with continuous reinforcing fibers without

When the thermoplastic resin is polyphenylene ether, chloroform is used as a solvent regardless of the type of continuous reinforcing fiber, and the sample is prepared in the same manner as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, Interfacial coverage can be determined. In addition, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage is:
(Interface coverage) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100
is.

When the thermoplastic resin is polyvinyl alcohol, it can be prepared using water as a solvent regardless of the type of continuous reinforcing fiber. At this time, the temperature for stirring the composite material and solvent was 95 ° C., the temperature for drying and nitrogen blow was 120 ° C., and the temperature for vacuum drying was 120 ° C., except that the thermoplastic resin was polyamide, continuous A sample can be prepared in the same manner as in the case where the reinforcing fiber is glass fiber, and the interfacial coverage can be determined. In addition, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage is:
(Interface coverage) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100
is.

When the thermoplastic resin is polyvinyl acetate, regardless of the type of continuous reinforcing fiber, use acetone as the solvent and prepare the sample in the same way as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber. , the interfacial coverage can be determined. In addition, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage is
(Interface coverage) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100
is.

When the thermoplastic resin is polylactic acid, chloroform is used as a solvent regardless of the type of continuous reinforcing fiber, and the sample is prepared in the same manner as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber, Interfacial coverage can be determined. In addition, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage is
(Interface coverage) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100
is.

When the thermoplastic resin is polyvinyl chloride, regardless of the type of continuous reinforcing fiber, use Ascentone as a solvent and prepare the sample in the same manner as when the thermoplastic resin is polyamide and the continuous reinforcing fiber is glass fiber. , the interfacial coverage can be determined. In addition, when the continuous reinforcing fiber is glass fiber, the formula for calculating the interfacial coverage is:
(Interface coverage) (%) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100
is.

The interfacial coverage change index is the interfacial coverage of the interfacial resin of the continuous fiber reinforced resin composite material (interfacial coverage of the continuous fiber reinforced resin composite material not subjected to the destructive test) after the destructive test (for example, in the examples described later It can be obtained by dividing by the interface coverage of the continuous fiber reinforced resin composite material after conducting the one-handed bending fatigue test described in 1).
When the interfacial coverage change index is within the above range, high interfacial recovery characteristics can be exhibited, and variations in physical properties (for example, strength) can be reduced.
In order to adjust the interfacial coverage change index to the above range, for example, the speed at which the thermoplastic resin impregnates the continuous reinforcing fibers is the speed at which the thermoplastic resin impregnates the coupling continuous reinforcing fibers treated only with the coupling agent. 0.8 to 1.2 times, preferably 0.85 to 1.15 times, more preferably 0.9 to 1.1 times, the coupling continuous reinforcing fiber treated only with the above coupling agent The bending strength of the coupling continuous fiber reinforced resin composite material made of the thermoplastic resin is 0.6 times or more, preferably 0.6 to 1.2 times the bending strength of the continuous fiber reinforced resin composite material. Examples include a method using a combination of reinforcing fibers and a thermoplastic resin, and a method using a combination of glass fibers to which a surface treatment agent is added by the method described in Examples and PA66 produced by the method described in Examples.
As a combination of the continuous reinforcing fiber and the thermoplastic resin in which the bending strength is within the above range, polyamide resin (preferably polyamide 66, polyamide 6I, polyamide 6, polyamide 610, polyamide 410) and glass fiber or carbon fiber and a combination of polyolefin resin (preferably polypropylene, modified polypropylene, polyethylene, modified polyethylene) and glass fiber or carbon fiber.
If the impregnation speed and/or bending strength are within the above ranges, compatibility between the thermoplastic resin and the sizing agent (for example, the coupling agent in the sizing agent) on the surface of the continuous reinforcing fiber is improved.
Here, the impregnation speed is determined by, for example, laminating the continuous reinforcing fiber base material and the thermoplastic resin base material, performing hot press molding, the maximum temperature of the continuous fiber reinforced resin composite material is the melting temperature of the thermoplastic resin + 15 ° C., and the molding pressure is is 5 MPa, the cooling press is water-cooled (water temperature 20 ° C.), the pressure is performed to room temperature so that the pressure is 5 MPa, the obtained continuous reinforcing fiber composite material is cut with a band saw or the like, and the cross section is polished. , From the image obtained by SEM observation, etc., the occupied area of each of the continuous reinforcing fiber bundles, the thermoplastic resin, and the voids is determined, and the ratio of the void area to the continuous reinforcing fiber bundle (total) area is determined, and the following formula:
Impregnation rate (%) = {1-(void area/continuous reinforcing fiber bundle area)} x 100
The impregnation rate (%) calculated by is calculated by the time when the temperature of the thermoplastic resin at the time of hot press molding and cold press is above the melting point for thermoplastic resins with a melting point, and at the glass transition temperature or above for resins without a melting point. It can be obtained by dividing by the time (minutes).
The bending strength of a continuous fiber-reinforced resin composite material can be obtained, for example, by cutting a strip-shaped test piece from the continuous fiber-reinforced resin composite material and performing a three-point bending test in an environment of 23°C and 50% RH. can be done.

In the composite material of this embodiment, if the compatibility between the thermoplastic resin and the sizing agent (for example, coupling agent) on the surface of the continuous reinforcing fibers is good, the sizing agent on the surface of the continuous reinforcing fibers and the surroundings of the sizing agent Bonds or adheres with a thermoplastic resin in Here, in the sample from which the thermoplastic resin was removed with a solvent by the above method, only the thermoplastic resin bound or adhered to the sizing agent remained around the continuous reinforcing fibers, and the thermoplastic resin not bound to the sizing agent was removed. be. That is, by using this sample, it is possible to measure the proportion of the thermoplastic resin that is present on the surface of the continuous reinforcing fiber and that is bound or adhered to the sizing agent.
When the destructive test is performed, the thermoplastic resin that is not bonded or adhered to the sizing agent and the thermoplastic resin that is weakly bonded or adhered to the sizing agent, which is present on the surface of the continuous reinforcing fiber, falls off due to the impact. When there is a large amount of thermoplastic resin firmly bonded or adhered to the sizing agent on the surface of the continuous reinforcing fibers, the thermoplastic resin is less likely to fall off during the destructive test, and the thermoplastic resin on the continuous reinforcing fibers after the destructive test is reduced. It becomes difficult for the coverage ratio to decrease. A large amount of the thermoplastic resin remains on the surface of the continuous reinforcing fiber even after the destructive test, and the change in the interface coverage of the continuous fiber reinforced resin composite material before and after the destructive test is small.
In the above example, an example in which a sizing agent is present on the surface of the continuous reinforcing fiber was used for explanation. , can be similarly evaluated.

The continuous fiber reinforced resin composite material of the present embodiment preferably has a reinforcing fiber exposure change index represented by the following formula of 0.8 to 1.2.
(Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material before breaking test) / (Reinforcing fiber exposure ratio of composite material after breaking test)
The reinforcing fiber exposure change index is more preferably 0.85 to 1.15, even more preferably 0.90 to 1.10. When the reinforcing fiber exposure change index is within the above range, higher interfacial recovery characteristics can be exhibited, and variations in physical properties can be further reduced.
The reinforcing fiber exposure change index is the exposure ratio of continuous reinforcing fibers after dissolution of the thermoplastic resin of the continuous fiber reinforced resin composite material after a destructive test (for example, after conducting a single-handed bending fatigue test described in the examples below). ) can be obtained by dividing by the exposed ratio of continuous reinforcing fibers after dissolution of the thermoplastic resin in the continuous fiber reinforced resin composite material.
The exposed proportion of the continuous reinforcing fibers after the thermoplastic resin is dissolved is, for example, the thermoplastic resin contained in the continuous fiber reinforced resin composite material is dissolved in a solvent by the above method, the solvent is removed, and the remaining continuous reinforcing fibers are It is derived from the continuous reinforcing fibers obtained by washing with the fresh solvent, removing the thermoplastic resin other than the thermoplastic resin bound to the continuous reinforcing fibers, drying, and then measuring by X-ray photoelectron spectroscopy (XPS). It can be obtained by dividing the relative element concentration of the element by the relative element concentration of the element derived from the continuous reinforcing fiber raw material not treated with the sizing agent.
For example, when the continuous reinforcing fiber is glass fiber, the reinforcing fiber exposure ratio of the composite material is
(Reinforcing fiber exposure ratio of composite material) = [Al] / [Al0]
is required. [Al] is the relative elemental concentration of aluminum determined by XPS measurement. [Al0] is the relative element concentration of aluminum obtained when continuous reinforcing fibers without a sizing agent such as a sizing agent are treated in the same manner and subjected to XPS measurement.
For example, when the continuous reinforcing fiber is carbon fiber,
(Reinforcing fiber exposure ratio of composite material) = [O] / [O0]
is required. [O] is the relative elemental concentration of oxygen determined by XPS measurement. [O0] is the relative element concentration of oxygen obtained when continuous reinforcing fibers without a surface treatment agent such as a sizing agent are treated in the same manner and subjected to XPS measurement.

