JP2023158352A - Thermoplastic resin composition and molded product of the same - Google Patents

Abstract

To provide a thermoplastic resin composition which has high mechanical strength and excellent moist heat resistance, and a molded product of the same.SOLUTION: A thermoplastic resin composition contains a thermoplastic resin (A), a thermoplastic resin (B), and a thermoplastic resin (C), and has a morphology of a co-continuous structure, wherein the first phase of the co-continuous structure is mainly composed of the thermoplastic resin (A), the second phase of the co-continuous structure is mainly composed of a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C), in the first phase, the mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) is dispersed in the thermoplastic resin (A), and in the second phase, the thermoplastic resin (A) is dispersed in the mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C).SELECTED DRAWING: Figure 1

Description

The present invention relates to a thermoplastic resin composition and a molded article thereof.

In recent years, particularly in the field of automobiles, improvements in fuel efficiency by reducing the weight of automobiles have been studied. For example, there is a growing movement to replace conventional metal structural members with fiber-reinforced plastics, and fiber-reinforced plastics with excellent strength are in demand.

Reinforced fiber composite materials (for example, carbon fiber reinforced thermoplastic resins, sometimes abbreviated as CFRTP) that have a thermoplastic resin as a matrix have the advantage of being easy to mold and recycle, and have been put into practical use. Studies are currently underway (Patent Documents 1 and 2).

Japanese Patent Application Publication No. 2018-145245 International Publication No. 2020/174748

When a thermoplastic resin is used as the matrix, as described above, it has advantages such as ease of molding and ease of recycling. However, there were problems with mechanical strength and moist heat resistance.

An object of the present invention is to provide a thermoplastic resin composition that has high mechanical strength and excellent heat and humidity resistance, and a molded article thereof.

In view of the above problems, the present inventors studied the morphology of thermoplastic resin compositions. As a result, mechanical strength is high when three types of thermoplastic resins are used in combination to develop a co-continuous structure morphology, and each phase constituting the co-continuous structure has a sea-island morphology. The inventors have discovered that a thermoplastic resin composition having heat and humidity resistance can be obtained, and have completed the present invention.

According to the present invention, the following thermoplastic resin compositions and the like are provided.
1. Including thermoplastic resin (A), thermoplastic resin (B) and thermoplastic resin (C),
It has a co-continuous morphology,
The first phase of the co-continuous structure mainly consists of the thermoplastic resin (A), and the second phase of the co-continuous structure mainly consists of the thermoplastic resin (B) and the thermoplastic resin (C). ) consists of a mixed phase of
In the first phase, a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) is dispersed in the thermoplastic resin (A),
A thermoplastic resin composition in which the thermoplastic resin (A) is dispersed in a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) in the second phase.
2. The average diameter of the mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) present in the first phase is 500 nm or less,
2. The thermoplastic resin composition according to 1, wherein the thermoplastic resin (A) present in the second phase has an average diameter of 500 nm or less.
3. 1 or 2, wherein the thermoplastic resin (A) and the thermoplastic resin (C) have a polar functional group, and the thermoplastic resin (B) and the thermoplastic resin (C) are completely compatible. thermoplastic resin composition.
4. 4. The thermoplastic resin composition according to 3, wherein the polar functional groups of the thermoplastic resin (A) and the thermoplastic resin (C) are carboxyl groups or amino groups.
5. 5. The thermoplastic resin composition according to any one of 1 to 4, wherein the thermoplastic resin (A) and the thermoplastic resin (B) are crystalline resins.
6. 6. The thermoplastic resin composition according to any one of 1 to 5, wherein the thermoplastic resin (C) is a polyarylene ether.
7. 7. The thermoplastic resin composition according to any one of 1 to 6, wherein the thermoplastic resin (B) is syndiotactic polystyrene.
8. The mass ratio of the thermoplastic resin (A) to the sum of the thermoplastic resin (B) and the thermoplastic resin (C) ((A):((B)+(C))) is 40:60 to 8. The thermoplastic resin composition according to any one of 1 to 7, which has a ratio of 60:40.
9. The thermoplastic resin (C) is added to 100 parts by mass of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C) ((A) + (B) + (C)). ) is 3 to 15 parts by mass, the thermoplastic resin composition according to any one of 1 to 8.
10. 10. The thermoplastic resin composition according to any one of 1 to 9, further comprising reinforcing fibers (D).
11. 11. The thermoplastic resin composition according to 10, wherein the reinforcing fiber (D) is one or more selected from glass fiber and carbon fiber.
12. 12. The thermoplastic resin composition according to 10 or 11, wherein the surface of the reinforcing fiber (D) is coated with the first phase.
13. A molded article made of the thermoplastic resin composition according to any one of 1 to 9.
14. A molded article made of the thermoplastic resin composition according to any one of 10 to 12.
15. 15. The molded article according to 14, which has a strength retention rate of 80% or more after a moist heat treatment at 80° C./95% RH for 500 hours, represented by the following formula (1).

According to the present invention, it is possible to provide a thermoplastic resin composition that has high mechanical strength and excellent heat and humidity resistance, and a molded article thereof.

1 is a cross-sectional scanning electron microscope (SEM) image of the thermoplastic resin composition obtained in Example 1. 1 is a SEM image of a thermoplastic resin composition obtained in Comparative Example 1. It is an enlarged image of the SEM image (Example 1) of FIG. It is an enlarged image of the SEM image (comparative example 1) of FIG. 2. 1 is a cross-sectional SEM image of carbon fibers in the thermoplastic resin composition obtained in Example 1. 1 is a cross-sectional SEM image of carbon fibers in a thermoplastic resin composition obtained in Comparative Example 1.

Hereinafter, the thermoplastic resin composition of the present invention and its molded article will be explained in detail. In this specification, the preferred provisions can be arbitrarily adopted, and combinations of preferred provisions are more preferred. In this specification, the description "XX to YY" means "XX or more and YY or less".

The thermoplastic resin composition according to the first embodiment of the present invention includes a thermoplastic resin (A), a thermoplastic resin (B), and a thermoplastic resin (C) that are different from each other. It is characterized in that the following morphologies A and B are observed by cross-sectional scanning electron microscopy (SEM).
Morphology A: co-continuous structure, where the first phase of the co-continuous structure mainly consists of thermoplastic resin (A), and the second phase of co-continuous structure mainly consists of thermoplastic resin (B) and thermoplastic resin (A). Consists of a mixed phase of plastic resin (C).
Morphology B: In the enlarged observation of the first phase, a mixed phase of thermoplastic resin (B) and thermoplastic resin (C) is dispersed in the thermoplastic resin (A) (sea-island structure); In the enlarged phase observation, the thermoplastic resin (A) is dispersed in a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) (sea-island structure).

Here, the co-continuous structure means a structure in which a plurality of components are mixed with each other while forming a continuous phase.
The sea-island structure means a structure in which other components are dispersed in the form of particles (islands) among a plurality of components that form a continuous phase (matrix).
Regarding the co-continuous structure and the sea-island structure, for example, refer to "Basic Polymer Science One Point 7, Structure I: Polymer Alloy, The Society of Polymer Science, Kyoritsu Publishing Co., Ltd., p. 22."

In the co-continuous structure, the first phase and the second phase are three-dimensionally continuous, form non-spherical and periodic phases, and mix with each other. In this embodiment, the first phase mainly consists of a thermoplastic resin (A), and the second phase having a co-continuous structure mainly consists of a mixed phase of a thermoplastic resin (B) and a thermoplastic resin (C). Become.

Observation of morphology A is carried out, for example, by using an SEM image (photograph) of a cross section of the thermoplastic resin composition polished for SEM observation at a magnification of approximately 5000 times to 15000 times.
Note that the first phase mainly consists of thermoplastic resin (A) means that the area of a similar color (for example, white) in the continuous phase of the first phase in the above SEM image is 80% or more. means. The area of similar colors may be 90% or more. The second phase is mainly composed of a mixed phase of thermoplastic resin (B) and thermoplastic resin (C), which means that the area of a similar color (for example, black) in the continuous phase of the second phase in the SEM image is 80% or more. The area of similar colors may be 90% or more.

