joint

Abstract

To provide a joined body of two moldings which has a high joint strength and is composed of dissimilar materials.SOLUTION: A joined body is obtained by joining a molding 1 and a molding 2, wherein the molding 1 is formed from a thermoplastic resin composition (A), and contains 10-80 pts.mass of polyphenylene ether with respect to 100 pts.mass of the thermoplastic resin composition (A), the molding 2 is formed from a thermoplastic resin composition (B), and contains 20-90 pts.mass of a crystalline thermoplastic resin with respect to 100 pts.mass of the thermoplastic resin composition (B), and the molding 1 and the molding 2 are welded and joined to each other in at least a part of an interface between the molding 1 and the molding 2.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a joined body. In particular, it relates to a battery case used for a large-capacity storage battery, particularly an alkaline storage battery.

Background Art

[0002] Conventionally, metals have been used for containers for storing and pouring highly hydrophobic organic solvents. However, attention has been paid to the feature that plastics are lightweight, and various resin materials have been developed recently, and non-metallic containers with high resistance to liquids are being used. In particular, when storing a strongly acidic or strongly basic aqueous solution, there is a risk of corrosion for metals, so the utility value of engineering plastics that are resistant to both hydrophilic and hydrophobic liquids has been increasing. As such a resin material that is resistant to both hydrophilic and hydrophobic liquids, crystalline resins can be mentioned, and taking advantage of the characteristics of crystalline resins and their high gas barrier properties, they are used for containers in various applications for storing or transporting liquids and solids. Alkaline storage batteries have a high energy density and excellent reliability, and are widely used as power sources in modern times. Among them, open-type nickel-cadmium storage batteries and lead storage batteries, which are medium- and large-sized batteries with high energy density and are used as mobile power sources from household appliances to electric vehicles, require refilling during use, and the problem of maintenance complexity is raised. Therefore, maintenance-free, that is, sealing of the battery is required.

[0003] For joining resin molded products, various joining techniques such as adhesives and heat welding are provided. However, the technique of joining resin molded products with an adhesive can join the resin molded products without deformation, but generally, it takes several hours for the adhesive to cure, resulting in poor productivity, and it is required to select an appropriate adhesive for the type and application of the thermoplastic resin used.

[0004] However, when using crystalline resins, the low solvent affinity of the material makes it difficult to select an appropriate adhesive for joining materials. For example, lithium-ion batteries contain an electrolyte in which lithium salts are dissolved in an aprotic solvent, or a polymer gel impregnated with the electrolyte. Substances such as LiPF6 and LiBF4 are used as lithium salts, but these salts generate hydrofluoric acid through hydrolysis reactions with water. Therefore, the resins and adhesives used in the design must have resistance to the electrolyte. Furthermore, in automotive applications, use in harsh environments is expected. Therefore, a decrease in the strength of the adhesive after curing in high-temperature environments and a decrease in durability after immersion in the electrolyte are undesirable.

[0005] Traditional heat welding techniques for thermoplastic resin molded products, such as hot plate welding, vibration welding, and ultrasonic welding, can result in burrs and thermal deformation on the joined resin molded products, or damage to internal components. Alkaline batteries for electric vehicles require not only high output and high energy, but also miniaturization and weight reduction for vehicle installation. Furthermore, these welding techniques become less efficient and difficult to achieve high-precision welding when components are miniaturized. Laser welding minimizes burrs, deformation, and impact on internal components, enabling the design of highly precise parts. It also reduces the risk of dust contamination between processes and achieves high joint strength (Prior Reference 1). Furthermore, in recent years, the market price of laser welding machines has tended to decline, and they are increasingly being adopted as a welding method. However, these thermal welding technologies have the problem that they are limited to joining molded products made of resins with high chemical affinity (compatibility), that is, basically the same material (Previous Reference 2).

[0006] However, in industrial applications of thermoplastic resins, including protective housing components for automotive and industrially used battery units, battery cases (containers) for secondary batteries such as lithium metal batteries, lithium-ion batteries, polymer-ion batteries, nickel-metal hydride batteries, lead-acid batteries, and nickel-cadmium batteries, and secondary battery cases suitable for use as sheet or film materials constituting secondary batteries, the resins used to make up the components are not necessarily designed using the same material. In particular, in alkaline batteries, repeated charging and discharging causes swelling of the electrode plates, and even when external pressure is applied, swelling of approximately 10% is unavoidable. Therefore, the battery case and lid that house the electrode plates need to withstand stress deformation. If the battery case is designed from a material that does not easily stretch, a large amount of stress will be applied. When the required resin properties differ greatly depending on the component, it is expected that welding technology will be used during the design phase, and it is desirable that welding of dissimilar materials be achieved.

[0007] As a means to solve this phenomenon, a joining method for joining resin molded articles made of resin compositions is known, in which ultraviolet light is irradiated onto the regions to be joined of a first molded article made of a resin composition that transmits laser light and / or a second molded article made of a resin composition that absorbs laser light, the second molded article is positioned so that the region of the first molded article is in contact with the region of the second molded article, laser light is irradiated from the first molded article side so that the laser light that has passed through the first molded article is absorbed by the region of the second molded article, the interface where the regions of the first and second molded articles are in contact is heated and melted, and then cooled and solidified to join the first and second molded articles. (Patent Document 1)

[0008] However, the above method requires a step of irradiating with ultraviolet light before performing laser welding, which is difficult to achieve with general-purpose laser welding machines.

[0009] As a method for improving the weldability of dissimilar materials, in the case of heat welding, an approach has been taken by changing the composition of the materials. (Patent Documents 3 and 4)

[0010] Polyphenylene ether alloy technology is known as a method for improving the properties of resins. A sealed secondary battery case made of a polyphenylene ether resin and a polystyrene resin has been disclosed, but the battery case molded from this resin composition has problems such as stress cracks occurring due to thermal strain when the lid is heat-sealed and insufficient hydrolysis resistance (Patent Document 5).

[0011] PPS / PPE resins have been developed by alloying PPS, a crystalline resin, with polyphenylene ether (hereinafter sometimes referred to as "PPE"), an amorphous resin. The present invention relates to a polyphenylene sulfide resin composition that is excellent in toughness (impact strength), weld strength, heat creep resistance, water vapor permeability resistance, oil resistance, chemical resistance, and heat resistance, and further relates to a polyphenylene sulfide resin composition for secondary battery cases that can be suitably used as a battery case (container) for secondary batteries such as lithium metal batteries, lithium-ion batteries, polymer-ion batteries, nickel-metal hydride batteries, lead-acid batteries, and nickel-cadmium batteries, as well as a sheet or film material constituting the secondary battery (Patent Document 6). It is known that... [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] Patent No. 47562839 [Patent Document 2] International Publication No. 2018 / 216804 [Patent Document 3] Patent No. 4781219 [Patent Document 4] Patent No. 3749331 [Patent Document 5] Japanese Patent Application Publication No. 6-203814 [Patent Document 6] Patent No. 4917211 [Overview of the project] [Problems that the invention aims to solve]

[0013] By using crystalline resins such as polyamide and polyphenylene sulfide, it has become possible to use them in various applications for storing or transporting liquids in secondary battery cases, such as protective housing components for battery units used in automobiles and industrial applications, battery cases (containers) for secondary batteries such as lithium metal batteries, lithium-ion batteries, polymer-ion batteries, nickel-metal hydride batteries, lead-acid batteries, and nickel-cadmium batteries, and as sheet or film materials that constitute secondary batteries. Here, medium to large batteries with high energy density, such as open-type nickel-cadmium batteries and lead-acid batteries used as mobile power sources from home appliances to electric vehicles, require fluid replenishment during their service life, which presents the challenge of complicated maintenance. Therefore, maintenance-free operation, i.e., sealing of batteries, is required. Typical welding methods for achieving battery sealing include bonding components using adhesives and heat welding. In particular, when designing battery cases using adhesives, it has been difficult to select an appropriate adhesive when joining materials because crystalline resins have low solvent affinity. Furthermore, lithium-ion batteries contain an electrolyte solution in which lithium salts are dissolved in an aprotic solvent, or a polymer gel impregnated with the electrolyte solution. While substances such as LiPF6 and LiBF4 are used as lithium salts, these salts generate hydrofluoric acid through hydrolysis with water. Therefore, the resins and adhesives used in the design must have resistance to the electrolyte. Moreover, automotive applications are expected to operate in harsh environments. Therefore, a decrease in adhesive strength after curing in high-temperature environments and a decrease in durability after immersion in the electrolyte are undesirable. On the other hand, with heat welding, the battery case suffers from problems such as stress cracks due to thermal distortion when the lid is heat-welded, and insufficient hydrolysis resistance.

[0014] Therefore, the object of the present invention is to provide a jointed body of two molded bodies made of different materials that has high bonding strength. [Means for solving the problem]

[0015] As a result of intensive studies to solve the above problems, the inventors have found that a molded body made of a resin composition containing 10 to 80 parts by mass of polyphenylene ether with respect to 100 parts by mass of the thermoplastic resin composition (A) and a molded body made of a resin composition containing 20 to 90 parts by mass of a crystalline thermoplastic resin with respect to 100 parts by mass of the thermoplastic resin composition (B) are welded and joined at at least a part of the interface without an adhesive layer, so that the two molded bodies are strongly joined at the interface and there is little deformation during joining.