The ratio of exposed reinforcing fibers is the ratio of the portion of the continuous reinforcing fibers exposed after the above treatment on the surface of the raw material continuous reinforcing fibers. Since there is little change in the reinforcing fiber exposure ratio before and after the destructive test, a composite material with stable strength can be obtained even when vibration or impact occurs.

The relative element change index of interfacial nitrogen in the continuous fiber-reinforced resin composite material of the present embodiment is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
The relative element change index of interfacial carbon in the continuous fiber-reinforced resin composite material of the present embodiment is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
The interface aluminum relative element change index of the continuous fiber-reinforced resin composite material of the present embodiment is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
The relative element change index of interfacial silicon in the continuous fiber-reinforced resin composite material of the present embodiment is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
The relative element change index of interfacial calcium in the continuous fiber-reinforced resin composite material of the present embodiment is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
The relative element change index of interfacial oxygen in the continuous fiber-reinforced resin composite material of the present embodiment is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
When the relative element change index is within the above range, high interfacial recovery characteristics can be exhibited, and variations in physical properties can be reduced.

The relative element change index is the relative element concentration after dissolution of the thermoplastic resin of the continuous fiber reinforced resin composite material, and the continuous fiber reinforced after conducting a destructive test (for example, the single-handed bending fatigue test described in the examples below). It can be obtained by dividing by the relative element concentration after dissolving the resin in the resin composite material. The thermoplastic resin dissolution of the continuous fiber reinforced resin composite material can be performed by the method described above.
In order to adjust the relative element change index to the above range, for example, the speed at which the thermoplastic resin impregnates the continuous reinforcing fibers is 0, which is the speed at which the thermoplastic resin impregnates the coupling continuous reinforcing fibers treated only with the coupling agent. .8 to 1.2 times, preferably 0.85 to 1.15 times, more preferably 0.9 to 1.1 times, a method in which the coupled continuous reinforcing fibers treated only with the above coupling agent and the above A combination of continuous reinforcing fibers and a thermoplastic resin such that the flexural strength of the coupled continuous fiber reinforced resin composite material made of thermoplastic resin is 0.6 to 1.2 times the flexural strength of the continuous fiber reinforced resin composite material. A method using

[Form of continuous fiber reinforced resin composite material]
The form of the continuous fiber-reinforced resin composite material is not particularly limited, and includes the following various forms. For example, a woven or knitted fabric of continuous reinforcing fibers, a braid, a form in which a pipe-shaped thing and a thermoplastic resin are combined, a form in which continuous reinforcing fibers aligned in one direction and a thermoplastic resin are combined, continuous reinforcing fibers and a thermoplastic resin yarn are pulled in one direction and shaped, and a continuous reinforcing fiber and a thermoplastic resin yarn are woven, knitted, braided, and shaped into a pipe. .
The continuous fiber-reinforced resin composite material of the present embodiment may be a flat plate, or may be a laminate including a continuous reinforcing fiber layer and a thermoplastic resin layer. For example, the length direction of the continuous reinforcing fibers may be arranged substantially parallel to the surface of the flat plate. The layer of continuous reinforcing fibers is a layer containing continuous reinforcing fibers (for example, a continuous reinforcing fiber substrate), and may be a layer in which the inside of the continuous reinforcing fibers is impregnated with a thermoplastic resin.
The form of the intermediate material before shaping of the continuous fiber reinforced resin composite material is not particularly limited, and may be a mixed yarn of continuous reinforcing fibers and resin fibers, a coated yarn in which a bundle of continuous reinforcing fibers is coated with a resin, Continuous reinforcing fibers impregnated with resin in advance and made into a tape shape, continuous reinforcing fibers sandwiched between resin films, continuous reinforcing fibers with resin powder attached, and a bundle of continuous reinforcing fibers as a core material around are braided with resin fibers, resin impregnated between reinforcing fibers in advance, continuous reinforcing fibers and molten resin are brought into contact with each other, and the like.

[Method for producing continuous fiber reinforced resin composite]
The method for producing the continuous fiber-reinforced resin composite material of the present embodiment is not particularly limited, and includes the following various methods.

In one method, for example, a substrate constituting a continuous fiber reinforced resin composite material (for example, a substrate made of continuous reinforcing fibers, a substrate made of a thermoplastic resin) is cut or shaped according to the desired composite material. , The necessary number of sheets is stacked in consideration of the thickness of the target product, or the necessary number of sheets is stacked, and set in the mold according to the shape of the mold.

The cutting of the base material may be performed one by one, or may be performed after stacking the desired number of sheets. From the viewpoint of productivity, it is preferable to cut the sheets while they are stacked. Any cutting method may be used, and examples thereof include water jet, blade press, hot blade press, laser, and plotter. Among them, a hot blade press is preferable because it has an excellent cross-sectional shape and is easy to handle by welding the end faces when cutting a plurality of layers. An appropriate cutting shape can be adjusted by repeating trial and error, but it is preferable to set by performing a simulation by CAE (computer aided engineering) according to the shape of the mold.

The shaping of the base material may be performed by any method, and for example, it may be shaped into a sheet-like shape.

After setting the substrate in the mold, the mold is closed and compressed. Then, the temperature of the mold is adjusted to a temperature equal to or higher than the melting point of the thermoplastic resin constituting the continuous fiber-reinforced resin composite material, and the thermoplastic resin is melted and shaped. The clamping pressure is not particularly specified, but is preferably 1 MPa or higher, more preferably 3 MPa or higher. Alternatively, the mold may be clamped once for degassing and the clamping pressure of the mold may be temporarily released after compression molding. From the viewpoint of strength development, it is preferable that the compression molding time is long as long as the thermoplastic resin used does not thermally deteriorate, but from the viewpoint of productivity, it is preferably within 2 minutes, more preferably within 1 minute. is suitable.

The continuous fiber reinforced resin composite material may be further injection-filled with a hybrid thermoplastic resin composition to form a hybrid composite material. In the process of producing a hybrid composite material, the base material is set in a mold, the mold is closed, pressure is applied, and after a predetermined time, a predetermined thermoplastic resin composition for hybrid is injected and filled to mold. A hybrid composite material may be produced by bonding a thermoplastic resin as a substrate and a predetermined thermoplastic resin composition for hybrid.

The timing of injection filling of a predetermined hybrid thermoplastic resin composition greatly affects the interfacial strength between the two thermoplastic resins. The timing of injecting and filling the predetermined thermoplastic resin composition for hybrid is determined by setting the base material in the mold and closing the mold, and the mold temperature is equal to or higher than the melting point of the thermoplastic resin constituting the base material or the glass transition. Within 30 seconds after raising the temperature above the temperature is preferable.
The mold temperature when injection-filling the predetermined thermoplastic resin composition for hybrid is above the melting point or above the glass transition temperature of the thermoplastic resin forming the base material, which is bonded to the thermoplastic resin composition for hybrid. is preferred. More preferably, the melting point +10°C or higher or the glass transition temperature +10°C or higher of the thermoplastic resin constituting the base material, which is bonded to the thermoplastic resin composition for hybrid, and more preferably the melting point +20°C or higher or the glass transition temperature +20°C or higher, more preferably +30°C or higher to the melting point or +30°C or higher to the glass transition temperature.

In the hybrid composite material, it is preferable that the joint portion between the thermoplastic resin constituting the base material and the hybrid thermoplastic resin composition formed by injection molding has an uneven structure that is mixed with each other.
Setting the mold temperature above the melting point of the hybrid thermoplastic resin composition to be injected and setting the resin holding pressure at the time of injection molding to a high value, for example, 1 MPa or higher are effective in increasing the interfacial strength. In order to increase the interfacial strength, the holding pressure is preferably 5 MPa or more, more preferably 10 MPa or more.
In addition, holding the pressure for a long time, for example, 5 seconds or longer, preferably 10 seconds or longer, and more preferably until the mold temperature reaches the melting point of the thermoplastic resin composition or lower increases the interfacial strength. preferable from this point of view.