In the sea-island structure, island-like phases are dispersed within the matrix (sea). In the present embodiment, in the enlarged observation of the first phase, a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) is dispersed in the thermoplastic resin (A) (sea-island structure); In the enlarged observation of phase 2, the thermoplastic resin (A) is dispersed in the mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C).

The enlarged observation of the morphology B is performed, for example, by using an SEM image (photograph) of a cross section of the thermoplastic resin composition polished for SEM observation at a magnification of about 25,000 times to 35,000 times.

In this embodiment, when the cross section of the thermoplastic resin composition is observed at a relatively low magnification, a co-continuous structure is observed, and when observed at a high magnification, each phase constituting the co-continuous structure is observed. A sea-island structure is observed in the area. By having such a morphology, the thermoplastic resin composition has high mechanical strength and moist heat resistance when formed into a molded article.

The above morphology can be developed by melt-kneading a mixture containing the thermoplastic resins (A) to (C). During mixing, the thermoplastic resins (A) to (C) may each be in the form of powder or pellets. Alternatively, for example, the thermoplastic resin (B) and the thermoplastic resin (C) are melt-kneaded in advance, and then the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C) are mixed together. It may be melt-kneaded. Furthermore, as will be described later, the thermoplastic resin composition of the present invention may be melt-kneaded with known fillers and additives added thereto in order to impart various functions to the molded article or to improve its properties. As long as the purpose of the present invention is not impaired, additives known per se may be incorporated in small proportions.

Known means can be used for melt-kneading. For example, a single-screw kneader (a kneader is also called an extruder), a multi-screw kneader with two or more screws, a continuous kneader such as a kneading roll or a calendar roll, a pressure kneader, a Banbury mixer, etc. A known kneader may be used. Among these, a twin-screw kneader is preferred.

L/D (barrel effective length/barrel inner diameter) of the extruder is preferably 20 or more and 60 or less, more preferably 30 or more and 50 or less.
Although the screw configuration is not particularly limited, it is preferable to provide first to third kneading zones. For example, it is preferable to provide kneading zones upstream, midstream, and downstream with respect to the flow direction of the raw material.
The configuration of the extruder is not particularly limited, but for example, it is preferable to provide first to third vacuum vents. For example, it is preferable to provide a first vacuum vent behind the midstream kneading zone and a second vacuum vent behind the downstream kneading zone with respect to the raw material flow direction.

The rotation speed of the screw is not particularly limited, but is preferably 100 to 500 rpm, and more preferably 200 to 400 rpm from the viewpoint of controlling morphology and controlling shear heat generation.
The set temperature of the extruder is not particularly limited, but is preferably +10° C. or higher and +150° C. or lower relative to the higher melting point or glass transition point of the thermoplastic resin used. From the viewpoint of suppressing thermal decomposition of the thermoplastic resin and controlling morphology, the temperature is more preferably +20°C or more and +100°C or less. Here, when two or more types of thermoplastic resins are used, the melting point or glass transition point of the resin having the highest melting point or glass transition point among the resins used becomes the reference.

The method of supplying the raw material is not particularly limited, but it is preferable to supply it from the first to third raw material supply ports. For example, it is preferable that raw materials containing a thermoplastic resin are dry blended in the flow direction of the raw materials and supplied from a first raw material supply port upstream. When reinforcing fibers are added as a filler, it is preferable to supply them from a second raw material supply port installed between the midstream and the downstream.

The morphology of the present invention can be expressed by adjusting the fluidity of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C). Fluidity can be measured, for example, by performing MFR measurement.

In morphology B (sea-island structure), it is preferable that the average diameter of the mixed phase (island portion) of thermoplastic resin (B) and thermoplastic resin (C) present in the first phase is 500 nm or less. Further, it is preferable that the average diameter of the thermoplastic resin (A) (island portion) present in the second phase is 500 nm or less. This allows each resin to play complementary roles and exhibit excellent mechanical properties.
The average diameter of the island portion is preferably 400 nm or less, more preferably 300 nm or less. Although the lower limit of the average diameter of the island portion is not particularly specified, it is usually about 50 nm.

The average diameter can be measured by observing the morphology of a cross section of a molded resin composition using an optical microscope, SEM (scanning electron microscope), TEM (transmission electron microscope), or the like.
Specifically, when observing using a SEM analyzer, for example, the core part of the cross section of the molded product (the part excluding the surface layer with a depth of less than 20 μm, the center of the cross section, the cross section parallel to the flow direction of the resin composition) ) can be observed at a magnification of 25,000 to 35,000 times under an accelerating voltage of 15 kV. Regarding the island component having an area of 0.20 μm ² or less from the observed image, the equivalent diameter obtained by converting it into a circle having the area is defined as the particle diameter, and is defined as the island component diameter. The average diameter of the island portion is calculated by the arithmetic mean from the results of the diameters of 100 island components observed in 10 non-overlapping observation images taken in the same manner.

In one embodiment, the thermoplastic resin (A) and the thermoplastic resin (C) have polar functional groups. Thereby, the interfacial strength between the thermoplastic resin (A) and the thermoplastic resin (C) can be improved, and the size of the morphology can be made finer.
Examples of the polar functional group include a carboxyl group, an amino group, a hydroxyl group, a halogen group, an epoxy group, a sulfonic acid group, an imide group, an isocyanate group, and the like.

In one embodiment, thermoplastic resin (A) and thermoplastic resin (B) are crystalline resins. Thereby, heat resistance, water resistance, and chemical resistance can be imparted.
Hereinafter, the constituent components of the thermoplastic resin composition of this embodiment will be explained.

<Thermoplastic resin (A)>
The thermoplastic resin (A) mainly forms the first phase of a co-continuous structure.
The thermoplastic resin (A) is not particularly limited as long as it is a resin that is incompatible with the thermoplastic resin (B) and the thermoplastic resin (C). Thermoplastic resin (A) specifically includes polyamide resin, acrylic resin, polyphenylene sulfide resin, polyvinyl chloride resin, polyolefin, polyacetal resin, polycarbonate resin, polyurethane, polybutylene terephthalate, and acrylonitrile butadiene styrene (ABS) resin. , phenoxy resin, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, aromatic polyester and the like. Among these, polyamide resin is preferred.

As the polyamide, known polyamides can be used.
Examples of the polyamide include polyamide-4, polyamide-6, polyamide-6, 6, polyamide-3, 4, polyamide-12, polyamide-11, polyamide-4, 10, polyamide-6, 10, polyamide-4T, polyamide Examples include polyamide-6T, polyamide-9T, polyamide-10T, and polyamide obtained from adipic acid and m-xylylene diamine. Among these, polyamide-6, polyamide-6, 6, and polyamide-6, 10 are preferred.

In the thermoplastic resin composition of the present invention, the blending amount of the thermoplastic resin (A) is 40 parts by mass to 100 parts by mass in total of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C). Preferably, it is 60 parts by mass. More preferably, it is 45 parts by mass to 55 parts by mass.

<Thermoplastic resin (B)>
The thermoplastic resin (B) mainly forms the second phase of the thermoplastic resin composition by being compatible with the thermoplastic resin (C) described in detail below.
The thermoplastic resin (B) is not particularly limited as long as it is compatible with the thermoplastic resin (C). Specifically, acrylic resin, polyphenylene sulfide resin, polyvinyl chloride resin, polystyrene resin, polyolefin, polyacetal resin, polycarbonate resin, polyurethane, polybutylene terephthalate, acrylonitrile butadiene styrene (ABS) resin, phenoxy resin, polysulfone, poly Examples include ether sulfone, polyether ketone, polyether ether ketone, and aromatic polyester. Among these, polystyrene resins are preferred.

The polystyrene resin is not particularly limited, but rubber-like polymers are dispersed in particles in a matrix consisting of a homopolymer of a styrene compound, a copolymer of two or more styrene compounds, or a polymer of styrene compounds. Examples include rubber-modified polystyrene resin (high impact polystyrene). Examples of the styrene compounds used as raw materials include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, and 2,4-dimethyl. Examples include styrene, monochlorostyrene, p-tert-butylstyrene, and the like.