[0016] That is, the present invention is as follows. [1] A molded body 1 and a molded body 2 are joined, the molded body 1 is made of a thermoplastic resin composition (A), the thermoplastic resin composition (A) The thermoplastic resin composition (A) comprises polyphenylene ether. contains, with respect to 100 parts by mass, The aforementioned polyphenylene ether 50~78 in parts by mass, the molded body 2 is made of a thermoplastic resin composition (B), the thermoplastic resin composition (B) The thermoplastic resin composition (B) comprises a crystalline thermoplastic resin. contains, with respect to 100 parts by mass, The aforementioned 20 to 90 parts by mass of a crystalline thermoplastic resin, The thermoplastic resin composition (B) further contains an amorphous component, The amorphous component is selected from the group consisting of polyphenylene ether and semi-aromatic polyamide. the molded body 1 and the molded body 2 are welded and joined at at least a part of the interface between the molded body 1 and the molded body 2 Occasionally, The laser transmittance of the molded body 1 at a wavelength of 940 nm is 20% or more. and are characterized in that a joined body 。 [2 The thermoplastic resin composition (A) contains a dye that transmits laser light having a wavelength of 800 nm or more, the joined body according to [1 ] described. [3] The thermoplastic resin composition (B) contains a black coloring agent, the joined body according to [1] or [2] described. [4] ​ The molded body 2 has a laser transmittance of 3% or less at a wavelength of 800 nm, [1]~ [3] A joint described in any of the following. [5] The thermoplastic resin composition (A) and / or the thermoplastic resin composition (B) contains 0.1 to 60 parts by mass of inorganic filler per 100 parts by weight of the thermoplastic resin composition, [1]~ [4] A joint described in any of the following. [6] The thermoplastic resin composition (B) contains 20 parts by mass or more of at least one selected from the group consisting of polyamide and polyphenylene sulfide per 100 parts by mass of the thermoplastic resin composition (B), [1]~ [5] A joint described in any of the following. [7] The joint according to any one of [1] to [6], wherein the type of thermoplastic resin most abundantly present in the molded body 1 and the molded body 2 is different. [8] The joint according to any one of [1] to [7], wherein the thermoplastic resin composition (B) has a ratio of the amount of amorphous component to the amount of crystalline thermoplastic resin (amount of amorphous component: amount of crystalline thermoplastic resin) of 5:5 to 2:8. [9] The connector is a sealed battery case used as a power source for mobile devices, as described in any of [1] to [8].

[10] The joint is an insulating component for a solar cell module, as described in any of [1] to [8]. [Effects of the Invention]

[0017] The present invention provides a joint between two molded bodies made of different materials that exhibits minimal thermal deformation and high joint strength. [Modes for carrying out the invention]

[0018] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "these embodiments"). These embodiments are illustrative examples for explaining the present invention, and the present invention is not limited to these embodiments. Furthermore, the present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0019] [zygote] The joint in this embodiment is a joint formed by joining a molded body 1 and a molded body 2. The joint 1 and the joint 2 are welded together at least a portion of the interface between the molded body 1 and the molded body 2. The joint may be joined over the entire interface between the molded body 1 and the molded body 2. The joining is preferably done by thermal welding (for example, welding by laser light). In this embodiment, it is preferable that the joined body does not contain any other layer (for example, an adhesive layer) between the molded body 1 and the molded body 2. The molded body 1 and the molded body 2 described above may be made of different materials with different compositions. For example, they may be made of different types of thermoplastic resins that are most abundant in the molded body.

[0020] The above-mentioned molded article 1 is made of a thermoplastic resin composition (A) containing 10 to 80 parts by mass of polyphenylene ether per 100 parts by mass of the thermoplastic resin composition (A). Preferably, the molded article 1 is made of thermoplastic resin composition (A) alone. The adhesive strength between the molded body 1 and the molded body 2 is improved by the fact that the molded body 1 is made of a thermoplastic resin composition (A) containing polyphenylene ether within the above range. From the viewpoint of further improving the adhesive strength, it is preferable that the resin (preferably thermoplastic resin) contained in the thermoplastic resin composition (A) is only polyphenylene ether and / or polystyrene. Furthermore, from the viewpoint of further improving the adhesive strength, it is preferable that the total mass ratio of polyphenylene ether and polystyrene per 100 parts by mass of thermoplastic resin composition (A) is 70 to 95 parts by mass. Furthermore, from the viewpoint of further improving the adhesive strength, it is preferable that the mass ratio of polystyrene per 100 parts by mass of thermoplastic resin composition (A) is 3 to 27 parts by mass. Furthermore, from the viewpoint of further improving the adhesive strength, it is preferable that the mass ratio of crystalline thermoplastic resin in 100 parts by mass of thermoplastic resin composition (A) is 0 to 50 parts by mass, and that it does not contain crystalline thermoplastic resin. From the viewpoint of further improving the adhesive strength with the molded body 2, it is preferable that the molded body 1 has a laser transmittance of 20% or more at a wavelength of 940 nm. In particular, it is preferable that the laser transmittance is 20% or more at all wavelengths from 900 nm to 1100 nm.

[0021] The molded article 2 described above is made of a thermoplastic resin composition (B) containing 20 to 90 parts by mass of crystalline thermoplastic resin per 100 parts by mass of thermoplastic resin composition (B). Preferably, the molded article 2 is made of thermoplastic resin composition (B) alone. The adhesive strength between the molded body 2 and the molded body 1 is improved by making the molded body 2 from a thermoplastic resin composition (B) containing a crystalline thermoplastic resin within the above range. From the viewpoint of further improving the adhesive strength with the molded body 1, it is preferable that the molded body 2 has a laser transmittance of 3% or less at a wavelength of 800 nm.

[0022] From the viewpoint of further improving the adhesive strength with the molded body 2, the above thermoplastic resin composition (A) preferably contains a dye that transmits laser light with a wavelength of 800 nm or more. Furthermore, from the viewpoint of further improving the adhesive strength with the molded body 2, the above thermoplastic resin composition (A) preferably contains 0.1 to 60 parts by mass of an inorganic filler per 100 parts by mass of the resin composition.

[0023] The above thermoplastic resin composition (B) is preferably included with a black coloring agent from the viewpoint of further improving the adhesive strength with the molded body 1. Furthermore, from the viewpoint of further improving the adhesive strength with the molded body 1, the above thermoplastic resin composition (B) preferably contains 0.1 to 60 parts by mass of an inorganic filler per 100 parts by mass of the resin composition. From the viewpoint of further improving the adhesive strength with the molded article 1, the above thermoplastic resin composition (B) preferably contains 20 parts by mass or more of at least one selected from the group consisting of polyamide and polyphenylene sulfide per 100 parts by mass of thermoplastic resin composition (B). Furthermore, from the viewpoint of further improving the adhesive strength with the molded article 1, the above crystalline thermoplastic resin preferably is at least one selected from the group consisting of polyamide and polyphenylene sulfide. From the viewpoint of further improving the adhesive strength with the molded article 1, the above thermoplastic resin composition (B) preferably further contains an amorphous component, and the amorphous component is preferably at least one selected from the group consisting of polyphenylene ether and semi-aromatic polyamide. From the viewpoint of further improving adhesive strength, it is preferable that the mass ratio of crystalline thermoplastic resin (for example, at least one selected from the group consisting of polyamide and polyphenylene sulfide) to 100 parts by mass of the total mass of resins contained in thermoplastic resin composition (B) is 50 parts by mass or more. When a crystalline thermoplastic resin contains polyamide, it is preferable to include a crystalline aromatic polyamide resin from the viewpoint of bonding strength. For example, the aromatic polyamide resin is preferably 20 to 100% by mass, and more preferably 30 to 100% by mass, relative to 100% by mass of polyamide in the thermoplastic resin composition (B). Furthermore, the aliphatic polyamide is preferably 80% by mass or less, and more preferably 70% by mass or less, relative to 100% by mass of polyamide in the thermoplastic resin composition (B). The mass percentage of polystyrene in 100% by mass of thermoplastic resin composition (A) is 10% by mass or less, and if the crystalline thermoplastic resin contains polyphenylene sulfide, it is preferable that the cross-linked polyphenylene sulfide is present at 60% by mass or more, and more preferably 70% by mass or more, relative to 100% by mass of the polyphenylene sulfide. Furthermore, the linear polyphenylene sulfide is preferably 30% by mass or less, and more preferably 25% by mass or less.

[0024] The joint of this embodiment will be described in detail below.

[0025] <Molded body 1> The above-mentioned molded body 1 is made of a thermoplastic resin composition (A).

[0026] [Thermoplastic resin composition (A)] The above thermoplastic resin composition (A) contains at least a polyphenylene ether. The polyphenylene ether may be a modified polyphenylene ether (mPPE). The above thermoplastic resin composition (A) contains 10 to 80 parts by mass of polyphenylene ether per 100 parts by mass of the above thermoplastic resin composition (A). The above thermoplastic resin composition (A) may further contain amorphous resins other than polyphenylene ether, dyes that transmit laser light with a wavelength of 800 nm or more, inorganic fillers, and the like.

[0027] (Polyphenylene ether) The above-mentioned polyphenylene ether can also be mixed with other resins to form an alloy, such as a polyphenylene ether / polystyrene alloy, a polyphenylene ether / high-impact polystyrene alloy, and a polyphenylene ether / polystyrene / high-impact polystyrene alloy. Among these, it is preferable to use polyphenylene ether alone from the viewpoint of dimensional accuracy and chemical resistance of the molded article 1.