In the above-described method for producing a composite material of the present embodiment, the speed at which the thermoplastic resin impregnates the continuous reinforcing fibers is 0% of the speed at which the thermoplastic resin impregnates the coupling continuous reinforcing fibers treated only with the coupling agent. 0.8 to 1.2 times is preferable. Here, the coupled continuous reinforcing fibers refer to continuous reinforcing fibers produced in the same manner as the continuous reinforcing fibers, except that the sizing agent is changed to only the coupling agent. It is preferable to use a sizing agent containing a coupling agent and a lubricant and/or a binding agent for continuous reinforcing fibers, and to use the coupling agent for coupling continuous reinforcing fibers.
In the above-described method for producing a composite material of the present embodiment, the bending strength of the continuous coupling fiber reinforced resin composite material composed of the continuous coupling reinforcing fiber and the thermoplastic resin is equal to the bending strength of the continuous fiber reinforced resin composite material. is preferably 0.6 times or more. Here, the coupling continuous fiber reinforced resin composite material refers to a composite material produced by the same method as the continuous fiber reinforced resin composite material, except that the coupling continuous reinforcing fiber is used as the continuous reinforcing fiber. It is preferable to use a sizing agent containing a coupling agent and a lubricant and/or a binding agent for continuous reinforcing fibers, and to use the coupling agent for coupling continuous reinforcing fibers.

(Thermoplastic resin composition for hybrid)
The hybrid thermoplastic resin composition for injection molding used to produce the hybrid composite material is not particularly limited as long as it is a thermoplastic resin composition used for general injection molding.
The thermoplastic resin contained in the hybrid thermoplastic resin composition is not limited to the following, but examples include polyethylene, polypropylene, polyvinyl chloride, acrylic resins, styrene resins, polyethylene terephthalate, polybutylene terephthalate, A type of thermoplastic resin such as polyarylate, polyphenylene ether, modified polyphenylene ether resin, wholly aromatic polyester, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide resin, polysulfone, polyetheretherketone, polyetherketone, etc. Alternatively, a mixture obtained by mixing two or more kinds may be used.

The hybrid thermoplastic resin composition may contain various fillers. The hybrid thermoplastic resin composition may be a black resin composition containing a coloring agent.
Examples of various fillers include short fibers and long fiber materials, which are discontinuous reinforcing materials of the same type as the continuous reinforcing fibers.
When short glass fibers or long fibers are used as the discontinuous reinforcing material, the same bundling agent as that applied to the continuous reinforcing fibers constituting the continuous fiber-reinforced resin composite material of the present embodiment may be used. The sizing agent is preferably at least one selected from the group consisting of coupling agents (preferably silane coupling agents), lubricants, and sizing agents. As for the types of silane coupling agent, lubricant, and binding agent, the same ones as those used for the above continuous reinforcing fiber binding agent can be used.

The thermoplastic resin contained in the hybrid thermoplastic resin composition used for injection molding is similar to the thermoplastic resin of the joint surface constituting the continuous fiber reinforced resin composite material from the viewpoint of the interfacial strength with the thermoplastic resin to be joined. are preferred, and those of the same type are more preferred. Specifically, when polyamide 66 is used as the thermoplastic resin of the joint surface, polyamide 66 is preferable as the resin material of the hybrid thermoplastic resin composition for injection molding.

As other methods, there is a molding method in which the base material is placed in a mold and compressed by a double belt press machine, or a formwork is set up so as to surround the set base material on all four sides, and a double belt press machine is used to pressurize and mold. A method or a heating compression molding machine set to one or more temperatures and a cooling compression molding machine set to one or more temperatures are prepared, and the molds with the base material are placed in order, Examples include a molding method in which the material is put into a compression molding machine and molded, a continuous compression molding machine, and the like.

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

-Sizing agent-
A sizing agent is preferably attached to the continuous reinforcing fibers.
If glass fibers are selected as continuous reinforcing fibers, a sizing agent may be used.
The sizing agent (sizing agent) may contain one or more selected from the group consisting of coupling agents, lubricants, and binding agents, and preferably contains at least a binding agent or a coupling agent. More preferably, it consists of only one or more selected from the group consisting of ring agents, lubricants, and binding agents.
A coupling agent is a compound that bonds materials with different properties, mainly inorganic and organic materials. Examples of the coupling agent include, but are not limited to, silane coupling agents, polymer coupling agents, and polymerizable coupling agents. A coupling agent is preferred.
Also, the sizing agent may consist of a coupling agent (preferably a silane coupling agent) and a binding agent, or may consist of a coupling agent (preferably a silane coupling agent), a lubricant, and a binding agent. .
By being a sizing agent that creates a strong bond between the continuous reinforcing fibers (preferably glass fibers) and the resin surrounding them, it is possible to obtain a continuous fiber-reinforced resin composite material with a low porosity.
The sizing agent may be added externally to the material used or included internally in the material used. For example, lubricants may be included in the commercially available thermoplastic resins used.

--Silane coupling agent--
A silane coupling agent is usually used as a surface treatment agent for glass fibers and carbon fibers, and contributes to the improvement of interfacial adhesive strength.
Silane coupling agents include, but are not limited to, aminosilanes such as γ-aminopropyltrimethoxysilane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; mercaptosilanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes, maleic acids and the like. When a polyamide is used as the thermoplastic resin, it is preferable to select one that easily bonds with the carboxyl group or amino group that is the terminal group of the polyamide resin, and aminosilanes are preferable.

--lubricant--
Lubricants contribute to improving the openability of continuous reinforcing fibers (preferably glass fibers).
As the lubricant, any general liquid or solid lubricating material suitable for the purpose can be used as long as it does not interfere with the coupling agent and the binding agent. Animal and plant-based or mineral-based waxes such as waxes and lanolin waxes; and surfactants such as fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters and aromatic ethers.

--Binding agent--
The binding agent contributes to improving the bundling property of the continuous reinforcing fibers (preferably glass fibers) and improving the interfacial adhesive strength.
As the binding agent, polymers suitable for the purpose and thermoplastic resins other than the thermoplastic resins described above as the main material of the continuous fiber reinforced resin composite material can be used.
Polymers as binding agents include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, copolymers of methacrylic acid esters and copolymerizable monomers, and Salts with these primary, secondary and tertiary amines are included. 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 suitable. used for
The homopolymer of acrylic acid preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.
The copolymerizable monomers constituting the copolymer of acrylic acid and other copolymerizable monomers are not limited to the following, but for example, among monomers having a hydroxyl group and/or a carboxyl group, acrylic acid, maleic acid , methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid (except for acrylic acid alone). As a copolymerizable monomer, it is preferable to have one or more ester-based monomers.
Copolymers of methacrylic acid esters and copolymerizable monomers include methyl methacrylate or ethyl methacrylate (preferably methyl methacrylate), acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotone. acid, fumaric acid, itaconic acid, citraconic acid, trimellitic anhydride, pyromellitic dianhydride, and mesaconic acid with one or more copolymerizable monomers (preferably maleic anhydride) It is preferably a polymerizable monomer. For example, it may be a copolymer of one methacrylic acid ester and one copolymerizable monomer. The mass ratio of structural units derived from a methacrylic acid ester is preferably 30 to 98% by mass, more preferably 60 to 95% by mass, with respect to 100% by mass of a copolymer of a methacrylic acid ester and a copolymerizable monomer. . The mass ratio of the structural unit derived from the copolymerizable monomer to 100% by mass of the copolymer of the methacrylic acid ester and the copolymerizable monomer is preferably 2 to 70% by mass, more preferably 5 to 40% by mass. be. The weight average molecular weight of the copolymer of methacrylic acid ester and copolymerizable monomer is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.
Salts of homopolymers and copolymers of acrylic acid with primary, secondary and tertiary amines include, but are not limited to, triethylamine salts, triethanolamine salts and glycine salts. mentioned. The degree of neutralization is preferably 20 to 90%, preferably 40 to 60%, from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (silane coupling agent, etc.) and reducing the amine odor. is more preferred.
The weight average molecular weight of the salt-forming acrylic acid polymer is not particularly limited, but is preferably in the range of 3,000 to 50,000. It is preferably 3,000 or more from the viewpoint of improving bundling properties of the continuous reinforcing fibers, and preferably 50,000 or less from the viewpoint of improving the properties of a composite molded article.
When polyamide is used as the thermoplastic resin, it is preferable to use, as the binding agent, a resin with good wettability or a surface tension close to that of the polyamide resin. Specifically, for example, a polyurethane resin emulsion, a polyamide resin emulsion, or a modified product thereof can be selected.

Thermoplastic resins used as binders are not limited to the following, but examples include polyolefin resins, polyamide resins, polyurethane resins, polyacetal resins, polycarbonate resins, polyester resins, and polyether ketones. , polyether ether ketone, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, thermoplastic fluororesin, and modified thermoplastic resin obtained by modifying these. If the thermoplastic resin used as the binding agent is the same type of thermoplastic resin and/or modified thermoplastic resin as the resin that coats the continuous reinforcing fibers, after the composite material is formed, the glass fibers and the thermoplastic resin are combined. Adhesion is improved, which is preferable.