Although the polystyrene resin may be a copolymer obtained by using two or more styrene compounds in combination, polystyrene obtained by polymerizing styrene alone is particularly preferable. For example, polystyrene having a stereoregular structure such as atactic polystyrene, isotactic polystyrene, and syndiotactic polystyrene can be mentioned. Among the thermoplastic resins (B) contained in the resin composition of the present invention, syndiotactic polystyrene is preferred.

Syndiotactic polystyrene means a styrenic resin (hereinafter sometimes abbreviated as SPS) having a highly syndiotactic structure. In this specification, "syndiotactic" means that the phenyl rings in adjacent styrene units are arranged alternately with respect to the plane formed by the main chain of the polymer block (hereinafter referred to as syndiotacticity). This means that a high percentage of
Tacticity can be quantitatively identified by nuclear magnetic resonance method ( ¹³ C-NMR method) using carbon isotope. By the ¹³ C-NMR method, the abundance ratio of a plurality of consecutive structural units, for example, two consecutive monomer units as a dyad, three monomer units as a triad, and five monomer units as a pentad, can be determined.

"Styrenic resin having a highly syndiotactic structure" is usually 75 mol% or more, preferably 85 mol% or more in racemic dyad (r), or usually 30 mol% or more in racemic pentad (rrrr), Preferably polystyrene, poly(hydrocarbon-substituted styrene), poly(halogenated styrene), poly(halogenated alkylstyrene), poly(alkoxystyrene), poly(vinyl benzoate) having syndiotacticity of 50 mol% or more ), hydrogenated polymers or mixtures thereof, or copolymers containing these as main components.

Poly(hydrocarbon-substituted styrene) includes poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenyl)styrene, poly(vinylnaphthalene) and poly( (vinylstyrene), etc. Examples of poly(halogenated styrene) include poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), and examples of poly(halogenated alkylstyrene) include poly(chloromethylstyrene). can. Examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene).

Among the above polystyrene resins, particularly preferred are polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-methylstyrene), -chlorostyrene) and poly(p-fluorostyrene).
Further examples include copolymers of styrene and p-methylstyrene, copolymers of styrene and p-tert-butylstyrene, and copolymers of styrene and divinylbenzene.

There is no particular restriction on the molecular weight of the syndiotactic polystyrene, but from the viewpoint of the fluidity of the resin during molding and the mechanical properties of the molded product obtained, the weight average molecular weight should be 1 x 10 ⁴ or more and 1 x 10 ⁶ or less. It is preferably 50,000 or more and 500,000 or less, and even more preferably 50,000 or more and 300,000 or less. When the weight average molecular weight is 1×10 ⁴ or more, a molded article having sufficient mechanical properties can be obtained. On the other hand, if the weight average molecular weight is 1×10 ⁶ or less, there will be no problem in the fluidity of the resin during molding.

When the melt flow rate (MFR) is measured under the conditions of a temperature of 300° C. and a load of 1.2 kg, it is preferably 2 g/10 minutes or more, more preferably 4 g/10 minutes or more. Moreover, it is preferably 50 g/10 minutes or less, more preferably 35 g/10 minutes or less. If the MFR value of SPS is 2 g/10 minutes or more, there is no problem with the fluidity of the resin during molding, and if it is 50 g/10 minutes or less, a molded product with sufficient strength can be obtained.

The blending amount of the thermoplastic resin (B) is preferably 25 to 57 parts by mass based on a total of 100 parts by mass of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C). More preferably, it is 40 to 50 parts by mass.

It is preferable that the thermoplastic resin (B) is completely compatible with the thermoplastic resin (C) described below. "Completely compatible" means that the glass transition temperature of the mixed resin of the thermoplastic resin (B) and the thermoplastic resin (C) is the same. A single glass transition temperature indicates the glass transition temperature when the mixed resin is measured using a differential scanning calorimetry system at a heating rate of 10°C/min according to JIS K-7121. This means that only one peak appears.

<Thermoplastic resin (C)>
The thermoplastic resin (C) is mainly compatible with the above thermoplastic resin (B) to form the second phase of the thermoplastic resin composition.
The thermoplastic resin (C) is not particularly limited as long as it is compatible with the thermoplastic resin (B). For example, polyarylene ether can be mentioned.
From the viewpoint of compatibility with the thermoplastic resin (B), polyarylene ether is preferred, and polyarylene ether modified with a functional group is more preferred.
Polyarylene ethers modified with functional groups can be obtained by reacting polyarylene ethers with modifiers.

The polyarylene ether used as a raw material for the polyarylene ether modified with a functional group is not particularly limited. For example, poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxy ethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly( 2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1, 4-phenylene ether], poly(2-phenyl-1,4-phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly( 2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4- phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl- 1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1, 4-phenylene ether) and poly(2,6-dimethyl-1,4-phenylene ether). Also, the polymers and copolymers described in the specifications of U.S. Patent Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358 is also appropriate. Further examples include graft copolymers and block copolymers of vinyl aromatic compounds such as polystyrene and the above-mentioned polyphenylene ethers. Among these, poly(2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.

The degree of polymerization of polyarylene ether is not particularly limited and can be appropriately selected depending on the purpose of use, etc., and can usually be selected from the range of 60 to 400. If the degree of polymerization is 60 or more, as will be described in detail later, the strength of the resin composition containing the polyarylene ether (A) modified with a functional group can be improved. If it is 400 or less, good moldability can be maintained.

Modifiers for modifying the polyarylene ether include acid modifiers, amino group-containing modifiers, phosphorus compounds, hydroxyl group-containing modifiers, halogen-containing modifiers, epoxy group-containing modifiers, unsaturated hydrocarbon group-containing modifiers, etc. can be mentioned. Examples of acid modifiers include dicarboxylic acids and derivatives thereof.

Dicarboxylic acids used as modifiers include maleic anhydride and its derivatives, fumaric acid and its derivatives. A derivative of maleic anhydride is a compound having an ethylenic double bond and a polar group such as a carboxyl group or an acid anhydride group in the same molecule. Specifically, for example, maleic acid, maleic acid monoester, maleic acid diester, maleimide and its N-substituted products (for example, N-substituted maleimide, maleic acid monoamide, maleic acid diamide, etc.), ammonium salts of maleic acid, maleic acid Examples include metal salts, acrylic acid, methacrylic acid, methacrylic esters, glycidyl methacrylate, and the like. Specific examples of fumaric acid derivatives include fumaric acid diesters, fumaric acid metal salts, fumaric acid ammonium salts, fumaric acid halides, and the like. Among these, fumaric acid or maleic anhydride is particularly preferably used.

As the polyarylene ether modified with a functional group, dicarboxylic acid-modified polyarylene ether is preferred, and fumaric acid-modified polyarylene ether or maleic acid-modified polyarylene ether is more preferred. Specifically, modified polyphenylene ether polymers such as (styrene-maleic anhydride)-polyphenylene ether graft polymer, maleic anhydride-modified polyphenylene ether, fumaric acid-modified polyphenylene ether, glycidyl methacrylate-modified polyphenylene ether, amine-modified polyphenylene ether, etc. can be mentioned. Among them, modified polyphenylene ether is preferred, maleic anhydride modified polyphenylene ether or fumaric acid modified polyphenylene ether is more preferred, and fumaric acid modified polyphenylene ether is particularly preferred.

The degree of modification (degree of modification or amount of modification) of polyarylene ether modified with a functional group can be determined by infrared (IR) absorption spectroscopy or titration.
When determining the degree of modification from infrared (IR) absorption spectroscopy, it can be determined from the spectral intensity ratio of the peak intensity indicating absorption of the compound used as a modifier and the peak intensity indicating absorption of the corresponding polyarylene ether. . For example, in the case of fumaric acid-modified polyphenylene ether, the ratio (B) of the peak intensity at 1790 cm ^-1 indicating the absorption of fumaric acid and the peak intensity at 1704 cm ^-1 indicating the absorption of polyphenylene ether (PPE) is calculated from the formula: degree of modification. It is determined by using =(A)/(B). The degree of modification of the polyarylene ether modified with a functional group is preferably 0.05 to 20.