[0028] The structure of the polyphenylene ether described above is not particularly limited, but it is preferably a homopolymer and / or copolymer polyphenylene ether consisting of repeating units represented by the following bonding unit formula (1), and having an intrinsic viscosity of 0.16 to 0.36 dL / g, more preferably 0.20 to 0.34 dL / g, as measured using an Ubbelohde-type viscosity tube in chloroform at 30°C. [ka] ...(1) (Here, R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, hydrocarbon oxy group, or halohydrocarbon oxy group in which at least two carbon atoms separate the halogen atom and the oxygen atom, and may be the same or different from each other. Also, n is an integer of 1 or more.)

[0029] By setting the intrinsic viscosity of polyphenylene ether to 0.16 dL / g or higher, a good balance between mechanical properties, fluidity, and mold release properties can be achieved. By setting it to 0.36 dL / g or lower, fluidity (e.g., SFD characteristics at 0.5 mm) and flame retardancy can be enhanced, especially in the high-shear region.

[0030] Specific examples of the above-mentioned polyphenylene ethers include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether). Polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol with other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. Among these, poly(2,6-dimethyl-1,4-phenylene ether) and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is even more preferred.

[0031] The above-mentioned method for producing polyphenylene ether is not particularly limited. For example, it can be easily produced by using a complex of cuprous salt and amine by Hay as described in U.S. Patent No. 3,306,874 as a catalyst and oxidative polymerization of, for example, 2,6-xylenol. It can also be easily produced by adjusting the intrinsic viscosity using methods described in U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357 and U.S. Patent No. 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Unexamined Patent Publication No. 50-51197 and Japanese Unexamined Patent Publication No. 63-152628, etc.

[0032] As mentioned above, it is preferable that the polyphenylene ether is 100% by mass. When used as a polymer alloy, polymer alloys with a polyphenylene ether content of 1 to 99% by mass can also be used.

[0033] When polyphenylene ether is used as a polymer alloy as described above, the resin used with the polyphenylene ether may be a copolymer obtained by using two or more styrene compounds in combination or high-impact polystyrene, but polystyrene obtained by polymerizing styrene alone is preferred. Furthermore, polystyrene resins having a stereoregular structure, such as atactic polystyrene and syndiotactic polystyrene, can be effectively used as the resin used with the polyphenylene ether.

[0034] Polystyrenes that can be used with polyphenylene ether include homopolymers of styrene compounds and copolymers of two or more styrene compounds. High-impact polystyrenes include rubber-modified styrene, in which a rubbery polymer is dispersed in particulate form within a matrix of polymers of styrene compounds. Examples of styrene compounds that yield these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, and p-tert-butylstyrene.

[0035] The mass ratio of the polyphenylene ether to 100 parts by mass of the thermoplastic resin composition (A) is 10 to 80 parts by mass, preferably 30 to 79 parts by mass, and more preferably 50 to 78 parts by mass, from the viewpoint of achieving higher bonding strength.

[0036] (Amorphous thermoplastic resins other than polyphenylene ether) Examples of amorphous thermoplastic resins other than polyphenylene ether include thermoplastic resins that do not exist in a crystalline state, or that exhibit extremely low crystallinity even if crystallization occurs, and thermoplastic polymer alloys as exemplified below. "Not existing in a crystalline state" or "extremely low crystallinity even if crystallization occurs" means that no exothermic peak associated with crystallization is observed (i.e., there is no crystalline region), or even if observed, the degree of crystallinity is extremely low, such that the heat of fusion is, for example, 10 J / g or less. The heat of fusion can be measured using a differential scanning calorimeter.

[0037] Specifically, the amorphous thermoplastic resins other than polyphenylene ether are not particularly limited as long as they are amorphous resins, and examples include styrene-based resins such as polystyrene, rubber-reinforced polystyrene (high-impact polystyrene), and acrylonitrile-butadiene-styrene copolymer (hereinafter also referred to as "ABS"); polycarbonate-based resins such as polycarbonate, polycarbonate / ABS alloy, and polycarbonate / polybutylene terephthalate alloy; and so on.

[0038] (Dyes that transmit laser light with wavelengths of 800 nm or higher) The thermoplastic resin composition (A) described above preferably contains a dye that transmits laser light with a wavelength of 800 nm or more, from the viewpoint of not reducing the adhesive strength with the molded body 2 and improving the aesthetic appearance. As the dye that transmits laser light with a wavelength of 800 nm or more, the LTW dye masterbatch manufactured by Orient Chemical Industries, Ltd. is preferred. The mass ratio of the dye that transmits laser light with a wavelength of 800 nm or more to 100 parts by mass of the thermoplastic resin composition (A) is preferably 1 to 10 parts by mass, more preferably 3 to 8 parts by mass, and even more preferably 4 to 6 parts by mass, from the viewpoint of not reducing the adhesive strength with the molded body 2 and improving the design.

[0039] (Inorganic fillers) The thermoplastic resin composition (A) described above preferably further contains an inorganic filler. As the inorganic filler, at least one selected from the group consisting of glass fibers, carbon fibers, carbon nanotubes, cellulose fibers, silicon carbide fibers, ceramic fibers, aramid fibers, alumina fibers, gypsum fibers, metal fibers, calcium titanate whiskers, calcium carbonate whiskers, and wollastonite can be used. Among these, glass fibers are preferred from the viewpoint of heat resistance and adhesion to the resin. Examples of the glass fibers mentioned above include, and are preferred to be, the same as the glass fibers in the thermoplastic resin composition (B) described later. The mass ratio of the inorganic filler to 100 parts by mass of the thermoplastic resin composition (A) is preferably 1 to 60 parts by mass, more preferably 20 to 50 parts by mass, and even more preferably 30 to 40 parts by mass, from the viewpoint of further improving the bonding strength with the molded body 2.

[0040] <Molded body 2> The molded body 2 described above is made of a thermoplastic resin composition (B).

[0041] [Thermoplastic resin composition (B)] The above thermoplastic resin composition (B) comprises at least a crystalline thermoplastic resin. The above thermoplastic resin composition (B) contains 20 to 90 parts by mass of crystalline thermoplastic resin per 100 parts by mass of the above thermoplastic resin composition (B). The above thermoplastic resin composition (B) may further contain a colorant, an inorganic filler, a flame retardant, etc., and it is preferable that it contains an inorganic filler and a flame retardant. The thermoplastic resin composition (B) described above has a different composition from the thermoplastic resin composition (A). From the viewpoint of having higher bonding strength, it is preferable that the thermoplastic resin with the highest mass percentage in thermoplastic resin composition (A) is the polyphenylene ether described above, and that the thermoplastic resin with the highest mass percentage in thermoplastic resin composition (B) is a polyamide or polyphenylene sulfide.

[0042] (Crystalline thermoplastic resin) The above thermoplastic resin composition (B) includes a crystalline thermoplastic resin. By including a crystalline thermoplastic resin, the chemical resistance of the polymer alloy containing an amorphous resin can be improved. The above-mentioned crystalline thermoplastic resins are not particularly limited, but examples include polyphenylene sulfide, polyethylene, polypropylene, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, and syndioctatic polystyrene. From the viewpoint of further improving chemical resistance, polyphenylene sulfide, polyamide, and polyethylene terephthalate are preferred among these.

[0043] ((Polyphenylene sulfide)) Polyphenylene sulfide is divided into two types depending on its manufacturing method: linear polyphenylene sulfide resin (hereinafter sometimes abbreviated as "linear PPS") and cross-linked polyphenylene sulfide resin (hereinafter sometimes abbreviated as "cross-linked PPS"). The former linear PPS is a polymer containing typically 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more, of repeating units of arylene sulfide represented by the following general formula (Formula 2). [-Ar-S-] ···(2) (Here, Ar represents an arylene group, and examples of arylene groups include p-phenylene group, m-phenylene group, substituted phenylene group (preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group as a substituent), p,p'-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylene carbonyl group, naphthylene group, etc.) Linear PPS may be a homopolymer having only one type of arylene group as its constituent unit, or it may be a copolymer obtained by mixing two or more different types of arylene groups from the viewpoint of processability and heat resistance. Among these, linear polyphenylene sulfide resin having repeating units of p-phenylene sulfide as its main constituent unit is preferred because it has excellent processability and heat resistance and is readily available industrially.

[0044] Methods for producing this linear PPS typically include polymerizing halogen-substituted aromatic compounds, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate; polymerizing sodium sulfide or sodium hydrogen sulfide with sodium hydroxide or hydrogen sulfide with sodium hydroxide or sodium aminoalkanoate in a polar solvent; and self-condensation of p-chlorothiophenol. Among these, the method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfone solvent such as sulfolane, is particularly suitable.

[0045] These manufacturing methods are publicly known, and linear PPS can be obtained by methods described in, for example, U.S. Patent No. 2,513,188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-3368, Japanese Patent Publication No. 52-12240, Japanese Unexamined Patent Publication No. 61-225217, U.S. Patent No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Unexamined Patent Publication No. 5-222196, etc., or by prior art methods exemplified in these patents, etc.

[0046] A preferred linear PPS is a linear polyphenylene sulfide resin in which the amount extracted with methylene chloride is 0.7% by mass or less, preferably 0.5% by mass or less, and the terminal-SX group (S is a sulfur atom, X is an alkali metal or hydrogen atom) is 20 μmol / g or more, preferably 20 to 60 μmol / g.