Furthermore, the adhesiveness between the continuous reinforcing fibers and the thermoplastic resin covering them is further improved, and when the sizing agent is attached to the continuous reinforcing fibers (for example, glass fibers) as an aqueous dispersion, the ratio of the emulsifier component is reduced. Alternatively, a modified thermoplastic resin is preferable as the thermoplastic resin used as the binding agent from the viewpoint of eliminating the need for an emulsifier.
Here, the modified thermoplastic resin means, in addition to the monomer component that can form the main chain of the thermoplastic resin, copolymerization of different monomer components for the purpose of changing the properties of the thermoplastic resin, resulting in hydrophilicity and crystallinity. , means modified thermodynamic properties.
The modified thermoplastic resin used as the binding agent is not limited to the following, but examples thereof include modified polyolefin-based resins, modified polyamide-based resins, and modified polyester-based resins.

The modified polyolefin resin as a binding agent is a copolymer of an olefin monomer such as ethylene or propylene and an olefin monomer such as an unsaturated carboxylic acid and/or its ester and a monomer that can be copolymerized, or an unsaturated carboxylic acid. It is a homopolymer of a monomer copolymerizable with an olefinic monomer such as a saturated carboxylic acid and/or its ester, and can be produced by a known method. A random copolymer obtained by copolymerizing an olefin monomer and an unsaturated carboxylic acid and/or an ester thereof, or a graft copolymer obtained by grafting an unsaturated carboxylic acid to an olefin may be used.
Examples of olefinic monomers include, but are not limited to, ethylene, propylene, 1-butene, and the like. These may be used individually by 1 type, or may be used in combination of 2 or more types.
Monomers that can be copolymerized with olefinic monomers include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Saturated carboxylic acids, esters of these unsaturated carboxylic acids (methyl esters, ethyl esters, etc.), etc., and these may be used alone or in combination of two or more. may
When the modified polyolefin resin is a copolymer of an olefin monomer and a monomer copolymerizable with the olefin monomer, the monomer ratio is 60 to 95 mass of the olefin monomer, with the total mass of the copolymerization being 100 mass%. %, preferably 5 to 40% by mass of monomers copolymerizable with olefinic monomers, more preferably 70 to 85% by mass of olefinic monomers, and 15 to 30% by mass of monomers copolymerizable with olefinic monomers. preferable. If the olefinic monomer is 60% by mass or more, the affinity with the matrix is good, and if the olefinic monomer is 95% by mass or less, the modified polyolefinic resin has good water dispersibility. , uniform application to continuous reinforcing fibers is easy.

In the modified polyolefin resin used as the binding agent, 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 the binding agent is not particularly limited, but is preferably 5,000 to 200,000, more preferably 50,000 to 150,000. It is preferably 5,000 or more from the viewpoint of improving the bundling property of glass fibers, and preferably 200,000 or less from the viewpoint of emulsion stability when water-dispersible.

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

The modified polyester resin used as a binding agent is a copolymer of polycarboxylic acid or its anhydride and polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. .
Hydrophilic groups include, for example, polyalkylene oxide groups, sulfonate groups, carboxyl groups, and neutralized salts thereof. Examples of polycarboxylic acids or anhydrides thereof include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, tri- or higher functional polycarboxylic acids, 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. etc.
Examples of the sulfonate-containing aromatic dicarboxylic acid include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, 5-sulfoorthophthalate, and the like.
Aliphatic dicarboxylic acids or alicyclic dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1 ,4-cyclohexanedicarboxylic acid, succinic anhydride, maleic anhydride and the like.
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-based resin, it is preferable that 40 to 99 mol % of the total polycarboxylic acid component is the aromatic dicarboxylic acid. 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 the sulfonate-containing aromatic dicarboxylic acid.

Examples of polyols constituting the modified polyester-based 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 its alkylene oxide adducts, and the like. Trimethylolpropane, glycerin, pentaerythritol and the like can be mentioned as tri- or higher functional polyols.

The copolymerization ratio of the polycarboxylic acid or its anhydride and the polyol constituting the modified polyester resin is 40 to 60% by mass of the polycarboxylic acid or its anhydride and the polyol, with the total mass of the copolymer components being 100% by mass. It 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, more preferably 10,000 to 30,000. It is preferably 3,000 or more from the viewpoint of improving bundling properties of continuous reinforcing fibers (for example, glass fibers), and preferably 100,000 or less from the viewpoint of emulsion stability when water-dispersible.

Polymers and thermoplastic resins used as binding agents may be used singly or in combination of two or more.
With the total amount of the binding agent as 100% by mass, it is selected from homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts of these with primary, secondary and tertiary amines. It is preferable to use 50% by mass or more of one or more polymers, more preferably 60% by mass or more.

When the sizing agent consists of a coupling agent (e.g., silane coupling agent) and a binding agent, the total adhering mass of the coupling agent and the binding agent with respect to 100% by mass of the continuous reinforcing fiber (e.g., glass fiber) is preferably is 0.1 to 3% by mass, more preferably 0.15 to 2% by mass, and still more preferably 0.2 to 1% by mass. From the viewpoint of bundling control of continuous reinforcing fibers (e.g., glass fibers) and improvement of interfacial adhesive strength, the attachment amount of the sizing agent is 100% by mass of the continuous reinforcing fibers (e.g., glass fibers), and the coupling agent and the binding agent is preferably 0.1% by mass or more, and preferably 3% by mass or less from the viewpoint of yarn handleability.
Further, when the sizing agent consists of a coupling agent (preferably a silane coupling agent), a lubricant, and a binding agent, the coupling agent, the lubricant, and the The total adhering mass of the binding agent is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, still more preferably 0.2 to 1% by mass. From the viewpoint of bundling control of continuous reinforcing fibers (for example, glass fibers) and improvement of interfacial adhesive strength, the amount of adhesion of the sizing agent is the total mass of the coupling agent, the lubricant and the binding agent with respect to 100% by mass of the continuous reinforcing fibers. is preferably 0.1% by mass or more, and preferably 3% by mass or less from the viewpoint of yarn handleability.
The amount of the coupling agent attached to 100% by mass of the continuous reinforcing fiber is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.9% by mass.

--Composition of sizing agent for glass fiber--
The amount of the coupling agent in the sizing agent for glass fibers is preferably 0.1 to 2% by mass from the viewpoint of improving the sizing properties of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite molded product. More preferably 0.1 to 1 mass %, still more preferably 0.2 to 0.5 mass %.
The content of the lubricant in the glass fiber sizing agent is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of providing sufficient lubricity. From the viewpoint of improving the mechanical strength of the composite molded article, the content is preferably 1.5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
The content of the binding agent in the glass fiber sizing agent is preferably 1 to 25% by mass, more preferably 1 to 25% by mass, from the viewpoints of controlling the sizing properties of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite molded product. 3 to 15% by mass, more preferably 3 to 10% by mass.

When glass fibers are used as the continuous reinforcing fibers and the sizing agent is composed of a silane coupling agent, a lubricant, and a sizing agent, the sizing agent for the glass fibers contains 0.00% of the silane coupling agent. It preferably contains 1 to 2% by mass, 0.01 to 1.5% by mass of lubricant, and 1 to 25% by mass of binding agent, and these components are diluted with water to make the total mass 100% by mass. Adjusting is preferred.

--Usage mode 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, etc., depending on the mode of use. 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 continuous fiber-reinforced resin composite material of the present embodiment is obtained by applying the above-described sizing agent to the glass fiber using a known method such as a roller applicator in a known glass fiber manufacturing process. It is obtained continuously by drying the glass fiber produced by applying it to the fiber.
The sizing agent for glass fibers may also be used by immersing the glass fibers in a liquid containing the sizing agent or by immersing the glass fiber substrate in a liquid containing the sizing agent.

Similarly, when carbon fibers are selected as continuous reinforcing fibers, a sizing agent may be used, and the sizing agent preferably comprises a coupling agent, a lubricant, and a binding agent. Coupling agents that are compatible with the hydroxyl groups present on the surface of the carbon fibers, binding agents that have good wettability with the selected thermoplastic resin and similar surface tension, and coupling agents and binding agents as lubricants. Those that do not inhibit the agent can be selected.
A known sizing agent can be used for the carbon fiber. Specifically, for example, the one described in JP-A-2015-101794 can be used.

When using other continuous reinforcing fibers, the type and amount of sizing agent that can be used for glass fibers and carbon fibers may be appropriately selected according to the properties of the continuous reinforcing fibers. It is preferable to set the type and application amount of the sizing agent as described above.