When determining the amount of modification by titration, the acid content can be determined from the neutralization titer measured in accordance with JIS K 0070-1992. The amount of modification of the polyarylene ether modified with a functional group is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1.0 to 15% by mass, based on the mass of the polyarylene ether. Modification amounts of 10% by weight, particularly preferably from 1.0 to 5.0% by weight can be used.

The polyarylene ether modified with a functional group can be produced by, for example, reacting the polyarylene ether with various modifiers in the presence or absence of a radical generator, optionally in the presence of a solvent or other resin. It can be prepared by Solution modification or melt modification is known as a modification method.

When using the above-mentioned fumaric acid or its derivative as a modifier, polyarylene ether and fumaric acid or its derivative are optionally mixed in the presence of an aromatic hydrocarbon solvent and other resins in the presence or absence of a radical generator. By reacting in the presence of the fumaric acid-modified polyarylene ether, a fumaric acid-modified polyarylene ether can be obtained. The aromatic hydrocarbon solvent is not particularly limited as long as it can dissolve the polyarylene ether, fumaric acid or its derivative, and an optionally used radical generator, and is inert to generated radicals. Specifically, suitable examples include benzene, toluene, ethylbenzene, xylene, chlorobenzene, and tert-butylbenzene. Among them, it is preferable to use benzene, toluene, chlorobenzene, and tert-butylbenzene, which have small chain transfer constants. The solvents may be used alone or in combination of two or more. The proportion of the aromatic hydrocarbon solvent to be used is also not particularly limited, and may be appropriately selected depending on the situation. In general, it may be determined in a range of 1 to 20 times (mass ratio) to the polyarylene ether used.

The proportion of fumaric acid or its derivative used as a modifier is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of polyarylene ether. If it is 1 part by mass or more, a sufficient amount of modification (degree of modification) can be obtained. If it is 20 parts by mass or less, post-treatments such as purification after modification can be appropriately performed.

The radical generator optionally used for solution modification of polyarylene ether is not particularly limited. It is preferable to have a decomposition temperature suitable for the reaction temperature and a large hydrogen abstraction ability in order to effectively graft the modifier onto the polyarylene ether. Specifically, for example, di-tert-butyl peroxide, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3 , 5-trimethylcyclohexane, benzoyl peroxide, decanoyl peroxide and the like. The proportion of the radical generator used is preferably 15 parts by mass or less based on 100 parts by mass of polyarylene ether. It is preferable that the radical generator is 15 parts by mass or less because it is less likely to generate insoluble components. When the above modification is carried out in the absence of a radical generator, a polyarylene ether with a low modification amount (degree of modification) (for example, a modification amount of 0.3 to 0.5% by mass) is obtained.

When polyarylene ether is solution-modified, specifically, polyarylene ether and a modifier such as fumaric acid or a derivative thereof are dissolved in an aromatic hydrocarbon solvent to become homogeneous, and then a radical generator is used. The radical generator is added at an arbitrary temperature at which the half-life of the radical generator is 1 hour or less, and the reaction is carried out at that temperature. A temperature at which the half-life of the radical generator used exceeds 1 hour is not preferred because a long reaction time is required.
Although the reaction time can be selected as appropriate, in order for the radical generator to act effectively, it is preferable to conduct the modification reaction at a predetermined reaction temperature for a time longer than three times the half-life of the radical generator.
After the reaction is completed, the reaction solution is added to a poor solvent for polyarylene ether such as methanol, and the precipitated modified polyarylene ether is collected and dried to obtain the desired polyarylene ether modified with a functional group. .

When melt-modifying polyarylene ether, the polyarylene ether and a modifier such as fumaric acid or a derivative thereof are melt-kneaded using an extruder in the presence or absence of a radical generator. Polyarylene ethers modified with functional groups can be obtained. The proportion of fumaric acid or its derivative used is preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, based on 100 parts by weight of polyarylene ether. If it is 1 part by mass or more, the amount of modification (degree of modification) is sufficient, and if it is 5 parts by mass or less, the modification efficiency of fumaric acid and its derivatives is maintained well, and the amount of fumaric acid, etc. remaining in the pellet is suppressed. can do.

The radical generator used for melt modification of polyarylene ether preferably has a half-life of 1 minute at a temperature of 300° C. or higher. Those having a half-life of less than 300°C, such as peroxides and azo compounds, do not have a sufficient modifying effect on polyarylene ether.
Specific examples of the radical generator include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, and 2,3-diethyl-2,3-diphenylhexane. , 2,3-dimethyl-2,3-di(p-methylphenyl)butane, and the like. Among these, 2,3-dimethyl-2,3-diphenylbutane, which has a half-life of 1 minute at a temperature of 330° C., is preferably used.
The proportion of the radical generator to be used is preferably selected in the range of 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of polyarylene ether. If it is 0.1 parts by mass or more, a high modification effect can be obtained, and if it is 3 parts by mass or less, the polyarylene ether can be efficiently modified and insoluble components are hardly generated.

As a method for melt-modifying polyarylene ether, for example, polyarylene ether, fumaric acid or its derivative, and a radical generator are uniformly dry-blended at room temperature, and then the mixture is heated to a temperature of 300 to 300°C, which is substantially the kneading temperature of polyarylene ether. A method of carrying out a melting reaction in a range of 350°C can be mentioned. If it is 300°C or higher, the melt viscosity can be maintained appropriately, and if it is 350°C or lower, the decomposition of polyarylene ether can be suppressed.

Among polyarylene ethers modified with functional groups obtained by the method detailed above, in the case of particularly preferred fumaric acid-modified polyarylene ethers, the amount of modification (modifier content) determined by the titration method described above is as follows: It is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, even more preferably 1 to 10% by weight, particularly preferably 1.0 to 5.0% by weight. When the amount of modification is 0.1% by mass or more, a polyarylene ether having sufficient mechanical properties and heat resistance can be obtained. It is sufficient that the amount of modification is 20% by mass or less.

The blending amount of the thermoplastic resin (C) is preferably 3 to 15 parts by mass based on a total of 100 parts by mass of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C). More preferably 5 to 12 parts by weight, still more preferably 7 to 10 parts by weight.

In the thermoplastic resin composition of the present embodiment, the mass ratio of the thermoplastic resin (A) to the total of the thermoplastic resin (B) and the thermoplastic resin (C) [(A):((B)+(C) ))] is preferably 40:60 to 60:40. More preferably, the ratio is 45:55 to 55:45. By setting it within this range, the cross section of the thermoplastic resin composition tends to have the above-mentioned morphology.

The thermoplastic resin composition of the present embodiment is not particularly limited as long as it contains the above-mentioned thermoplastic resins (A) to (C) and has a predetermined morphology. Reinforcing fibers, rubber-like elastic bodies, antioxidants, crosslinking agents, crosslinking aids, nucleating agents, mold release agents, plasticizers, compatibilizers, coloring agents, antistatic agents, etc., within the range that does not impede the purpose of the present invention. , known fillers and additives can be used.

In the thermoplastic resin composition of the present embodiment, the content of the thermoplastic resins (A) to (C) with respect to the entire resin component (thermoplastic resin, rubber-like elastic body) may be 80% by mass or more, It may be 90% by mass or more, or 95% by mass or more. Further, in one embodiment, the resin component (thermoplastic resin, rubber-like elastic body) may substantially consist only of thermoplastic resins (A) to (C). In this case, it may contain inevitable impurities.
Below, constituent components other than the above-mentioned thermoplastic resins (A) to (C) will be illustrated.

<Reinforced fiber (D)>
Examples of reinforcing fibers (D) include glass fibers and carbon fibers, with carbon fibers being preferred.
Various types of carbon fibers are available, including PAN-based fibers made from polyacrylonitrile, pitch-based fibers made from coal tar pitch found in petroleum and coal, and phenol-based carbon fibers made from thermosetting resins such as phenolic resin. Can be used.
The carbon fiber may be obtained by a vapor phase growth method, or may be recycled carbon fiber (RCF). The carbon fiber is not particularly limited, but may be selected from the group consisting of PAN carbon fiber, pitch carbon fiber, thermosetting carbon fiber, phenolic carbon fiber, vapor grown carbon fiber, and recycled carbon fiber (RCF). It is preferable that at least one kind of carbon fiber is used.