[0047] The amount extracted by methylene chloride can be measured by the following method. Specifically, 5 g of linear PPS powder is added to 80 ml of methylene chloride, and Soxhlet extraction is performed for 6 hours. After cooling to room temperature, the extracted methylene chloride solution is transferred to a weighing bottle. Furthermore, the container used for the extraction is washed in three separate washes using a total of 60 ml of methylene chloride, and the washing solution is collected in the weighing bottle. Next, the weighing bottle is heated to approximately 80°C to evaporate and remove the methylene chloride, and the residue is weighed. From this residue amount, the amount extracted by methylene chloride, i.e., the proportion of oligomers present in linear PPS, can be determined.

[0048] The quantification of the -SX group can be carried out by the following method. Specifically, linear PPS powder is dried at 120°C for 4 hours, then 20 g of the dried linear PPS powder is added to 150 g of N-methyl-2-pyrrolidone and vigorously stirred and mixed at room temperature for 30 minutes until no powder aggregates remain, resulting in a slurry. After filtering this slurry, it is washed seven times using 1 liter of warm water at approximately 80°C each time. The resulting filtered cake is then slurryed again in 200 g of pure water, and then 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Next, the mixture is stirred at 25°C for 30 minutes, filtered, and then washed six times using 1 liter of warm water at approximately 80°C each time. The resulting filtered cake is then slurryed again in 200 g of pure water, and then titrated with 1N sodium hydroxide. The amount of -SX groups present in the linear PPS can be determined from the amount of sodium hydroxide consumed.

[0049] Here, a specific example of a method for producing linear PPS that satisfies the extraction amount by methylene chloride being 0.7% by mass or less and the terminal-SX group being 20 μmol / g or more is described in Japanese Patent Application Publication No. Hei 8-253587, which involves reacting an alkali metal sulfide with a dihalo-aromatic compound in an organic amide solvent, and during the reaction, cooling the gas phase portion of the reaction vessel to condense a portion of the gas phase inside the reaction vessel, which is then refluxed to the liquid phase above the reaction solution to reduce the oligomer component. Furthermore, cross-linked (including semi-cross-linked) polyphenylene sulfide resins are produced by polymerizing the linear polyphenylene sulfide resin described above, and then further heating it in the presence of oxygen at a temperature below the melting point of the polyphenylene sulfide resin to promote oxidative crosslinking and appropriately increase the polymer molecular weight and viscosity.

[0050] The most preferred type of cross-linked PPS is a cross-linked polyphenylene sulfide resin in which the volatile content collected in the molten state at 320°C is 1000 ppm or less. The quantitative determination of the volatile content collected in the molten state at 320°C can be determined by the following method. Specifically, 0.5 g of cross-linked PPS powder is weighed into a sealed test tube with an air inlet and outlet. While immersed in a solder bath heated to 320°C for 30 minutes, nitrogen gas is injected into the air inlet of the test tube at a flow rate of 100 cc / min. The gas containing volatile components derived from the cross-linked PPS generated in the test tube is purged from the air outlet. The purged gas is then bubbled in acetone inside another sealed test tube containing acetone, dissolving the volatile components in the acetone. The volatile components of the cross-linked PPS dissolved in the acetone can be quantified using a gas chromatograph-mass spectrometer (GC-MS) by performing a temperature-controlled analysis from 50°C to 290°C, assuming the same sensitivity as monochlorobenzene, thereby determining the volatile components in the cross-linked PPS.

[0051] To obtain crosslinked PPS with a volatile content of 1000 ppm or less collected in the molten state at 320°C, it is usually possible to obtain crosslinked PPS with the desired volatile content by devising the polymer concentration and solvent composition during the polymerization stage of linear PPS, devising the washing method for recovering the polymer at the polymerization stage, and changing the temperature and time of the high-temperature treatment in the subsequent crosslinking stage.

[0052] Furthermore, these PPS (linear PPS, cross-linked PPS) may also be acid-modified PPS. Here, acid-modified PPS is obtained by modifying the above-mentioned PPS with an acid compound, and examples of such acid compounds include unsaturated carboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and maleic anhydride, as well as saturated aliphatic carboxylic acids and aromatically substituted carboxylic acids. Furthermore, inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, and carbonic acid can also be listed as such acid compounds.

[0053] The melt viscosity of the linear PPS and crosslinked PPS described above at 300°C is preferably 1 to 10,000 Pa·s, more preferably 50 to 8,000 Pa·s, and even more preferably 100 to 5,000 Pa·s.

[0054] The above melt viscosity was measured using a flow tester (CFT-500 model, manufactured by Shimadzu Corporation) with JIS K-7210 as the reference test method. The PPS was preheated to 300°C for 6 minutes, and the value was measured with a load of 196N and a die length (L) / die diameter (D) = 10mm / 1mm.

[0055] The mass ratio of the crystalline thermoplastic resin to 100 parts by mass of the thermoplastic resin composition (B) is 20 to 90 parts by mass, preferably 20 to 80% by mass, more preferably 25 to 75% by mass, and even more preferably 30 to 70% by mass. By having a crystalline thermoplastic resin content of 20% by mass or more, chemical resistance can be ensured. Furthermore, by having a crystalline resin content of 80% by mass or less, burrs can be suppressed and outgassing from the molded product can be suppressed.

[0056] The thermoplastic resin composition (B) described above preferably contains a crystalline thermoplastic resin and an amorphous component, and the ratio of the content of the amorphous component to the content of the crystalline thermoplastic resin ((b):(a)) is preferably 5:5 to 2:8, more preferably 4:6 to 2.2:7.8, and even more preferably 3.5:6.5 to 2.4:7.6. By setting the ratio of the content of the amorphous component to the content of the crystalline thermoplastic resin ((b):(a)) to 5:5 or less, chemical resistance of the wetted parts can be ensured, and by setting the ratio to 2:8 or more, burrs can be suppressed and outgassing from the molded product can be suppressed.

[0057] -A nucleating agent for polyphenylene sulfide- The thermoplastic resin composition (B) described above may contain a polyphenylene sulfide crystal nucleating agent. By including a polyphenylene sulfide crystal nucleating agent in the thermoplastic resin composition (B), the gas barrier properties can be further improved when polyphenylene sulfide is used as the crystalline resin, and the dimensional accuracy of the thin-walled portion can also be improved. Furthermore, the nucleating agent for the polyphenylene sulfide mentioned above is a component other than the crystalline thermoplastic resin.

[0058] The nucleating agent for polyphenylene sulfide is not particularly limited as long as it is an additive that increases the rate of formation of polyphenylene sulfide nuclei, but examples include inorganic nucleating agents such as silica, kaolin, talc, Hytron, and boron nitride, organic carboxylic acid metal salts such as calcium stearate, aluminum stearate, dipotassium succinate, calcium benzoate, disodium phthalate, trisodium trimellitate, and tetrapotassium pyromellitate, and polymers with a higher melting point than polyphenylene sulfide such as polyphenylene sulfide ketone and nylon 46. Among these, inorganic nucleating agents are preferred, and talc is more preferred. More specifically, talc can be a plate-like crystal with an average particle size of 1 to 50 μm and mainly composed of hydrated magnesium silicate (SiO2: 58 to 64%, MgO: 28 to 32%, Al2O3: 0.5 to 5%, Fe2O3: 0.3 to 5%). The average particle size of the talc is more preferably 10 to 40 μm, and even more preferably 20 to 35 μm.

[0059] The nucleating agent for polyphenylene sulfide may be surface-treated with a silane coupling agent, a titanate coupling agent, or aliphatic metal salt; it may be organically treated with an ammonium salt or the like by intercalation; or it may be binder-treated with a resin such as urethane resin or epoxy resin.

[0060] -Emulsifying dispersant, phase solvent- The above thermoplastic resin composition (B) is preferably further enriched with an emulsifying dispersant or a phase solvent. Using an emulsifying dispersant is even more preferable from the viewpoint of finely dispersing the islands in the sea-island structure.

[0061] --Emulsifying and dispersing agent-- Examples of the emulsifying dispersants mentioned above include (1) epoxy resins, (2) silane coupling agents, and (3) copolymers containing epoxy groups and / or oxazolyl groups. Among these, copolymers of an unsaturated monomer having epoxy groups and / or oxazolyl groups and a monomer mainly composed of styrene are more preferably used. The emulsifying dispersant mentioned above is a component other than the crystalline thermoplastic resin mentioned above.

[0062] The monomers primarily composed of styrene, as used herein, are acceptable if they contain 100% by mass of styrene. However, if other monomers copolymerizable with styrene are present, it is preferable that they contain at least 65% by mass of styrene monomer, and more preferably 75-95% by mass. Specific examples of these include copolymers of unsaturated monomers having epoxy and / or oxazolyl groups with styrene monomer, and copolymers of unsaturated monomers having epoxy and / or oxazolyl groups with styrene / acrylonitrile = 90-75% by mass / 10-25% by mass.

[0063] Examples of epoxy group-containing unsaturated monomers include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, and glycidyl itaconate, with glycidyl methacrylate being the most preferred. Furthermore, as an oxazolyl group-containing unsaturated monomer, for example, 2-isopropenyl-2-oxazoline is industrially available and can be preferably used.