(Shape of continuous reinforcing fiber)
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 handling.
The single yarn diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, and even more preferably 6 to 20 μm from the viewpoint of strength and handleability. Most preferably it is between 8 and 18 μm.
The product RD of the single filament diameter R (μm) of the continuous reinforcing fiber and the density D (g/cm ³ ) is preferably 5 to 100 μm·g/cm ³ from the viewpoint of the handleability of the continuous reinforcing fiber and the strength of the composite material. , more preferably 10 to 50 μm·g/cm ³ , still more preferably 15 to 45 μm·g/cm ³ , still more preferably 20 to 45 μm·g/cm ³ .

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。 Density D can be measured with a hydrometer.
On the other hand, the single yarn diameter R (μm) is obtained from the density D (g/cm ³ ), the fineness (dtex), and the number of single yarns (threads) by the following formula:

It can be calculated by In addition, the single yarn diameter R (μm) can be determined, for example, by SEM observation of the continuous reinforcing fiber single yarn.

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

Continuous reinforcing fibers, for example, glass fibers, are made by weighing and mixing raw glass, making molten glass in a melting furnace, spinning this into glass filaments, applying a sizing agent, passing through a spinning machine, direct winding roving (DWR ), cakes, twisted yarns, and the like.
The continuous reinforcing fiber may be in any form, but it is preferable that it is wound around yarn, cake, or DWR, because the productivity and production stability in the step of coating with resin are increased. DWR is most preferable from the viewpoint of productivity.

The form of the continuous reinforcing fiber is not particularly limited, and includes various forms such as woven fabric, knitted fabric, braid, pipe-shaped one, non-crimp fabric, and unidirectional material, preferably woven fabric, non-crimp fabric, and unidirectional. It is the form of the material.

(Thermoplastic resin)
Examples of thermoplastic resins include, but are not limited to, polyolefin resins such as polyethylene and polypropylene; polyamide 6, polyamide 66, polyamide 46, polyamide 612, polyamide 6I, polyamide 6T, polyamide 6I/6T, polyamide MXD6, polyamide 11, polyamide 12, polyamide 610, polyamide resins such as polyamide 1010; polyethylene terephthalate, polybutylene terephthalate, polyester resins such as polytrimethylene terephthalate; polyacetal resins such as polyoxymethylene; Polyether resins such as ether ketone, polyether ether ketone, polyether glycol, polypropylene glycol, polytetramethylene ether glycol; polyether sulfone; polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluorine-based resins; polyurethane-based resins; acrylic resins; polyphenylene ether; and modified thermoplastic resins obtained by modifying these.

Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyether sulfones, polyphenylene sulfides, thermoplastic polyether imides, thermoplastic fluorine resins, and polyphenylene ethers are preferred. -based resin, modified polyolefin-based resin, polyamide-based resin, polyester-based resin, polyurethane-based resin, polyphenylene ether and acrylic-based resin are more preferable from the viewpoint of mechanical properties and versatility. More preferred are resins, polyphenylene ethers and polyester resins. Polyamide-based resins are more preferable from the viewpoint of durability against repeated loading.

-Polyester resin-
A polyester resin means a polymer compound having a --CO--O-- (ester) bond in its main chain.
Examples of polyester resins include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalene carboxylate and the like.
The polyester-based resin may be homopolyester or copolyester.
In the case of copolyester, homopolyester is preferably copolymerized with a third component. Examples of the third component include, but are not limited to, diethylene glycol, neopentyl glycol, and polyalkylene glycol. and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid and 5-sodiumsulfoisophthalic acid.
In addition, it is also possible to use polyester-based resins using raw materials derived from biomass resources, and although not limited to the following, for example, aliphatic resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate Polyester-based resins, aromatic polyester-based resins such as polybutylene adipate terephthalate, and the like are included.

-Polyamide resin-
A polyamide-based resin means a polymer compound having a —CO—NH—(amide) bond in its main chain. Examples thereof include aliphatic polyamides, aromatic polyamides, and wholly aromatic polyamides.

Examples of polyamide resins include, but are not limited to, polyamides obtained by ring-opening polymerization of lactams, polyamides obtained by self-condensation of ω-aminocarboxylic acids, and by condensing diamines and dicarboxylic acids. The resulting polyamides, as well as copolymers thereof, may be mentioned.
Polyamide-based resins may be used singly or as a mixture of two or more.
Examples of lactams include, but are not limited to, pyrrolidone, caprolactam, undecanelactam and dodecanelactam.
Examples of ω-aminocarboxylic acids include, but are not limited to, ω-amino fatty acids, which are water ring-opening compounds of lactams. Lactams or ω-aminocarboxylic acids may be condensed using two or more monomers in combination.
Examples of diamines (monomers) include, but are not limited to, linear aliphatic diamines such as hexamethylenediamine and pentamethylenediamine; 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, adipic acid, aliphatic dicarboxylic acids such as pimelic acid and sebacic acid; aromatic dicarboxylic acids such as phthalic acid and isophthalic acid; cyclohexane; Alicyclic dicarboxylic acids such as dicarboxylic acids can be mentioned. Diamines and dicarboxylic acids as monomers may be condensed either singly or in combination of two or more.

Examples of polyamide resins include, but are not limited to, polyamide 4 (polyα-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), and polyamide 12 (polydodecanamide). , Polyamide 46 (polytetramethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, polyamide 1010 and other aliphatic polyamides, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T ( polynonamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide MXD6, semi-aromatic polyamides such as polyamide 6I/6T, and copolymerized polyamides containing these as constituents.
Examples of copolyamides include, but are not limited to, a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and hexamethylene Copolymers of methylene terephthalamide and 2-methylpentanediamine terephthalamide are included.

[Additive]
The continuous fiber-reinforced resin composite material of the present embodiment may contain additives as necessary. The composite material of the present embodiment includes, for example, a coloring agent, an anti-aging agent, an antioxidant, a weathering agent, a metal deactivator, a light stabilizer, a heat stabilizer, an ultraviolet absorber, an antibacterial/antifungal agent, and a deodorant. , conductivity imparting agent, dispersant, softener, plasticizer, cross-linking agent, co-cross-linking agent, vulcanizing agent, vulcanizing aid, foaming agent, foaming aid, flame retardant, vibration damping agent, nucleating agent, medium Additives such as blending agents, lubricants, anti-blocking agents, dispersants, fluidity improvers and release agents may be contained. In addition, the above-mentioned additives refer to those other than the above-mentioned components (eg, the thermoplastic resin, the continuous reinforcing fiber, the components contained in the thermoplastic resin composition for hybrid, and the components contained in the sizing agent).
The content of the additive may be 3% by mass or less with respect to 100% by mass of the composite material.

(coloring agent)
Colorants include carbon black, nigrosine, aluminum pigment, titanium dioxide, ultramarine blue, cyanine blue, cyanine green, quinacridone, diatomaceous earth, monoazo salt, perylene, disazo, condensed azo, isoindoline, red iron oxide, nickel titanium yellow, diketone pyrrolo. Pyrrole, metal salts, perylene red, metal oxides, bismuth vanadate, cobalt green, cobalt blue, anthraquinone, phthalocyanine green, phthalocyanine blue and the like. Among them, black colorants are preferred, and carbon black and nigrosine are more preferred.

The continuous fiber reinforced resin composite material of the present embodiment preferably has a continuous reinforcing fiber content of 90 to 525 parts by mass and a content of other components of 0 to 2 parts by mass with respect to 100 parts by mass of the thermoplastic resin. More preferably, the content of the continuous reinforcing fiber is 150 to 340 parts by mass and the content of the other components is 0 to 1 part by mass with respect to 100 parts by mass of the thermoplastic resin.
The continuous-fiber-reinforced resin composite material of the present embodiment may be a composite material composed only of a thermoplastic resin and continuous reinforcing fibers.