Some carbon fibers have different degrees of graphitization depending on the raw material quality and firing temperature during manufacture, but they can be used regardless of the degree of graphitization. The shape of the carbon fiber is not particularly limited, and carbon having at least one shape selected from the group consisting of milled fiber, chopped strand, short fiber, roving, filament, tow, whisker, nanotube, etc. Fibers can be used. In the case of chopped strands, those with an average fiber length of 0.1 to 50 mm and an average fiber diameter of 5 to 20 μm are preferably used.
The density of the carbon fiber is not particularly limited, but is preferably 1.75 to 1.95 g/cm ³ .

The carbon fibers may be in the form of a single fiber or a fiber bundle, or a mixture of both single fibers and fiber bundles. The number of single fibers constituting each fiber bundle may be substantially uniform in each fiber bundle, or may be different. Although the average fiber diameter of the carbon fibers varies depending on the form, for example, carbon fibers having an average fiber diameter of preferably 0.0004 to 15 μm, more preferably 3 to 15 μm, and even more preferably 5 to 10 μm can be used.

When the member containing carbon fibers is a woven fabric, a nonwoven fabric, or a unidirectional material, single fibers having an average fiber diameter of preferably 3 to 15 μm, more preferably 5 to 7 μm can be used. Furthermore, when the member containing carbon fibers has the form of a woven fabric, a nonwoven fabric, or a unidirectional material, a unidirectional bundle of carbon fibers (fiber bundle) can be used. The member containing carbon fibers may include 6,000 (6K), 12,000 (12K), 24,000 (24K), or 60,000 (60K) carbon fiber single fibers supplied by a carbon fiber manufacturer as a fiber bundle. A bundled product may be used as is, or a product obtained by further bundling these may be used.
The fiber bundle may be non-twisted yarn, twisted yarn, or untwisted yarn. The fiber bundle may be included in the molded body in a spread state, or may be included as a fiber bundle without being spread.
When the member containing carbon fibers is a woven fabric, a nonwoven fabric, or a unidirectional material, a molded body is formed by immersing the member in thermoplastic resin (A), thermoplastic resin (B), and thermoplastic resin (C). Obtainable.

It is preferable that members containing carbon fibers, especially woven fabrics, nonwoven fabrics, and unidirectional materials, be thin. From the viewpoint of obtaining a thin carbon fiber composite material, the thickness of the member containing carbon fibers is preferably 3 mm or less. In particular, in the case of a unidirectional material, the thickness is preferably 0.2 mm or less. The lower limit of the thickness of the member containing carbon fibers is not particularly limited, but it is preferably 7 μm or more, and from the viewpoint of quality stability, it is 10 μm or more, more preferably 20 μm or more.

The carbon fiber may have a sizing agent attached to its surface. When carbon fibers to which a sizing agent is attached are used, the type of sizing agent can be appropriately selected depending on the types of carbon fibers and thermoplastic resin, and is not particularly limited. Carbon fibers are manufactured into various products, such as those treated with epoxy sizing agents, urethane sizing agents, polyamide sizing agents, or those that do not contain sizing agents. It can be used regardless.

In the thermoplastic resin composition of the present invention, the reinforcing fiber (D) is preferably 1 to 100 parts by mass based on a total of 100 parts by mass of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C). 500 parts by weight, more preferably 1 to 400 parts by weight, even more preferably 1 to 350 parts by weight, even more preferably 1 to 200 parts by weight, even more preferably 1 to 100 parts by weight, even more preferably 1 to 50 parts by weight. Part included. Further, in order to obtain excellent strength, the content is preferably 15 parts by mass or more, more preferably 20 parts by mass or more. When the amount of carbon fiber is within the above range, the molded article of the present invention has excellent mechanical strength.

It is preferable that the surface of the reinforcing fiber (D) is covered with the first phase, not the second phase, of the first phase and the second phase forming a co-continuous morphology. This improves the adhesion with the reinforcing fiber (D) and allows the molded product to exhibit excellent mechanical strength.

In one embodiment, the thermoplastic resin composition preferably contains reinforcing fibers (D). This increases the mechanical strength of the molded body. Moreover, a molded article having a strength retention rate of 80% or more after a wet heat treatment at 80° C./95% RH for 500 hours as shown by the following formula (1) can be obtained.

<Others>
The following rubber-like elastic bodies and the like can be added within a range that does not affect the structure and effects of the present invention.
Various rubber-like elastic bodies can be used. For example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, chloroprene rubber, polysulfide rubber, thiokol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene- Butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated Styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene - Butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM);
Acrylonitrile-butadiene-styrene-core-shell rubber (ABS), Methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), Methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), Octyl acrylate-butadiene-styrene-core-shell rubber (MABS) ), core-shell type particulate elastomers such as siloxane-containing core-shell rubbers such as alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core-shell rubber (SBR), and methyl methacrylate-butyl acrylate siloxane; Alternatively, rubbers obtained by modifying these may be mentioned.
Among these, SBR, SBS, SEB, SEBS, SIR, SEP, SIS, SEPS, core-shell rubber, or rubber modified thereof are particularly preferably used.

Examples of modified rubbery elastic bodies include styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), and styrene-butadiene-styrene. Block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene -Styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer Examples include rubbers obtained by modifying polymers, styrene-ethylene-butylene random copolymers, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), etc. with a modifier having a polar group.

As a filler, an organic filler can also be added in addition to the reinforcing fiber (D). Examples of the organic filler include organic synthetic fibers and natural vegetable fibers. Specific examples of organic synthetic fibers include wholly aromatic polyamide fibers and polyimide fibers. The above organic filler may be used alone or in combination of two or more, and the amount added is determined by the amount of the above thermoplastic resin (A), thermoplastic resin (B) and thermoplastic resin (C). The amount is preferably 1 to 350 parts by weight, more preferably 5 to 200 parts by weight, based on a total of 100 parts by weight. If it is 1 part by mass or more, the effect of the filler can be sufficiently obtained, and if it is 350 parts by mass or less, the dispersibility is not inferior and the moldability is not adversely affected.

（式中、Ｒ^３０及びＲ^３１はそれぞれ独立に炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基あるいは炭素数６～２０のアリール基を示す。）
で表されるリン系化合物を用いることが好ましい。 There are various antioxidants, but especially phosphorus such as monophosphites and diphosphites such as tris(2,4-di-tert-butylphenyl) phosphite and tris(mono- and di-nonylphenyl) phosphite. Preferred are phenolic antioxidants and phenolic antioxidants.
As a diphosphite, the general formula

(In the formula, R ³⁰ and R ³¹ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
It is preferable to use a phosphorus compound represented by:

Specific examples of phosphorus compounds represented by the above general formula include distearyl pentaerythritol diphosphite; dioctyl pentaerythritol diphosphite; diphenyl pentaerythritol diphosphite; bis(2,4-di-tert-butylphenyl ) pentaerythritol diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite; dicyclohexyl pentaerythritol diphosphite and the like.

Known phenolic antioxidants can be used, and specific examples include 2,6-di-tert-butyl-4-methylphenol; 2,6-diphenyl-4-methoxyphenol; , 2'-methylenebis(6-tert-butyl-4-methylphenol);2,2'-methylenebis-(6-tert-butyl-4-methylphenol);2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol];1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;2,2'-methylenebis(4-methyl-6-cyclohexylphenol);2,2'-methylenebis(4-methyl-6-nonylphenol);1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 2,2-bis(5-tert -butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane; ethylene glycol-bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate]; 1,1- Bis(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane; 4,4'-thiobis(6-tert-butyl-3-methylphenol); 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene; 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid di Octadecyl ester; n-octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane Examples include.
In addition to the above-mentioned phosphorus antioxidants and phenolic antioxidants, amine antioxidants, sulfur antioxidants, and the like can be used alone or in combination.