[0064] Other unsaturated monomers copolymerized with these unsaturated monomers having epoxy and / or oxazolyl groups include vinyl aromatic compounds such as styrene, which are essential components, as well as vinyl cyanide monomers such as acrylonitrile, vinyl acetate, (meth)acrylic acid esters, etc., as copolymerization components. However, it is preferable that the copolymerized component contains at least 65% by mass of styrene monomer, excluding the unsaturated monomers having epoxy and / or oxazolyl groups. Furthermore, the unsaturated monomers having epoxy and / or oxazolyl groups are contained in this copolymer at a concentration of 0.3 to 20% by mass, preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.

[0065] Examples of copolymers of emulsifying and dispersing agent components obtained by copolymerizing copolymerizable unsaturated monomers include, for example, styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene-glycidyl methacrylate-acrylonitrile copolymer, styrene-vinyl oxazoline copolymer, and styrene-vinyl oxazoline-acrylonitrile copolymer.

[0066] The amount of this emulsifying dispersant admixture added is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin composition (B).

[0067] --Phase Solvent-- Examples of the above-mentioned phase solvents include hydrogenated styrene-based thermoplastic elastomers, and known ones can be used.

[0068] ((polyamide)) Examples of the polyamides mentioned above include crystalline aromatic polyamide resins and aliphatic polyamides.

[0069] -Crystalline aromatic polyamide resin- The above-mentioned crystalline aromatic polyamide resin refers to a polyamide that is crystalline and contains an aromatic ring in its molecule. A polyamide with "crystalline properties" refers to a polyamide whose heat of fusion (ΔH) is 1 J / g or more, measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121, at a heating rate of 10°C / min. Furthermore, polyamide resins containing aromatic rings in their molecules include polyamide resins obtained by condensing diamines and dicarboxylic acids, as well as copolymers of diamines and dicarboxylic acids with lactams or ω-aminocarboxylic acids, in which at least one of the diamines and dicarboxylic acids is aromatic.

[0070] In monomeric diamines and dicarboxylic acids, if either an aromatic diamine or an aromatic dicarboxylic acid is used, the other does not need to contain aromatic compounds. The above crystalline aromatic polyamide resin may also be a copolymerized polyamide. In that case, if a unit using either an aromatic diamine or an aromatic dicarboxylic acid is included, the other polyamide does not need to contain aromatic diamines or aromatic dicarboxylic acids. In addition to diamines and dicarboxylic acids, ω-aminocarboxylic acids, lactams, etc., may also be included. Among these, it is preferable from the viewpoint of improving appearance that the crystalline aromatic polyamide resin contains aromatic dicarboxylic acids as part of its constituent units.

[0071] Examples of aromatic diamines used as raw material monomers in crystalline aromatic polyamide resins include, but are not limited to, p-xylylenediamine and m-xylylenediamine. Examples of aromatic dicarboxylic acids used as raw material monomers in crystalline aromatic polyamide resins include, but are not limited to, isophthalic acid and terephthalic acid.

[0072] Examples of non-aromatic diamines used as raw material monomers in crystalline aromatic polyamide resins include linear diamines, branched diamines, and alicyclic diamines. Examples, though not limited to those listed below, include hexamethylenediamine, pentamethylenediamine, tetramethylenediamine, 2-methylpentadiamine, 2-ethylhexadiamine, cyclohexanediamine, cyclopentadiamine, and cyclooctadiamine.

[0073] Examples of dicarboxylic acids that do not contain aromatic compounds as raw material monomers include aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. Examples, though not limited to those listed below, include adipic acid, pimelic acid, sebacic acid, dodecanedioic acid, and cyclohexanedicarboxylic acid.

[0074] Furthermore, examples of ω-aminocarboxylic acids and lactams as raw material monomers include, but are not limited to, ε-caprolactam, enanthlactam, capryllactam, lauryllactam, 1,4-aminobutanoic acid, 1,6-aminohexanoic acid, 1,7-aminoheptanoic acid, 1,8-aminooctanoic acid, 1,11-aminoundecanoic acid, and 1,12-aminododecanoic acid.

[0075] The proportion of aromatic dicarboxylic acids and diamines is preferably 5 to 100% by mass relative to 100% by mass of the total monomers constituting the crystalline aromatic polyamide resin. From the viewpoint of appearance, 5% by mass or more is preferred.

[0076] Crystalline aromatic polyamide resins are not limited to the following, but include, for example, polyamide 6T (polyhexamethylene terephthalamide), polyamide 9T (polynonane methylene terephthalamide), polyamide MXD6 (poly m-xylylene adipamide), polymeta-xylylene dodecamide, polyamide 66 / 6I (polyhexamethylene adipamide / polyhexamethylene isophthalamide), polyamide 66 / 6I / 6 (polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide), polyamide 6 / 6I, and polyamide 6 Examples of aromatic polyamide resins include 6 / 6T, polyamide 66 / 6T / 6, polyamide 6 / 6T, polyamide 66 / 6I / 6T, polyamide 66 / 6I / 6T / 6, polyamide 6 / 6I / 6T, polyamide 610 / 6I (polyhexamethylene sevacamide / polyhexamethylene isophthalamide), polyamide 610 / 6I / 6, polyamide 610 / 6T, polyamide 610 / 6T / 6, polyamide 610 / 6I / 6T, polyamide 610 / 6I / 6T / 6, and polycondensates of terephthalic acid and / or isophthalic acid with adipic acid and metaxylylenediamine.

[0077] Among those listed above, polyamide resins containing isophthalic acid as a constituent unit as a raw material monomer are preferred from the viewpoint of improving appearance. Preferred polyamide resins possessing such properties include polyamide 66 / 6I, polyamide 66 / 6I / 6, polyamide 6 / 6I, polyamide 66 / 6I / 6T, polyamide 66 / 6I / 6T / 6, polyamide 6 / 6I / 6T, polyamide 610 / 6I, polyamide 610 / 6I / 6, polyamide 610 / 6T, polyamide 610 / 6T / 6, polyamide 610 / 6I / 6T, and polyamide Examples include 610 / 6I / 6T / 6, more preferably polyamide 66 / 6I, polyamide 66 / 6I / 6, polyamide 6 / 6I, polyamide 66 / 6I / 6T, polyamide 66 / 6I / 6T / 6, polyamide 6 / 6I / 6T, polyamide 6T / 6I, and even more preferably PA66 / 6I, PA66 / 6I / 6, PA66 / 6I / 6T, and PA66 / 6I / 6T / 6. The crystalline aromatic polyamide resins described above may be used individually or in combination of two or more types.

[0078] --Aliphatic polyamide-- Next, we will describe aliphatic polyamide resins obtained by condensing diamines and dicarboxylic acids. Examples of monomeric diamines include, but are not limited to, linear diamines, branched diamines, and alicyclic diamines. Examples include, but are not limited to, hexamethylenediamine, pentamethylenediamine, tetramethylenediamine, 2-methylpentadiamine, 2-ethylhexadiamine, cyclohexanediamine, cyclopentadiamine, and cyclooctadiamine.

[0079] Examples of monomeric dicarboxylic acids include, but are not limited to, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. Examples include, but are not limited to, adipic acid, pimelic acid, sebacic acid, dodecanedioic acid, and cyclohexanedicarboxylic acid.

[0080] The above monomers may be selected from one or more of the lactams, ω-aminocarboxylic acids, non-aromatic diamines, and non-aromatic dicarboxylic acids mentioned above, and used in combination.

[0081] Examples of aliphatic polyamides include, but are not limited to, polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), polyamide 12 (polydodecaneamide), polyamide 66 (polyhexamethylene adipamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 610 (polyhexamethylene sevacamide), polyamide 612 (polyhexamethylene dodecamide), and copolymer polyamides containing these as constituent components.

[0082] Among the aliphatic polyamides listed above, polyamide 66 (polyhexamethylene adipamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 610 (polyhexamethylene sevacamide), polyamide 612 (polyhexamethylene dodecamide), and copolymer polyamides containing these as constituent components are more preferred, and from the viewpoint of a high crystallization initiation temperature, polyamide 66 (polyhexamethylene adipamide), polyamide 46 (polytetramethylene adipamide), or polyamide 56 (polypentamethylene adipamide) are even more preferred. The aliphatic polyamides mentioned above may be used individually or in combination of two or more.

[0083] In the thermoplastic resin composition (B) described above, the mass percentage of crystalline aromatic polyamide resin in 100% by mass of polyamide is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 90% by mass or less, and even more preferably 50% by mass or more and 90% by mass or less. Furthermore, in the thermoplastic resin composition (B) described above, the mass percentage of aliphatic polyamide is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less. A crystalline aromatic polyamide resin of 30% by mass or more provides high appearance, and a crystalline aromatic polyamide resin of 95% by mass or less provides excellent tensile strength and processing stability. A crystalline aromatic polyamide resin of 5% by mass or more provides excellent tensile strength and processing stability, and a crystalline aromatic polyamide resin of 70% by mass or less provides high appearance.