[Applications of continuous fiber reinforced resin composite]
The continuous fiber-reinforced resin composite material of the present embodiment can be suitably used for structural material applications such as aircraft, automobiles, construction materials, and robots.
Car applications include, but are not limited to, chassis/frames, undercarriage, drive system parts, interior parts, exterior parts, functional parts, and other parts.
Specifically, steering axles, mounts, sunroofs, steps, souff trims, door trims, trunks, boot lids, bonnets, seat frames, seat backs, retractors, retractor support brackets, clutches, gears, pulleys, cams, args, elastic beams , baffling, lamp, reflector, glazing, front end module, back door inner, brake pedal, steering wheel, electrical material, sound absorbing material, door exterior, interior panel, instrument panel, rear gate, ceiling beam, seat, seat frame, wiper strut, EPS (Electric Power Steering), small motors, heat sinks, ECU (Engine Control Unit) boxes, ECU housings, steering gear box housings, plastic housings, EV (Electric Vehicle) motor housings, wire harnesses, in-vehicle meters, combination switches, Small motors, springs, dampers, wheels, wheel covers, frames, subframes, side frames, motorcycle frames, fuel tanks, oil pans, intake manifolds, propeller shafts, drive motors, monocoques, hydrogen tanks, fuel cell electrodes, panels, Floor panel, skin panel, door, cabin, roof, hood, valve, EGR (Exhaust Gas Recirculation) valve, variable valve timing unit, connecting rod, cylinder bore, member (engine mounting, front floor cloth, footwell cloth, seat cloth , inner side, rear cross, suspension, pillar reinforcement, front side, front panel, upper, dash panel cross, steering), tunnel, fastening insert, crash box, crash rail, corrugated, roof rail, upper body, side rail, braiding , door surround assembly, airbag components, body pillar, dash toe pillar gusset, suspension tower, bumper, body pillar lower, front body pillar, reinforcement (instrument panel, rail, roof, front body pillar, roof rail, roof side rail , locker, door belt line, front floor under, front body pillar upper, front body pillar lower , center pillar, center pillar hinge, door outside panel), side outer panel, front door window frame, MICS (Minimum Intrusion Cabin System) bulk, torque box, radiator support, radiator fan, water pump, fuel pump, electronically controlled throttle Body, engine control ECU, starter, alternator, manifold, transmission, clutch, dash panel, dash panel insulator pad, door side impact protection beam, bumper beam, door beam, bulkhead, outer pad, inner pad, rear seat rod, door panel, door trim board Sub-assemblies, energy absorbers (bumpers, shock absorbers), shock absorbers, shock-absorbing garnishes, pillar garnishes, roof side inner garnishes, resin ribs, side rail front spacers, side rail rear spacers, seat belt pretensioners, airbag sensors, Arm (suspension, lower, hood hinge), suspension link, shock absorption bracket, fender bracket, inverter bracket, inverter module, hood inner panel, hood panel, cowl louver, cowl top outer front panel, cowl top outer panel, floor silencer, Dump seat, hood insulator, fender side panel protector, cowl insulator, cowl top ventilator looper, cylinder head cover, tire deflector, fender support, strut tower bar, mission center tunnel, floor tunnel, radio core support, luggage panel, luggage floor, accelerator It can be suitably used as parts such as pedals and accelerator pedal bases.

[Molding of composite materials]
The continuous fiber reinforced resin composite material of this embodiment can be further molded. Examples of the above method include a method in which the continuous fiber-reinforced resin composite material of the present embodiment is cut into a predetermined size, heated with an infrared heater, and hot-pressed with a press molding machine.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples, and can be carried out with various modifications within the scope of the gist of the present invention. Needless to say.

[Interface coverage change index, reinforcing fiber exposure change index, relative element concentration change index of continuous fiber reinforced resin composite material]
When using 100 mg of continuous fiber reinforced resin composite material cut into thin pieces and resins 1 to 4, put HFIP, and when using resin 5, put 20 mL of xylene in the mix rotor. After stirring for 5 hours at a temperature of 90 ° C., remove the solvent by suction filtration, sprinkle 40 mL of fresh solvent on the filter to wash the continuous reinforcing fibers, air dry when using HFIP, 120 when using xylene It was dried with hot air in an environment of °C. The obtained continuous reinforcing fiber and 20 mL of a fresh solvent are placed in a mix rotor and stirred at a temperature of 23 ° C. when using HFIP or at a temperature of 90 ° C. when using xylene for 2 hours. After washing the continuous reinforcing fibers by sprinkling 40 mL of a suitable solvent, they were dried by blowing nitrogen at a temperature of 23° C. when using HFIP and at 120° C. when using xylene. Put the obtained continuous reinforcing fiber and 20 mL of fresh solvent in a mix rotor, stir at a temperature of 23 ° C. when using HFIP, or at a temperature of 90 ° C. when using xylene, for 2 hours. After washing the continuous reinforcing fiber by sprinkling 40 mL of a suitable solvent, it is air-dried when using HFIP, and dried with hot air in an environment of 120 ° C when using xylene. Dry overnight in the vacuum oven set. The obtained continuous reinforcing fiber is pressed into a flat plate, a 2 mm piece is taken out, and an excitation source mono. AlKα 20 kV × 5 mA 100 W, analysis size 100 μm × 1.4 mm, photoelectron extraction angle 45°, capture area (Survey scan): 117.4 eV, (Narrow scan): C1s, O1s, N1s, Si2p, Ca2p, Al2p, Pass Energy (Survey scan): 117.4 eV, (Narrow scan): Measurement was performed at 46.95 eV to determine the relative element concentrations of carbon, oxygen, nitrogen, silicon, aluminum, and calcium.
The interfacial coverage of the continuous fiber reinforced resin composite material was determined by the following formula 1 for Examples 1 to 4 and 6 and Comparative Examples 1 to 3, the following formula 2 for Example 5, and the following formula 3 for Example 7.
(Interface coverage) = [N]/([N] + [Si]) x 100 (1)
(Interface coverage) = [N]/([N] + [O]) x 100 (2)
(Interface coverage) = ([C] - [C0]) / ([C] - [C0] + [Si]) x 100 (3)
The reinforcing fiber exposure ratio of the composite material was obtained by the following formula 4 for Examples 1 to 4, 6 and 7 and Comparative Examples 1 to 3, and by the following formula 5 for Example 5.
(Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material) = [Al]/[Al0] (4)
(Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material) = [O] / [O0] (5)
[Al0] is the relative elemental concentration of aluminum when GF0 is used, and [C0] is the relative elemental concentration of aluminum when CF0 is used.
The interface coverage change index, the reinforcing fiber exposure change index, and the relative element change index of each element were obtained by the following formulas.
(Interfacial coverage change index) = (interfacial coverage of continuous fiber reinforced resin composite material before destructive test) / (interfacial coverage of composite material after destructive test)
(Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material before breaking test) / (Reinforcing fiber exposure ratio of composite material after breaking test)
(Interfacial nitrogen relative elemental change index) = (Interfacial nitrogen relative elemental index of continuous fiber reinforced resin composite material before fracture test) / (Interfacial nitrogen relative elemental index of composite material after fracture test)
(Relative elemental change index of interfacial oxygen) = (Relative elemental index of interfacial oxygen of continuous fiber reinforced resin composite material before fracture test) / (Relative elemental index of interfacial oxygen of composite material after fracture test)
(Relative elemental change index of interfacial carbon) = (Relative elemental index of interfacial carbon of continuous fiber reinforced resin composite material before fracture test) / (Relative elemental index of interfacial carbon of composite material after fracture test)
(Relative elemental change index of interfacial silicon) = (Relative elemental index of interfacial silicon of continuous fiber reinforced resin composite material before fracture test) / (Relative elemental index of interfacial silicon of composite material after fracture test)
(Relative elemental change index of interface aluminum) = (Relative elemental index of interface aluminum of continuous fiber reinforced resin composite material before fracture test) / (Relative elemental index of interface aluminum of composite material after fracture test)
(Relative elemental change index of interfacial calcium) = (Relative elemental index of interfacial calcium of continuous fiber reinforced resin composite material before fracture test) / (Relative elemental index of interfacial calcium of composite material after fracture test)
The destructive test is a one-handed bending vibration fatigue test, which will be described later.

[Impregnation speed]
As a molding machine, a hydraulic molding machine (Shoji Co., Ltd.) with a maximum clamping force of 50 tons was used. Five continuous reinforcing fiber substrates and six thermoplastic resin films are alternately laminated, placed in a mold equipped with a temperature sensor, and placed in a hot press molding machine set to the melting temperature of the thermoplastic resin + 65 ° C. After the temperature is monitored, the resin is pressed at a pressure of 5 MPa. After 30 seconds after reaching the melting temperature of the thermoplastic resin, it is taken out of the hot press molding machine, put into a cooling press, and is cooled with water at a pressure of 5 MPa. cooled. At this time, the maximum temperature of the continuous fiber-reinforced resin composite material was the melting point of the thermoplastic resin +15° C., and the time above the melting temperature of the thermoplastic resin was 1 minute. The obtained continuous reinforcing fiber composite material was cut with a band saw, and the cross section was polished so as not to damage the continuous reinforcing fibers. Then, from the image obtained by FE-SEM observation at a magnification of 50 times, the continuous reinforcing fiber bundle was obtained by ImageJ. , thermoplastic resin, and voids, and the ratio of the void area to the continuous reinforcing fiber bundle (total) area is calculated using the following formula:
Impregnation rate (%) = {1-(void area/continuous reinforcing fiber bundle area)} x 100
The impregnation rate (%/min) was obtained by dividing the impregnation rate (%) calculated by the time (minutes) during which the temperature of the thermoplastic resin was above the melting temperature during hot press molding and cold press. Here, the continuous reinforcing fiber bundle is a region in which fibers (bundles of single filaments) in the cross section of the injection-molded article are densely packed.
Here, the melting temperature is the melting point when the thermoplastic resin has a melting point, and the glass transition temperature when the thermoplastic resin does not have a melting point.