The above antioxidant is usually 0.005 parts by mass or more and 5 parts by mass or less, based on a total of 100 parts by mass of the thermoplastic resin (A), thermoplastic resin (B), and thermoplastic resin (C). . When the blending ratio of the antioxidant is 0.005 parts by mass or more, a decrease in the molecular weight of the thermoplastic resin (A) or the thermoplastic resin can be suppressed. If it is 5 parts by mass or less, mechanical strength can be maintained satisfactorily. When the composition contains multiple types of antioxidants, the total amount is preferably adjusted within the above range. The blending amount of the antioxidant is preferably 0.01 to 4 parts by mass, and even more preferably 0 to 100 parts by mass of the resin (S) or 100 parts by mass of the unmodified polyarylene ether and the thermoplastic resin. It is .02 to 3 parts by mass.

The nucleating agent is preferably one or more selected from the group consisting of inorganic crystallization nucleating agents and organic crystallizing nucleating agents. Among these, organic crystallization nucleating agents are preferred.
Examples of organic crystallization nucleating agents include alkali metal salts of organic carboxylic acids, alkaline earth metal salts of organic carboxylic acids, organic compounds of phosphoric acid or phosphorous acid and their metal salts, phthalocyanine derivatives, sorbitol derivatives, etc. Can be mentioned.

More specifically, examples include aluminum di(p-tert-butylbenzoate), sodium salt of benzoic acid, hydroxyaluminum salt of p-tert-butylbenzoic acid, aluminum hydroxy-di(p-tert-butylbenzoate) metal salts of carboxylic acids including [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]lithium, [phosphoric acid[2,2'-methylenebis(4,6-di-tert-butylphenyl)]]potassium, phosphorus Sodium bis(4-tert-butylphenyl) acid, sodium methylene(2,4-tert-butylphenyl) phosphate, aluminum bis(4,6',6,6'-tetra-tert-butyl-2,2) Metal salts of phosphoric acid such as '-methylene diphenyl phosphate) hydroxide, ammonium phosphoric acid [2,2'-methylenebis(4,6-di-tert-butylphenyl)]], etc. You can arbitrarily choose from. Moreover, complexes containing these can also be used.

The amount of the nucleating agent is not particularly limited, but preferably 0.01 to 5 parts by mass, based on a total of 100 parts by mass of the thermoplastic resin (A), thermoplastic resin (B), and thermoplastic resin (C). More preferably 0.04 to 2 parts by mass.

The mold release agent can be arbitrarily selected from known ones such as polyethylene wax, silicone oil, long chain carboxylic acids, long chain carboxylic acid metal salts, and the like. These mold release agents can be used alone or in combination of two or more. The amount of the mold release agent to be blended is not particularly limited, but is preferably 0.1 to 3 parts by mass based on a total of 100 parts by mass of the thermoplastic resin (A), thermoplastic resin (B), and thermoplastic resin (C). part, more preferably 0.2 to 1 part by weight.

<Method for manufacturing molded body>
In one embodiment of the present invention, the thermoplastic resin composition is a molded article. The molded article is produced by, for example, adding the above-mentioned thermoplastic resin (A), thermoplastic resin (B), and thermoplastic resin (C), optionally reinforcing fibers (D), additives, etc., to a molding machine (extrusion molding machine, They can be molded into a desired shape by putting them into an injection molding machine, etc., melting and kneading them in the molding machine, and shaping them with a mold.
Powder, pellets, or the like obtained by melt-kneading and granulating some or all of the constituent members of the thermoplastic resin composition may be fed into the molding machine.

In one embodiment, a step of producing an intermediate product of a thermoplastic resin composition containing a thermoplastic resin (B) and a thermoplastic resin (C), and a step of adding the thermoplastic resin (A) to the intermediate product. A molded article can also be molded by a method including.
Alternatively, a molded article can also be produced by immersing reinforcing fibers (D) in a thermoplastic resin composition containing thermoplastic resin (A), thermoplastic resin (B), and thermoplastic resin (C). . When this method is used, the reinforcing fiber (D) may have at least one form selected from chopped strands, woven fabrics, nonwoven fabrics, and unidirectional materials.

Further, a step of producing a reinforcing fiber member containing a thermoplastic resin (A) and a reinforcing fiber (D), and a step of producing a reinforcing fiber member containing a thermoplastic resin (A), a thermoplastic resin (B), and a thermoplastic resin ( A molded article can also be molded by a method including the step of adding a thermoplastic resin composition containing C).

The means for producing a reinforcing fiber member containing a thermoplastic resin (A) and reinforcing fibers (D) is not particularly limited. For example, methods include immersing reinforcing fibers (D) in thermoplastic resin (A) in an appropriate solvent, applying a mixture of thermoplastic resin (A) in an appropriate vehicle to reinforcing fibers, and applying heat to the sizing material. Examples include a method of mixing the plastic resin (A) and adding it to the reinforcing fiber (D). When this method is used, the reinforcing fiber (D) may have at least one form selected from chopped strands, woven fabrics, nonwoven fabrics, and unidirectional materials.

Further, a step of producing a reinforcing fiber member containing a thermoplastic resin (C) and a reinforcing fiber (D), and a step of producing a reinforcing fiber member containing a thermoplastic resin (A), a thermoplastic resin (B), and a thermoplastic resin ( A molded article can also be molded by a method including the step of adding a thermoplastic resin composition containing C).
The means for producing the reinforcing fiber member containing the thermoplastic resin (C) and the reinforcing fibers (D) may be the same as the means for producing the reinforcing fiber member containing the thermoplastic resin (A) and the reinforcing fibers (D). can. The form of the reinforcing fiber (D) used is also the same.

The reinforcing fiber member containing the thermoplastic resin (A) and the reinforcing fiber (D) or the reinforcing fiber member containing the thermoplastic resin (C) and the reinforcing fiber (D) obtained in the above step is heated in a subsequent step. A thermoplastic resin composition containing a plastic resin (A), a thermoplastic resin (B), and a thermoplastic resin (C) is added. The method of adding the thermoplastic resin composition to the reinforcing fiber member is not limited, and the thermoplastic resin composition may be in a solution state or in a molten state. Specifically, the methods include a method in which a reinforcing fiber member is immersed in a thermoplastic resin composition in an appropriate solvent, a method in which films containing a thermoplastic resin composition are laminated and melt-pressed, and a reinforcing fiber member is immersed in a thermoplastic resin composition. Examples include a method of directly adding powder of a substance and then melting it.

The reinforcing fiber member may contain a thermoplastic resin (A) and a reinforcing fiber (D) or a thermoplastic resin (C) and a reinforcing fiber (D). The composition may be added, or the thermoplastic resin composition may be added after a reinforcing fiber member having a form such as a woven fabric is cut into a chopped form. After adding the thermoplastic resin composition to the reinforcing fiber member, a molded article can be manufactured by various molding methods described below.

The shape of the molded product is not particularly limited, and examples thereof include sheets, films, fibers, woven fabrics, nonwoven fabrics, containers, injection molded products, blow molded products, press molded products, and the like. Depending on the form of the reinforcing fibers used, the molded article may be a unidirectional fiber reinforced material or a molded article containing at least one member selected from woven reinforcing fibers and nonwoven reinforcing fibers. A laminate can also be obtained by stacking a plurality of the molded bodies. This laminate is also included in the "molded body" in this specification.

A molded article containing at least one member selected from the group consisting of unidirectional fiber reinforcement, woven reinforcing fibers, and nonwoven reinforcing fibers has high mechanical strength. For example, in accordance with ISO 178:2010, the bending strength measured at a distance between fulcrums of 4 cm, a test speed of 2 mm/min, and a temperature of 23° C. has a mechanical strength of 250 MPa or more, more preferably 300 MPa or more.

The molded product of the present invention can be used for electric/electronic materials (connectors, printed circuit boards, etc.), industrial structural materials, automobile parts (vehicle connectors, wheel caps, cylinder head covers, etc.), home appliances, various mechanical parts, pipes, sheets, etc. Suitable as industrial materials such as trays and films.