[0084] The aromatic monomer ratio in the above polyamide, that is, the mass percentage of monomers having an aromatic structure as a constituent unit relative to 100% by mass of all monomers constituting the above polyamide, is preferably 5 to 21% by mass. More preferably 8.5 to 21% by mass, even more preferably 8.5 to 18% by mass, and even more preferably 8.5 to 15% by mass. Setting it to 5% by mass or more suppresses the exposure of glass fibers on the surface of the molded product, making it easier to obtain an excellent appearance as a polyamide resin composition molded product, while setting it to 21% by mass or less suppresses a decrease in crystallinity as a polyamide resin composition, and exhibits high mechanical properties. The method for calculating the aromatic monomer ratio in polyamide is not particularly limited, but it can be determined by methods such as nuclear magnetic resonance (NMR).

[0085] In addition to crystalline aromatic polyamide resins and aliphatic polyamides, the above-mentioned polyamides may be blended with other polyamides, to the extent that they do not impair the objectives of the present invention. Examples of other polyamides include aliphatic polyamides whose extrapolation onset temperature (Tic) is below that of crystalline aromatic polyamide resins.

[0086] Various polycondensation methods can be used to produce the above-mentioned polyamide, such as melt polymerization, solid-phase polymerization, bulk polymerization, solution polymerization, or combinations thereof, using adipic acid, isophthalic acid, and a salt of hexamethylenediamine. It can also be obtained from adipic acid chloride, isophthalic acid chloride, and hexamethylenediamine by methods such as solution polymerization and interfacial polymerization. Among these, melt polymerization or a combination of melt polymerization and solid-phase polymerization is preferred from an economic standpoint.

[0087] The above polyamide is preferably 10 to 45 Pa·s in viscosity of formic acid solution at 25°C ((5.5g polyamide) / (50mL 90% formic acid)) as measured in accordance with Annex JA of JIS-K6920-2. More preferably 15 to 35 Pa·s, even more preferably 25 to 35 Pa·s, and even more preferably 25 to 33 Pa·s. A formic acid solution viscosity of 10 Pa·s or higher suppresses embrittlement of the resin composition, resulting in molded articles with sufficient mechanical properties for practical use, and also reduces the likelihood of drawing from the nozzle tip of the cylinder during molding. A formic acid solution viscosity of 45 Pa·s or lower prevents the melt viscosity of the resin from becoming too high, suppresses partial lifting of inorganic fillers during molding, and maintains surface gloss.

[0088] The mass ratio of polyamide to 100% by mass of the above thermoplastic resin composition (B) is preferably 30% by mass or more and less than 50% by mass, more preferably 30 to 45% by mass, and even more preferably 35 to 45% by mass. By setting it to 30% by mass or more, the fluidity of the resin can be maintained, the resin can be filled even into thin-walled sections, and molded products with good surface gloss can be obtained. Furthermore, by setting it to less than 50% by mass, strength and rigidity can be ensured as an exterior material that can replace metal.

[0089] ((crystallization retarder)) The above thermoplastic resin composition (B) may further contain a crystallization retarder from the viewpoint of further improving the appearance and mechanical strength of the molded product. A crystallization retarder is a substance that, when blended with a polyamide, has the effect of lowering the crystallization initiation point of the polyamide. Examples of crystallization retarders are not particularly limited, but include azine dyes, phthalocyanine dyes, and lithium chloride. Among these, azine dyes or phthalocyanine dyes are preferred. Nigrosine is preferred as an azine dye, and copper phthalocyanine dyes are preferred as phthalocyanine dyes.

[0090] The content of the crystallization retarder is preferably 0.005 to 0.1 parts by mass, more preferably 0.005 to 0.04 parts by mass, and even more preferably 0.01 to 0.02 parts by mass, per 100 parts by mass of the thermoplastic resin composition (B). By setting the content of the crystallization retarder to 0.1 parts by mass or less, a polyamide resin composition with excellent appearance can be obtained, and by setting it to 0.005 parts by mass or more, a polyamide resin composition with excellent mechanical strength can be obtained.

[0091] The thermoplastic resin composition (B) described above preferably contains both a nucleating agent and a crystallization retarder from the viewpoint of improving the balance between appearance and strength. When used in combination, the mass ratio of the crystallization retarder to the nucleating agent contained in the thermoplastic resin composition (B) is preferably in the range of 0.05 to 1.0, and more preferably in the range of 0.25 to 0.5. From the viewpoint of improving the appearance of the molded product, a ratio of 0.05 or higher is preferred, and from the viewpoint of improving strength, a ratio of 1.0 or lower is preferred.

[0092] ((Lubricant)) A lubricant may be added to the above thermoplastic resin composition (B) from the viewpoint of further improving the appearance of the molded product. The lubricant is not limited to the following, but examples include one or more fatty acid compounds selected from fatty acid esters, fatty acid amides, and fatty acid metal salts. Lubricants may be used individually or in combination of two or more types.

[0093] The fatty acids that make up the fatty acid compounds are aliphatic monocarboxylic acids. Fatty acids with 8 or more carbon atoms are particularly preferred. More preferably, fatty acids with 8 to 40 carbon atoms are preferred. Examples of fatty acids, though not limited to those listed below, include saturated or unsaturated, linear or branched, aliphatic monocarboxylic acids. More specifically, although not limited to those listed below, examples include stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, montanic acid, etc.

[0094] Fatty acid esters are ester compounds formed by the interaction of fatty acids with alcohols. Examples of alcohols include, but are not limited to, 1,3-butanediol, trimethylolpropane, stearyl alcohol, behenyl alcohol, and lauryl alcohol. Examples of fatty acid esters include, but are not limited to, stearyl stearate, behenyl behenate, 1,3-butanediol montanate, trimethylolpropane montanate, trimethylolpropane trilaurate, and butyl stearate.

[0095] Fatty acid amides are amidated compounds of fatty acids. Examples of fatty acid amides include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylenebisstearyl amide, ethylenebisoleyl amide, N-stearylstearyl amide, and N-stearyleruka amide. In particular, stearic acid amide, erucic acid amide, ethylenebisstearyl amide, and N-stearyleruka amide are preferred, and ethylenebisstearyl amide and N-stearyleruka amide are more preferred.

[0096] Fatty acid metal salts are the metal salts of the fatty acids mentioned above. Examples of metallic elements that form salts with fatty acids include Group 1 elements (alkali metals), Group 2 elements (alkaline earth metals), Group 3 elements of the periodic table, zinc, and aluminum. Preferred metallic elements include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and aluminum.

[0097] The lubricant content is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and even more preferably 0.05 to 2 parts by mass, per 100 parts by mass of thermoplastic resin composition (B). By keeping the lubricant content within this range, a polyamide resin composition with even better appearance, release properties, mechanical strength, and plasticity can be obtained.

[0098] (Additives) Thermoplastic resin composition (the above thermoplastic resin compositions (A) and (B)) To the extent necessary and without impairing the objectives of the present invention, additives other than glass fibers, copper compounds, antioxidants, ultraviolet absorbers, heat stabilizers, photodegradation inhibitors, plasticizers, mold release agents, flame retardants, etc., which are normally added to crystalline thermoplastic resins such as polyamide resins, may be added as necessary.

[0099] -Colorants- To make the interface and welding marks between molded body 1 and molded body 2 less noticeable, a coloring agent may be added to the thermoplastic resin composition (B). The coloring agent may be a laser light-transmitting dye. This allows the molded body 2 to be made a single shade of black, for example. By adding an appropriate coloring agent according to the hue and color density of the thermoplastic resin contained in the thermoplastic resin composition (B), a molded body 2 exhibiting a homogeneous black color can be obtained. Such black coloring agents can be obtained, for example, by a combination of a blue coloring agent, a red coloring agent, and a yellow coloring agent, a combination of a purple coloring agent and a yellow coloring agent, or a combination of a green coloring agent and a red coloring agent.

[0100] Examples of colorants to be added to thermoplastic resin composition (B) include combinations of dyes that absorb in the visible region, have high compatibility with thermoplastic resins, and have low scattering characteristics with respect to laser light. Furthermore, a colorant that is resistant to fading even when exposed to high temperatures during molding of the molded body 2 or during melting by laser irradiation, has excellent heat resistance, and does not absorb in the near-infrared region of laser light is preferred. Specifically, a colorant containing at least an anthraquinone dye that is transparent to the laser light used in laser welding is preferred.

[0101] Such anthraquinone dyes are preferably anthraquinone-based oil-soluble dyes, specifically, for example, CISolvent Blue 11, 12, 13, 14, 26, 35, 36, 44, 45, 48, 49, 58, 59, 63, 68, 69, 70, 78, 79, 83, 87, 90, 94, 97, 98, 101, 102, 104, 105, 122, 129, and 132; CDisperse Blue 14, 35, 102, and 197; CISolvent Green 3, 19, 20, 23, 24, 25, 26, 28, 33, and 65; CISolvent Violet Examples of commercially available dyes include those with color indexes of 13, 14, 15, 26, 30, 31, 33, 34, 36, 37, 38, 40, 41, 42, 45, 47, 48, 51, 59, and 60.

[0102] Examples of anthraquinone dyes include those with a maximum absorption wavelength in the range of 590 to 635 nm. Such anthraquinone dyes often exhibit a blue color and have higher visibility compared to, for example, green anthraquinone dyes. When combining with black mixed dyes, a highly coloring agent with strong coloring power can be obtained by subtractive color mixing, such as combining a blue anthraquinone dye with a red or yellow dye.

[0103] Furthermore, it is preferable that the anthraquinone dye has a 940nm laser light transmittance of 60-95%. Examples of commercially available anthraquinone dyes include the "NUBIAN® BLUE series" and the "OPLAS® BLUE series" (both product names, manufactured by Orient Chemical Industry Co., Ltd.).