[Bending strength]
A strip-shaped test piece with a length of 100 mm, a width of 10 mm, and a thickness of 2 mm is cut out from the continuous fiber reinforced resin composite material, and the span is set to 32 mm using a jig for three-point bending with an Instron universal testing machine. The bending strength (MPa) was measured at a speed of 1 mm/min under an environment of 23° C. and 50% RH. Measurements were taken at 50 points, and the median value was taken as the bending strength.

[Bending vibration fatigue recovery characteristics]
A test piece of ASTM-D671 Type A is prepared from a continuous fiber reinforced resin composite material, and a repeated vibration fatigue tester (B-70, Toyo Seiki Seisakusho Co., Ltd.) is used at a test temperature of 23 ° C., a frequency of 20 Hz, and a sine wave waveform. A single-handed bending vibration fatigue test was performed, and the number of judgments (A) of the vibration fatigue test at a stress corresponding to 35% of the bending strength of the continuous fiber-reinforced resin composite material of each example was determined. Similarly, a vibration fatigue test was performed at a stress corresponding to 35% of the bending strength, and the test was stopped when the number of times reached half that of (A), and a post-breakage test piece was obtained. Place the test piece after the destructive test in a mold with a spigot structure, use a hydraulic molding machine (Shoji Co., Ltd.) with a maximum mold clamping force of 50 tons, heat the temperature inside the molding machine to 200 ° C., and then clamp the mold. The mold was clamped with a force of 5 MPa, and heat-pressed for 15 minutes to obtain a test piece after recovery. After recovery, the test piece was subjected to a bending vibration fatigue test under the same conditions, and the number of judgments (B) was obtained.
The bending vibration fatigue recovery characteristics were determined by the following formula.
(Bending vibration fatigue property) = (B) / (A)

[Measurement of variation]
A bending strength test is performed on 50 test pieces to measure the bending strength, and the average value of the bending strength is A, and the bending strength in the i-th measurement (i = 1 to 50) is Ai. The coefficient of variation was obtained according to the formula and taken as variation.

Materials used in Examples and Comparative Examples are as follows.
[Continuous reinforcing fiber]
(glass fiber)
Glass fiber 1 (GF1):
A glass fiber having a fineness of 1.15 g/m and a number of single filaments of 2000 was attached to 100% by mass of a sizing agent in an amount of 0.8% by mass. The wound form was DWR, and the average single yarn diameter was about 16 μm. For adhesion of the sizing agent, 0.8% by mass of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 1.2% by mass of caranauba wax, and 10% by mass of maleic anhydride. An aqueous sizing agent solution prepared by adjusting with deionized water so as to be 2% by mass of a copolymer compound having a weight average molecular weight of 15,000 obtained by copolymerizing 90% by mass of methyl methacrylate was used. Each component attached to the glass fiber was 0.16% by mass of γ-aminopropyltrimethoxysilane, 0.40% by mass of caranauba wax, and 0.24% by mass of a copolymer compound with respect to 100% by mass of the glass fiber. .
Glass fiber 2 (GF2):
Glass fibers obtained by treating GF1 at 650° C. for 3 hours in an electric furnace were treated with a 0.2% by mass aqueous solution of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent. for 30 minutes and dried at 110° C. for 3 hours. γ-Aminopropyltrimethoxysilane adhering to the glass fiber was 0.16% by mass with respect to 100% by mass of the glass fiber.
Glass fiber 0 (GF0):
GF1 was treated in an electric furnace at 650° C. for 3 hours to obtain GF0 containing no sizing agent.

(Carbon fiber)
Carbon fiber 1 (CF1):
A 100% by mass PAN-based carbon fiber with a single filament count of 12,000 was produced by attaching 1.0% by mass of a sizing agent. For adhesion of the sizing agent, 0.8% by mass of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3% by mass of caranauba wax, and 10% by mass of maleic anhydride. An aqueous sizing agent solution prepared by adjusting with deionized water so as to be 1% by mass of a copolymer compound having a weight average molecular weight of 20,000 obtained by copolymerizing 90% by mass of methyl methacrylate was used. Each component adhering to the carbon fiber was 0.38% by mass of γ-aminopropyltrimethoxysilane, 0.48% by mass of caranauba wax, and 0.14% by mass of the copolymer compound with respect to 100% by mass of the carbon fiber. .
Carbon fiber 2 (CF2):
A PAN-based carbon fiber with a single yarn count of 12,000 was immersed in an aqueous solution containing 0.38% by mass of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent at 60 ° C. for 12 hours, It was dried at 110° C. for 6 hours. γ-Aminopropyltrimethoxysilane adhering to the carbon fibers was 0.38% by mass with respect to 100% by mass of the carbon fibers.
Carbon fiber 0 (CF0): PAN-based carbon fiber with a single yarn count of 12000

[Preparation of continuous reinforcing fiber base material]
Glass cloth:
A glass cloth 1 (GC1) was manufactured by weaving using the above GF1 as warp and weft using a rapier loom (1 m weaving width). The resulting glass cloth had a plain weave, a weave density of 6.5 threads/25 mm, and a basis weight of 640 g/m ² .
GC2 was similarly obtained using GF2.
Carbon fiber cloth:
A carbon fiber cloth 1 (CC1) was manufactured by weaving using a rapier loom (with a weaving width of 1 m) using the carbon fibers 1 as warp and weft. The obtained carbon fiber cloth had a plain weave, a weave density of 6.5 threads/25 mm, and a basis weight of 425 g/m ² .
Further, CC2 was similarly obtained using carbon fiber 2.

[Thermoplastic resin]
Resin 1: Polyamide 66
The polymerization reaction of polyamide was carried out as follows by the "hot melt polymerization method".
A salt containing adipic acid (Wako Pure Chemical Industries) and hexamethylenediamine (Tokyo Chemical Industry) at a molar ratio of 45:55: 1500 g and adipic acid: 300 g were dissolved in distilled water: 1500 g, and 55 masses of raw material monomers were dissolved. % uniform aqueous solution was prepared. This aqueous solution was placed in an autoclave having an internal volume of 7.0 L, and the autoclave was purged with nitrogen. While stirring at a temperature of 130° C. or higher and 150° C. or lower, the solution was concentrated by removing steam gradually until the solution concentration reached 70% by mass. After that, the internal temperature was raised to 225°C. At this time, the autoclave was pressurized to 1.7 MPa. The mixture was allowed to react for 70 minutes while the pressure was maintained at 1.7 MPa by gradually removing water vapor until the internal temperature reached 255° C. for 2 hours. The pressure was then reduced over 1.7 hours. After that, the inside of the autoclave was maintained under a reduced pressure of 650 torr for 15 minutes. At this time, the final internal temperature of the polymerization was 265°C. Then, it was pressurized with nitrogen to form a strand from the lower spinneret (nozzle), cooled with water, cut, discharged in pellet form, and dried at 100° C. for 12 hours in a nitrogen atmosphere. The obtained pellets and lubricant (PEG400, Tokyo Kasei Kogyo) are molded with a single-screw extruder, water-cooled, cut, discharged in the form of pellets, dried at 100 ° C. for 12 hours in a nitrogen atmosphere, resin 1 (Polyamide 66) was obtained. Mw=42000, Mw/Mn=2.08, melting temperature (melting point (Tm))=264°C, glass transition temperature (Tg)=50°C.
Resin 2:
0.03% by mass of copper iodide and 0.2% by mass of potassium iodide are dry-blended with respect to 100% by mass of resin 1, and kneaded with a twin-screw kneader (TEM26SS, Toshiba Machine) set at 280 ° C. Then, it was water-cooled and cut, discharged in the form of pellets, dried at 100°C under a nitrogen atmosphere for 12 hours, and resin 2 having a melting temperature of 264°C was obtained.
Resin 3: Polyamide 6I
The polymerization reaction of polyamide was carried out as follows by the "hot melt polymerization method".
1,500 g of a salt containing an equimolar salt of isophthalic acid (Wako Pure Chemical Industries, Ltd.) and hexamethylenediamine at a molar ratio of 45:55, and 300 g of isophthalic acid were dissolved in 1,500 g of distilled water to form a uniform aqueous solution. made. While stirring at a temperature of 110° C. or higher and 140° C. or lower, the solution was concentrated by removing steam gradually until the solution concentration reached 70% by mass. After that, the internal temperature was raised to 235°C. The mixture was allowed to react for 70 minutes, while keeping the pressure constant by gradually removing water vapor until the internal temperature reached 245° C. for 2 hours. The pressure was then reduced over 90 minutes. After that, the inside of the autoclave was maintained under a reduced pressure of 650 torr for 10 minutes. At this time, the final internal temperature of the polymerization was 265°C. After that, it was pressurized with nitrogen, made into a strand form from a lower spinneret (nozzle), water-cooled and cut, and discharged in the form of pellets. The pellets were dried at 100° C. under a nitrogen atmosphere for 12 hours. The obtained pellets and lubricant (PEG400, Tokyo Kasei Kogyo) are molded with a single-screw extruder, water-cooled, cut, discharged in pellet form, dried at 100 ° C. for 12 hours in a nitrogen atmosphere, resin 3 (Polyamide 6I) was obtained. The obtained resin 3 (polyamide 6I) had Mw=18000, Mw/Mn=1.94, and melting temperature (glass transition temperature (Tg))=130°C.
In the case of an amorphous resin that does not have a crystalline melting point, the melting temperature is the glass transition temperature.
Resin 4:
Resin 1 and Resin 3 were dry blended at a weight ratio of 2:1 to obtain Resin 4 with a melting temperature of 259°C.
Resin 5:
Maleic acid-modified polypropylene (Sanyo Chemical Industries, Ltd., melting temperature (melting point) = 160°C)