Specifically, the molded article of the present invention can be used as carbon fiber reinforced thermoplastic (CFRTP) for a wide range of applications such as automobiles, aircraft, and sporting goods that require further weight reduction. Molded objects for this purpose can also be applied to improve engineering plastics, which are required to withstand high load and high temperature environments. A molded article containing the resin composition of the present invention has a short molding time and excellent recyclability, is easy to be immersed in resin during molding, and has sufficient mechanical strength, so it can be put to practical use in a wide range of applications.

Specifically, it can be used for automobiles, motorcycles/bicycles, water heaters and EcoCute related uses, home appliances/electronic devices, building materials, and daily necessities.
Automotive applications include sliding parts such as gears, automotive panel members, millimeter wave radomes, IGBT housings, radiator grills, meter hoods, fender supports, front engine covers, front strut tower panels, mission center tunnels, radio core supports, Front dash, door inner, rear luggage back panel, rear luggage side panel, rear luggage floor, rear luggage partition, roof, door frame pillar, seat back, headrest support, engine parts, crash box, front floor tunnel, front floor panel, Examples include automobile parts such as undercovers, undersupport rods, impact beams, front cowls, and front strut tower bars.

The molded article of the present invention is suitable for forming, for example, a power electronic unit, a quick charging plug, an in-vehicle charger, a lithium ion battery, a battery control unit, a power electronic control unit, a three-phase synchronous motor, a home charging plug, etc. It is possible.

In addition, solar twilight sensor, alternator, EDU (electronic injector driver unit), electronic throttle, tumble control valve, throttle opening sensor, radiator fan controller, stick coil, A/C pipe joint, diesel particulate filter, headlight reflector. plate, charge air duct, charge air cooling head, intake air temperature sensor, gasoline fuel pressure sensor, cam/crank position sensor, combination valve, engine oil pressure sensor, transmission gear angle sensor, continuously variable transmission oil pressure sensor, ELCM (evaporative pump) Leak check module) pump, water pump impeller, steering roll connector, ECU (engine computer unit) connector, ABS (anti-lock brake system) reservoir piston, actuator cover, etc. can be suitably configured.

The molded article containing the thermoplastic resin composition of the present invention is further suitably used as a sealing material for sealing a sensor included in an on-vehicle sensor module, for example. The sensor is not particularly limited, and specifically includes an atmospheric pressure sensor (for example, for high altitude correction), a boost pressure sensor (for example, for fuel injection control), an atmospheric pressure sensor (IC), and an acceleration sensor (for example, for airbags). , gauge pressure sensors (e.g. for seat condition control), tank internal pressure sensors (e.g. for fuel tank leak detection), refrigerant pressure sensors (e.g. for air conditioning control), coil drivers (e.g. for ignition coil control), EGR (exhaust gas recirculation) Examples include a valve sensor, an air flow sensor (for example, for fuel injection control), an intake pipe pressure (MAP) sensor (for example, for fuel injection control), an oil pan, a radiator cap, an intake manifold, and the like.

The molded article containing the thermoplastic resin composition of the present invention is not limited to the automobile parts exemplified above, but includes, for example, high voltage (harness) connectors, millimeter wave radomes, IGBT (insulated gate bipolar transistor) housings, and battery fuse terminals. , radiator grill, meter hood, water pump for inverter cooling, battery monitoring unit, structural parts, intake manifold, high voltage connector, motor control ECU (engine computer unit), inverter, piping parts, canister purge valve, power unit, bus bar, motor deceleration It is also suitable for use in machines, canisters, etc.
It is also suitably used for motorcycle parts and bicycle parts, and more specifically includes parts for motorcycles, cowls for motorcycles, parts for bicycles, and the like. Examples of motorcycle/bicycle applications include motorcycle parts, motorcycle cowls, and bicycle parts.

The molded article containing the resin composition of the present invention has excellent chemical resistance and can therefore be used for various electrical appliances. For example, it is also preferable to constitute a part of a water heater, specifically, a natural refrigerant heat pump water heater known as a so-called "EcoCute (registered trademark)" or the like. Such parts include, for example, shower parts, pump parts, piping parts, etc., and more specifically, single circulation fittings, relief valves, mixing valve units, heat-resistant traps, pump casings, composite water valves, and water inlet fittings. , resin joints, piping parts, resin pressure reducing valves, elbows for water faucets, etc.

The molded article containing the resin composition of the present invention is suitably used for home appliances and electronic devices, more specifically, telephones, mobile phones, microwave ovens, refrigerators, vacuum cleaners, office automation equipment, power tool parts, Electrical component applications, static electricity prevention applications, high frequency electronic components, high heat dissipation electronic components, high voltage components, electromagnetic shielding components, communication equipment products, AV equipment, personal computers, registers, electric fans, ventilation fans, sewing machines, ink peripheral components, ribbons Cassettes, air cleaner parts, heated toilet seat parts, toilet seats, toilet lids, rice cooker parts, optical pickup equipment, lighting equipment parts, DVDs, DVD-RAMs, DVD pickup parts, DVD pickup boards, switch parts, sockets, displays , video cameras, filaments, plugs, high-speed color copiers (laser printers), inverters, air conditioners, keyboards, converters, televisions, facsimiles, optical connectors, semiconductor chips, LED parts, washing machine/washer/dryer parts, dishwashers/ Examples include structural members such as parts for tableware dryers.
The molded product containing the resin composition of the present invention is also suitably used as a building material, and more specifically, structural members such as exterior wall panels, back panels, partition wall panels, signal lights, emergency lights, and wall materials can be mentioned. .

Molded objects containing the resin composition of the present invention can also be suitably used for miscellaneous goods, daily necessities, etc. More specifically, chopsticks, lunch boxes, tableware containers, food trays, food packaging materials, aquariums, tanks, toys, etc. , sporting goods, surfboards, door caps, door steps, pachinko machine parts, remote control cars, remote control cases, stationery, musical instruments, tumblers, dumbbells, helmet box products, shutter blades used in cameras, table tennis, tennis, etc. Examples include constituent members such as racket members, plate members for skiing and snowboarding, and the like.
Each of the various parts described above may be partially or entirely constituted by a molded article containing the thermoplastic resin composition of the present invention.

Hereinafter, the present invention will be specifically explained based on Examples. The invention is not limited to the examples.
The constituent materials used in the examples are as follows.
[Thermoplastic resin]
(A-1): Polyamide 6 (manufactured by Ube Industries, Ltd.: 1022B)
(B-1): Syndiotactic polystyrene (SPS, manufactured by Idemitsu Kosan Co., Ltd., racemic pentad: 98%, MFR: 28 g/10 minutes, melting point: 270°C)
(C-1): Fumaric acid-modified polyphenylene ether (manufactured by Idemitsu Kosan Co., Ltd., manufactured by melt modification, modification amount 1.7% by mass, glass transition point 220°C)
(C-2): Polyphenylene ether (manufactured by SABIC: PX-100L)
[Reinforced fiber]
(D-1): Chopped carbon fiber (manufactured by Mitsubishi Chemical Corporation: TR066AB4E)

The melt flow rate (MFR) of the resin was measured at a measurement temperature of 300° C. and a load of 1.2 kg in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011).

Example 1
100 parts by mass of a thermoplastic resin composition consisting of 50 parts by mass of polyamide 6 (A-1), 40 parts by mass of SPS (B-1), and 10 parts by mass of fumaric acid-modified polyphenylene ether (C-1) were dry blended, and The material is supplied from the raw material supply port upstream of the axial kneader, and 35 parts by mass of carbon fiber as reinforcing fiber (D-1) is side-fed from the second raw material supply port installed between the midstream and downstream, kneaded, and heated. A plastic resin composition (pellet) was obtained. At this time, a twin-screw kneader (manufactured by Thermo Fisher Scientific, Process 11) having a cylinder diameter of 11 mm was used.
The L/D of the twin-screw kneading machine is 40, and first to third kneading zones are provided upstream, midstream, and downstream with respect to the flow direction of the raw materials, and a kneading zone is provided behind the midstream kneading zone. A first vacuum vent was provided downstream of the kneading zone, and a second vacuum vent was provided downstream of the kneading zone.
The rotation speed of the screw was 250 rpm, and the set temperature was 300° C., which is 30° C. higher than the melting point of SPS.