[0104] --Carbon Black-- The above coloring agent is preferably a black coloring agent. The above black coloring agent may contain carbon black, or may consist of carbon black alone.

[0105] --Negrosin-- The above-mentioned black coloring agent may contain nigrosine, or it may contain nigrosine alone. Examples of colorants included in thermoplastic resin composition (B) include nigrosine and its derivatives, aniline black, phthalocyanine, naphthalocyanine, porphyrin, cyanine compounds, perylene, quaterylene, azo metal complexes, near-infrared absorbing anthraquinones, squamic acid derivatives, and immonium dyes. Among these, nigrosine and its derivatives are preferred.

[0106] The absorption coefficient εd (ml / g·cm) of the above coloring agent is preferably 1000 to 8000 (ml / g·cm), more preferably 1000 to 6000 (ml / g·cm), and even more preferably 3000 to 6000 (ml / g·cm). The method for measuring the absorption coefficient (extinction coefficient) εd involves accurately weighing 0.05 g of colorant, dissolving it in a 50 ml volumetric flask, for example in N,N-dimethylformamide (DMF), then diluting 1 ml of this solution with DMF in a 50 ml volumetric flask to prepare the measurement sample. The absorbance is then measured using a spectrophotometer (Shimadzu Corporation, product name: UV1600PC).

[0107] Nigrosine is preferably in the form of a sulfate. Nigrosine sulfate acts as a fluidity enhancer, surface gloss enhancer, and crystallization temperature lowering agent, thereby improving the fluidity of the resin composition during laser welding.

[0108] In the nigrosine production reaction system using iron chloride as a catalyst, the reaction takes place in the presence of iron chloride and excess hydrochloric acid, resulting in the production of nigrosine hydrochloride. To obtain nigrosine sulfate from nigrosine hydrochloride, any known reaction method can be used, as long as all or a substantial portion of the chloride ions constituting the salt in nigrosine are replaced with sulfate ions. Note that nigrosine sulfate is an oil-soluble black dye belonging to CISolvent Black 5, and not a water-soluble black dye belonging to CIAcid Black 2.

[0109] Nigrosine sulfate can be produced by, for example, dispersing nigrosine in dilute sulfuric acid and heating it to a moderate temperature (e.g., 50-90°C). Alternatively, it can be produced by dispersing the condensation reaction solution obtained from producing nigrosine in dilute sulfuric acid and heating it to a moderate temperature (e.g., 50-90°C). It can also be produced by dissolving nigrosine in concentrated sulfuric acid while adjusting the reaction solution temperature to a low temperature to prevent sulfonation, and then adding the solution to a large amount of ice water to precipitate crystals.

[0110] In nigrosine sulfate, a sulfate (ion) concentration of 0.3 to 5% by mass, preferably 0.5 to 3.5% by mass, significantly reduces the crystal temperature of the thermoplastic resin, allowing for simple and stable laser welding.

[0111] As an example of nigrosine, the NUBIAN BLACK series, manufactured by Orient Chemical Industries Co., Ltd., is commercially available.

[0112] Furthermore, the content of a coloring agent such as nigrosine, which adjusts the absorbance, is preferably 0.01 to 0.5% by mass in the thermoplastic resin composition (B) relative to 100% by mass of the crystalline thermoplastic resin. Specifically, when the crystalline thermoplastic resin contained in the thermoplastic resin composition (B) is a polyamide resin, a polycarbonate resin, or a polypropylene resin, the content of the coloring agent is preferably 0.001 to 0.5% by mass, and more preferably 0.002 to 0.2% by mass. Also, when this crystalline thermoplastic resin is a polybutylene terephthalate resin or a polyphenylene sulfide resin, the content of the coloring agent is preferably 0.001 to 0.2% by mass. If the content is below this lower limit, the amount of heat generated by the molded body that absorbs the energy of the laser light is insufficient, so they do not heat up sufficiently, and the bonding strength at the contact points is insufficient. Furthermore, if the content exceeds 0.3% by mass, the transmittance of the laser light decreases excessively, leading to a decrease in the welding strength between molded body 1 and molded body 2, and welding defects such as welding marks and charring due to excess energy.

[0113] Furthermore, nigrosine imparts a high gloss to the surface of resin components and acts as a crystallization temperature lowering agent, a flowability improver, and a surface gloss improver for thermoplastic resins.

[0114] The absorbance of thermoplastic resin composition (B), which is 0.2 to 3.8 (for example, in the wavelength range of a semiconductor laser of 940 nm), is lower than that of known laser light-absorbing resin components. Because the absorbance is within this range, the molded body 2 does not generate rapid and excessive heat due to laser light transmitted through the molded body 1. This absorbance is obtained by adjusting the content of the colorant based on the absorbance inherent in the crystalline thermoplastic resin contained in the raw material resin. Specifically, the content is preferably 0.03 to 2% by mass, and more preferably 0.04 to 0.8% by mass, based on 100% by mass of thermoplastic resin composition (B).

[0115] -Inorganic fillers- The inorganic filler is not particularly limited, but for example, at least one selected from the group consisting of glass fibers, carbon fibers, carbon nanotubes, cellulose fibers, silicon carbide fibers, ceramic fibers, aramid fibers, alumina fibers, gypsum fibers, metal fibers, calcium titanate whiskers, calcium carbonate whiskers, and wollastonite can be used. These fibrous inorganic fillers may be further treated with surface treatment agents such as silane-based coupling agents, titanate-based coupling agents, and aliphatic metal salts, or treated with resins such as urethane resins and epoxy resins as binders. Among these, glass fibers are preferred from the viewpoint of heat resistance and adhesion to resins.

[0116] --Glass Fiber-- The glass fibers used above are typically those used in crystalline thermoplastic resins, and there are no particular restrictions on fiber diameter or length. For example, chopped strands, rovings, or milled fibers with a diameter of 5 to 25 μm may be used. Chopped strands are preferred from the viewpoint of strength, rigidity, and dispersibility in the composition. When using chopped strands, their length can be appropriately selected and used within the range of 0.1 to 6 mm.

[0117] Glass fibers may be used with a commonly known silane-based coupling agent attached to their surface. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane can be used.

[0118] Glass fibers may be those to which a commonly known sizing agent has been attached. Examples include copolymers containing carboxylic acid anhydride-containing unsaturated vinyl monomers and unsaturated vinyl monomers excluding carboxylic acid anhydride-containing unsaturated vinyl monomers as constituent units, epoxy compounds, polycarbodiimide compounds, polyurethane resins, acrylic acid homopolymers, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, or tertiary amines. These may be used individually or in combination of two or more. Here, the average length of the inorganic filler can be determined as follows. First, the molded body can be incinerated, for example, in an electric furnace, and the inorganic filler can be collected from the residue (ash). Furthermore, the method for measuring the average length of the inorganic filler is not particularly limited as long as an image processing device can observe the inorganic filler with a microscope and binarize the obtained image. The average length of the inorganic filler can be obtained by arithmetic mean of the obtained major axis and minor axis values ​​over any 300 inorganic fillers.

[0119] The mass ratio of the inorganic filler in the resin composition is not particularly limited, but is preferably 0.1 to 60 parts by mass, more preferably 10 to 60 parts by mass, even more preferably 15 to 40 parts by mass, and most preferably 20 to 40 parts by mass per 100 parts by mass of the resin composition. By setting the content to 0.1 parts by mass or more, the mechanical strength can be further improved, and by setting the content to 60 parts by mass or less, higher gas barrier properties can be ensured.

[0120] -Flame retardant- The above thermoplastic resin composition may contain a flame retardant. To improve flame retardancy, a flame retardant commonly added to thermoplastic resins can be used, but it is preferable to add a halogen-free organophosphorus flame retardant. The organophosphorus flame retardant may be used alone or in combination of two or more types.

[0121] Examples of organophosphorus-based flame retardants include phosphate ester compounds and phosphazene compounds. Phosphate ester compounds are added to improve flame retardancy, and any organophosphorus ester commonly used as a flame retardant can be used.

[0122] Specific examples of phosphate ester compounds include, but are not limited to, triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bis[di(2,6-dimethylphenyl) phosphate], 2,2-bis{4-[bis(phenoxy)phosphoryloxy]phenyl}propane, and 2,2-bis{4-[bis(methylphenoxy)phosphoryloxy]phenyl}propane. In addition to the above, phosphorus-based flame retardants include, for example, phosphate ester flame retardants such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, and diisopropylphenyl phosphate, as well as diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphate, and diphenyl-4-hydroxy-3,5-dibromobenzyl phosphate. Examples include zyl phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl) phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate, and monophosphate ester compounds such as bis(chloropropyl) monooctyl phosphate hydroquinonyldiphenyl phosphate, phenylnonylphenyl hydroquinonyl phosphate, and phenyldinonylphenyl phosphate, as well as aromatic condensed phosphate ester compounds. Among these, aromatic condensed phosphate ester compounds are preferred because they generate less gas during processing and have excellent thermal stability.

[0123] Preferred flame retardants are phosphate ester compounds (condensed phosphate esters) represented by the following general formula (I) or general formula (II). Particularly preferred are phosphate ester compounds (condensed phosphate esters) represented by the following general formula (I). [ka] [ka] (In general formulas (I) and (II), Q1, Q2, Q3, and Q4 are substituents, each independently representing an alkyl group having 1 to 6 carbon atoms; R11 and R12 each represent a methyl group; R13 and R14 each independently represent a hydrogen atom or a methyl group; n is an integer of 1 or more; n1 and n2 each independently represent an integer from 0 to 2; and m1, m2, m3, and m4 each independently represent an integer from 0 to 3.)