[Preparation of thermoplastic resin film]
A thermoplastic resin film was obtained by molding using a T-die extrusion molding machine (manufactured by Soken Co., Ltd.). The thickness of the thermoplastic resin film was 180 μm.

[Example 1]
Using resin 1, thermoplastic resin film 1 was obtained by the above method.
Four pieces of glass cloth 1 (GC1) and five pieces of thermoplastic resin film 1 are prepared, and the glass cloth 1 and the thermoplastic resin film 1 are alternately laminated so that the thermoplastic resin film 1 is on the surface, and molding is performed. , a continuous fiber reinforced resin composite material having a thickness of 2 mm was obtained. A continuous compression molding machine was used as the molding machine. The glass cloth and the thermoplastic resin film 1 are stacked as described above and placed in a molding machine, the temperature of the heating zone in the molding machine is adjusted to 350 ° C., the cooling zone is adjusted by oil cooling, the pressure is 5 MPa, and the belt speed is adjusted. Compression molding was performed at 0.6 m/min.
In addition, in order to compare the bending strength, using the glass cloth 2 (coupling continuous reinforcing fiber) treated only with a coupling agent, a bending test material (coupling continuous fiber reinforced resin composite material) was obtained.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Example 2]
A continuous fiber reinforced resin composite material having a thickness of 2 mm and a bending test material (coupling continuous fiber reinforced resin composite material) were obtained in the same manner as in Example 1 except that Resin 2 was used as the thermoplastic resin.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Example 3]
A continuous fiber reinforced resin composite material having a thickness of 2 mm and a bending test material (coupling continuous fiber reinforced resin composite material) were obtained in the same manner as in Example 1 except that Resin 3 was used as the thermoplastic resin.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Example 4]
A continuous fiber reinforced resin composite material having a thickness of 2 mm and a bending test material (coupling continuous fiber reinforced resin composite material) were obtained in the same manner as in Example 1 except that Resin 4 was used as the thermoplastic resin.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Example 5]
Continuous fiber reinforcement with a thickness of 2 mm was performed in the same manner as in Example 1 except that a composite material composed of the carbon fiber cloth 1 and the thermoplastic resin film 1 was produced using the carbon fiber cloth 1 as the continuous reinforcing fiber base material. A resin composite material was obtained. As the thermoplastic resin film, a film prepared in the same manner as the thermoplastic resin film was used except that the thickness was 118 μm.
In addition, in order to compare bending strength, a bending test material (coupling continuous fiber reinforced resin composite material) having a thickness of 2 mm was similarly obtained using carbon fiber cloth 2 treated only with a coupling agent. .
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Example 6]
Instead of GF1, GF1 was treated with 20 wt% of an aqueous sodium aluminate solution as an additive for adjusting the aluminum concentration for 1 hour, and dried at 110 ° C. for 2 hours. A continuous fiber reinforced resin composite material having a thickness of 2 mm was obtained in the same manner as in Example 1. A bending test material (coupling continuous fiber reinforced resin composite material) was produced in the same manner as in Example 1.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Example 7]
A continuous fiber reinforced resin composite material having a thickness of 2 mm and a bending test material were obtained in the same manner as in Example 1 except that Resin 5 was used as the thermoplastic resin.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Comparative Example 1]
Instead of glass cloth 1, 0.16% by mass of 3-glycidoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.) as a sizing agent with respect to 100% by mass of the glass fiber used to produce GF1. , epoxy resin emulsion 0.40% by mass, using a glass fiber (GF4) to which a mixture of 0.24% by mass of carnauba wax is attached, a plain weave, a weave density of 6.5 / 25 mm, a basis weight of 600 g / m A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that the glass cloth (GC4) of No. ² was produced and used.
In addition, in order to compare the bending strength, 3-glycidoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.) 0 as a coupling agent was added to 100% by mass of the glass fiber used to produce GF1. Using glass fiber (coupling continuous reinforcing fiber, GF5) to which .16% by mass is attached, plain weave, weave density is 6.5 / 25 mm, basis weight 600 g / m ² using glass cloth (GC5), Similarly, a bending test material (coupling continuous fiber reinforced resin composite material) having a thickness of 2 mm was obtained.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Comparative Example 2]
Instead of the glass cloth 1, glass fibers (GF6) with a fineness of 1.15 g / m and a single yarn number of 2000, which are not treated with a sizing agent, are used in a plain weave, with a weave density of 6.5 / 25 mm and a basis weight of 640 g / A continuous fiber reinforced resin composite material and a bending test material were obtained in the same manner as in Example 1 except that m ² of glass cloth (GC6) was produced and used.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

[Comparative Example 3]
The same evaluation as in Example 1 was performed using “Tepex dynalite 101” manufactured by Bond Laminate in which a glass cloth impregnated with polyamide 66 was used.
Table 1 shows the physical properties of the obtained continuous fiber reinforced resin composite material.

Table 1 shows the impregnation speed and bending strength when the glass cloth 2 or the carbon fiber cloth 2 is used.

The continuous fiber reinforced resin composite material of the present embodiment can be used as a reinforcing material for materials that require a high level of mechanical properties, such as structural parts for various machines and automobiles, and for composite molding with a thermoplastic resin composition. It can be used industrially as a body material.

Claims (9)

A continuous fiber reinforced resin composite material containing continuous reinforced fibers and a thermoplastic resin,
A continuous fiber reinforced resin composite material, wherein the interface coverage change index represented by the following formula of the continuous fiber reinforced resin composite material is 0.8 to 1.2.
(Interfacial coverage change index) = (interfacial coverage of continuous fiber reinforced resin composite material before fracture test) / (interfacial coverage of continuous fiber reinforced resin composite material after fracture test) The continuous fiber reinforced resin composite material according to claim 1, wherein the reinforced fiber exposure change index represented by the following formula is 0.8 to 1.2.
(Reinforcing fiber exposure change index) = (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material before breaking test) / (Reinforcing fiber exposure ratio of continuous fiber reinforced resin composite material after breaking test) 3. The continuous fiber-reinforced resin composite material according to claim 1, wherein the relative element change index of interfacial nitrogen is 0.8 to 1.2. The continuous fiber-reinforced resin composite material according to any one of claims 1 to 3, wherein the interfacial carbon has a relative elemental change index of 0.8 to 1.2. The continuous fiber-reinforced resin composite material according to any one of claims 1 to 4, wherein the interface aluminum has a relative element change index of 0.8 to 1.2. The continuous fiber reinforced resin composite material according to any one of claims 1 to 5, wherein the interfacial silicon has a relative element change index of 0.8 to 1.2. The continuous fiber-reinforced resin composite material according to any one of claims 1 to 6, wherein the interfacial calcium has a relative elemental change index of 0.8 to 1.2. The continuous fiber-reinforced resin composite material according to any one of claims 1 to 7, wherein the interfacial oxygen has a relative elemental change index of 0.8 to 1.2. A method for producing a continuous fiber reinforced resin composite material according to any one of claims 1 to 8,
The speed at which the thermoplastic resin impregnates the continuous reinforcing fibers is 0.8 to 1.2 times the speed at which the thermoplastic resin impregnates the coupling continuous reinforcing fibers treated only with the coupling agent,
The bending strength of the continuous coupling fiber reinforced resin composite material comprising the continuous coupling reinforcing fiber and the thermoplastic resin is 0.6 times or more the bending strength of the continuous fiber reinforced resin composite material. A method for producing a continuous fiber reinforced resin composite.