Comparative examples 1 to 5
A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the type and composition of the thermoplastic resin were changed as shown in Table 1.

[evaluation]
The obtained thermoplastic resin composition was subjected to a bending test and evaluated for heat and humidity resistance, and its morphology was observed. The evaluation results are shown in Table 1.
<Mechanical property test: bending test>
A thermoplastic resin composition (pellet) was injection molded using an injection molding machine (Thermo Fisher Scientific, MiniJetPro) at a cylinder temperature of 300°C and a mold temperature of 150°C. ) was obtained. The mold used was ISO527-2-5A manufactured by Thermo Fisher Scientific.
The bending properties of the bending test pieces obtained above were measured in accordance with ISO 178:2010. Specifically, the bending strength (MPa) and bending elastic modulus (GPa) were measured under the conditions of a distance between fulcrums of 5 cm, a temperature of 23° C., and a bending speed of 3 mm/min. The larger the value, the better the bending properties.

<Evaluation of heat and humidity resistance>
The test piece was exposed to 80° C. and 95% RH for 500 hours in a small environmental tester (ESPEC SH-221) (moist heat treatment). The bending strength (MPa) of the treated test piece was measured under the conditions described above.
Regarding the bending strength after molding and the bending strength after moist heat treatment, the strength retention rate was determined using the following formula (1).

<Observation of morphology>
A sample approximately 1 cm square was cut from the thermoplastic resin composition (the above-mentioned bending test piece) using a wheel saw (ISOMET4000 (manufactured by BUEHLER)). The sample was placed in a φ32 mm cup dedicated to resin fixation, and the resin was fixed with epoxy resin (Epoxy cure J (manufactured by BUEHLER)).
The resin-fixed sample was polished using a precision polishing device (EcoMetTM250+AutMetTM250 (manufactured by BUEHLER)) using abrasive paper with silicon carbide fixed abrasive grains to obtain a cross section for observation.
The cross section for observation was dyed by immersing it in a phosphotungstic acid solution for 30 minutes to impart contrast to the observed components. In addition, a 10 nm thick coating of osmium metal was formed using Neoc-AN (manufactured by Meiwaforsys) to provide conductivity during electron microscopy.

(Observation of co-continuous structure)
Using a scanning electron microscope (SEM, IT500HR, manufactured by JEOL), the core part of the cross section of the molded product (the part excluding the surface layer with a depth of less than 20 μm, the center of the cross section, parallel to the flow direction of the resin composition) ) was magnified 10,000 times under the conditions of an accelerating voltage of 15 kV and a spot size of 50, and a backscattered electron image of the observation cross section was obtained.
FIG. 1 shows a cross-sectional SEM image of the thermoplastic resin composition obtained in Example 1. From FIG. 1, it was confirmed that the structure was co-continuous. When performing SEM observation after electronic staining with phosphotungstic acid, polyamide 6 was selectively stained and observed as a white region. The black region is mainly syndiotactic polystyrene and fumaric acid modified polyphenylene ether.
FIG. 2 shows a cross-sectional SEM image of the thermoplastic resin composition obtained in Comparative Example 1. From Figure 2, it was confirmed that it was a sea-island structure.

(Observation of each phase composing the co-continuous structure)
Using SEM, the core part of the cross section of the molded product (the part excluding the surface layer with a depth of less than 20 μm, the center of the cross section, the cross section parallel to the flow direction of the resin composition) was examined at an accelerating voltage of 15 kV and a spot size of 50. , a backscattered electron image of a cross section for observation was obtained with magnification of 30,000 times.
FIG. 3 is an enlarged image of the SEM image of FIG. 1 (Example 1). From Figure 3, a compatible solution of syndiotactic polystyrene and fumaric acid-modified polyphenylene ether is dispersed in the first phase forming a co-continuous structure, and polyamide 6 is dispersed in the second phase, both of which have a sea-island structure. It was confirmed that this is the case.
FIG. 4 is an enlarged image of the SEM image (comparative example 1) in FIG. 2. It was confirmed that no co-continuous structure was formed.

(Average diameter of island structure)
Regarding Example 1, from backscattered electron images of observation cross sections at 10 non-overlapping locations obtained by observing each phase constituting the above-mentioned co-continuous structure, each of 100 island portions having an area of 0.20 μm ² or less was obtained. The area of the island was measured. For each island, the equivalent diameter obtained by converting it into a circle having the area was calculated, and the particle diameter was determined. The average diameter was calculated by the arithmetic mean of 100 particle diameters. As a result, it was confirmed that the average diameter of the island structure was 500 nm or less. Regarding the comparative example, since a co-continuous structure was not obtained from the above observation of the co-continuous structure, it was not possible to observe each phase forming the co-continuous structure.

(Coating phase of reinforcing fiber)
A SEM image including a cross section of the reinforcing fibers was observed, and judgment was made visually.
FIG. 5 shows a cross-sectional SEM image of the carbon fibers in the thermoplastic resin composition obtained in Example 1. From FIG. 5, it can be confirmed that the carbon fibers are covered with the first phase forming a co-continuous structure.
FIG. 6 shows a cross-sectional SEM image of the carbon fibers in the thermoplastic resin composition obtained in Comparative Example 1. From FIG. 6, it can be confirmed that the carbon fibers are covered with both sea-island structures.

(A-1): Polyamide 6
(B-1): Syndiotactic polystyrene (C-1): Fumaric acid modified polyphenylene ether (C-2): Polyphenylene ether (D-1): Chopped carbon fiber

From Example 1, it can be seen that the molded article of the present invention has excellent mechanical properties. Furthermore, in the molded article of the present invention, deterioration in mechanical properties after wet heat treatment is suppressed.

Claims (15)

Including thermoplastic resin (A), thermoplastic resin (B) and thermoplastic resin (C),
It has a co-continuous morphology,
The first phase of the co-continuous structure mainly consists of the thermoplastic resin (A), and the second phase of the co-continuous structure mainly consists of the thermoplastic resin (B) and the thermoplastic resin (C). ) consists of a mixed phase of
In the first phase, a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) is dispersed in the thermoplastic resin (A),
A thermoplastic resin composition in which the thermoplastic resin (A) is dispersed in a mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) in the second phase. The average diameter of the mixed phase of the thermoplastic resin (B) and the thermoplastic resin (C) present in the first phase is 500 nm or less,
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) present in the second phase has an average diameter of 500 nm or less. Claim 1 or 2, wherein the thermoplastic resin (A) and the thermoplastic resin (C) have a polar functional group, and the thermoplastic resin (B) and the thermoplastic resin (C) are completely compatible. The thermoplastic resin composition described in . The thermoplastic resin composition according to claim 3, wherein the polar functional groups of the thermoplastic resin (A) and the thermoplastic resin (C) are carboxyl groups or amino groups. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin (A) and the thermoplastic resin (B) are crystalline resins. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin (C) is a polyarylene ether. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin (B) is syndiotactic polystyrene. The mass ratio of the thermoplastic resin (A) to the total of the thermoplastic resin (B) and the thermoplastic resin (C) ((A):((B)+(C))) is 40:60 to The thermoplastic resin composition according to any one of claims 1 to 7, which has a ratio of 60:40. The thermoplastic resin (C) is added to 100 parts by mass of the thermoplastic resin (A), the thermoplastic resin (B), and the thermoplastic resin (C) ((A) + (B) + (C)). ) is 3 to 15 parts by mass, the thermoplastic resin composition according to any one of claims 1 to 8. The thermoplastic resin composition according to any one of claims 1 to 9, further comprising reinforcing fibers (D). The thermoplastic resin composition according to claim 10, wherein the reinforcing fiber (D) is one or more selected from glass fiber and carbon fiber. The thermoplastic resin composition according to claim 10 or 11, wherein the surface of the reinforcing fiber (D) is coated with the first phase. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 9. A molded article made of the thermoplastic resin composition according to any one of claims 10 to 12. The molded article according to claim 14, which has a strength retention rate of 80% or more after a wet heat treatment at 80° C./95% RH for 500 hours as expressed by the following formula (1).