[0124] In the condensed phosphate esters represented by the above general formulas (I) and (II), n is an integer of 1 or more, preferably an integer from 1 to 3, in each molecule.

[0125] In the condensed phosphate esters represented by the above general formulas (I) and (II), preferred condensed phosphate esters are those in which m1, m2, m3, m4, n1, and n2 in formula (I) are zero and R13 and R14 are methyl groups, or those in which Q1, Q2, Q3, Q4, R13, and R14 in formula (I) are methyl groups, n1 and n2 are zero and m1, m2, m3, and m4 are integers from 1 to 3, and it is preferable that the condensed phosphate ester contains 50% by mass or more of a phosphate ester in which the range of n is an integer from 1 to 3, particularly n is 1.

[0126] These aromatic condensed phosphate ester compounds are generally available on the market, and examples include CR741, CR733S, and PX200 from Daihachi Chemical Industry Co., Ltd., and FP600, FP700, and FP800 from ADEKA Corporation.

[0127] Of these aromatic condensed phosphate ester compounds, those with an acid value of 0.1 or less (a value obtained in accordance with JIS K2501) are particularly preferred from the viewpoint of thermal stability.

[0128] Furthermore, as the phosphazene compound, phenoxyphosphazene and its crosslinked form are preferred, and particularly preferred are phenoxyphosphazene compounds having an acid value of 0.1 or less (a value obtained in accordance with JIS K2501) from the viewpoint of thermal stability.

[0129] The amount of flame retardant varies depending on the required level of flame retardancy, but is preferably in the range of 1 to 30 parts by mass, and more preferably in the range of 5 to 25 parts by mass, per 100 parts by mass of the thermoplastic resin composition. When the amount of flame retardant is 1 part by mass or more, the fluidity and flame retardancy of the resin composition are improved; when it is 30 parts by mass or less, the flame retardancy of the resin composition is sufficient; and when it is 30 parts by mass or less, the balance between fluidity, release properties, and burr suppression is improved.

[0130] -Other additives- In addition to the various materials mentioned above, the thermoplastic resin composition may also contain, as needed, various additives commonly added to thermoplastic resins, such as heat stabilizers, antioxidants, UV absorbers, other stabilizers, conductivity imparters, antistatic agents, and mold release agents.

[0131] [Method for producing thermoplastic resin compositions] The above thermoplastic resin composition can be processed using various melt kneaders and kneading extruders. Known kneaders can be used as melt kneaders and kneading extruders, including, for example, single-screw extruders, twin-screw extruders, and other multi-screw extruders; and heated melt kneaders such as rolls, kneaders, Brabender plastographs, and Banbury mixers. Among these, twin-screw extruders are preferred. A preferred method involves melt-kneading the components described above using a twin-screw extruder set to 280°C or higher, which has at least two vents and at least one side supply port. One more preferred method for manufacturing a resin composition using a twin-screw extruder involves simultaneously supplying resin components to the first supply port of the twin-screw extruder and melting and kneading them. With the basic resin composition composed of these components melted and kneaded, the first vent port of the twin-screw extruder is then vacuum-degassed to an absolute vacuum pressure of 95 kPa or less. Subsequently, if an optional additive (e.g., a flame retardant) is in liquid form, the additive is supplied by a liquid addition pump. The optional component is then supplied from the side 1 supply port of the twin-screw extruder located downstream, and an inorganic filler is supplied from the further downstream side 2 supply port. Each component is melted and kneaded, and finally, the second vent port of the twin-screw extruder is vacuum-degassed to an absolute vacuum pressure of 95 kPa or less.

[0132] <Molding conditions> When molding thermoplastic resin compositions, it is generally preferable to set the resin temperature to be above the melting point of the crystalline resin and the mold temperature to be below the glass transition temperature of the crystalline resin, and this is appropriately adjusted depending on the structure of the mold and injection molding machine.

[0133] Taking PPS / PPE as an example, in the generally known molding conditions for PPS / PPE, the resin temperature is set to 320°C or higher and the mold temperature to 60°C or lower in order to ensure fluidity during injection molding while suppressing the generation of burrs. However, in this embodiment, it is preferable to set the resin temperature to 280-320°C and the mold temperature to 120-160°C, and more preferably the resin temperature to 290-310°C and the mold temperature to 135-145°C. A resin temperature of 280°C or higher tends to ensure fluidity and prevent molding defects such as short shots and insufficient filling, while a temperature of 320°C or lower tends to appropriately control fluidity and prevent burrs that cause resin to leak out from the parting line.

[0134] Taking PA66 / amorphous PA as an example, in the generally known molding conditions for PA66 / amorphous PA, the resin temperature is set to 320°C or higher and the mold temperature to 60°C or lower in order to ensure fluidity during injection molding while suppressing the generation of burrs. However, in this embodiment, it is preferable to set the resin temperature to 280-320°C and the mold temperature to 120-160°C, and more preferably the resin temperature to 290-310°C and the mold temperature to 135-145°C. A resin temperature of 280°C or higher tends to ensure fluidity and prevent molding defects such as short shots and insufficient filling, while a temperature of 320°C or lower tends to appropriately control fluidity and prevent burrs that cause resin to leak out from the parting line.

[0135] Regarding mold temperature, temperatures higher than the glass transition temperature tend to result in good mold transfer and a desired level of gloss. Conversely, keeping the mold temperature below 160°C allows for sufficient cooling of the crystalline resin, preventing the resin from sticking to the mold during mold opening and thus preventing poor release and surface defects such as fuzziness on the molded product.

[0136] -Structure of the joint- The shape of the joint in this embodiment is not limited as long as it is achieved by laser welding from at least one molded body 1 and one molded body 2, but it is preferable that at least a part of the joint has a smooth surface or a fitting structure. Here, the term "joint" refers to any area formed by the fusion and bonding of two or more parts; its shape is not particularly limited and can be any shape, such as a circle, ellipse, or polygon. Furthermore, the joint is not limited to a smooth, flat surface; it may also have a structure in which two or more parts fit together to increase the joint strength. For the molded body 1 used as a laser-transmitting material to increase bonding strength, its thickness is preferably 5 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less.

[0137] In this embodiment, the parts of the joint other than the joint are not particularly limited and can be formed from any material such as resin or metal. Furthermore, the entire molded body can be formed from the same resin composition as the joint.

[0138] [Method for manufacturing a jointed body] The molded articles constituting the joint of this embodiment can be molded using the above-mentioned resin composition by conventionally known methods, such as injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, film molding, hot press molding, rotational molding, and lamination molding. The joint of this embodiment is manufactured using the above-mentioned molded articles by conventionally known methods, such as laser welding, ultraviolet welding, vibration welding, heat welding, and adhesive application.

[0139] [Applications of joints] The joint of this embodiment is not particularly limited, but can be, for example, a container and lid composed of two or more parts that require different properties such as mechanical strength and flame retardancy. It can be a container for storing or transporting chemicals, solutions, or solids, such as battery cases, while keeping them isolated from the external environment. The joint is not limited in any way to the combination of container and lid, and can be used to improve strength, design, or other design aspects. The joint of this embodiment is preferably a sealed battery case used in a mobile drive source. Furthermore, the joint of this embodiment is preferably an insulating component for a solar cell module.

[0140] When the joint of this embodiment is used for the above-mentioned applications, the wetted portion can be used as a member for partitioning (dividing) the space inside a container in which a liquid or solid exists or is filled, or as a lid and outer wall component for partitioning (dividing) the space inside the connecting member in which the liquid or solid exists or is filled, among the components that constitute a connecting member connecting such a container and equipment for using the liquid or solid. Furthermore, the partition portion is not limited in any way to a combination of a container and a lid, and the joint can also be used to improve design, including strength and aesthetics.

[0141] The assembled body of this embodiment can be suitably used as a protective housing member for battery units used in automobiles and industrial applications, as a battery case (container) for secondary batteries such as lithium metal batteries, lithium-ion batteries, polymer-ion batteries, nickel-metal hydride batteries, lead-acid batteries, and nickel-cadmium batteries, and as a container for storing or transporting liquids in secondary battery cases, where it is suitably used as a sheet or film material constituting secondary batteries. [Examples]

[0142] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples. Examples 4, 8, and 9 are provided for reference only.

[0143] First, the evaluation methods for the test specimens of the examples and comparative examples, and the components used to manufacture the test specimens are shown.

[0144] [Crystalline thermoplastic resin] (a-1): Linear PPS PPS DSP LR-1G (a-2): Cross-linked PPS PPS DSP K-2G (b-1): Polyamide 66 Leona 1300-301 (b-2): Semi-aromatic polyamide 6I (b-3): Polyamide 66, semi-aromatic polyamide copolymer (b-4): Polyamide 9T Genesta GC51010

[0145] [Amorphous components] (c-1) A polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol, with an intrinsic viscosity of 0.33 measured in chloroform at 30°C. (c-2) A polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol, with an intrinsic viscosity of 0.46 measured in chloroform at 30°C. (c-3): A mixture of rubber-reinforced polystyrene (manufactured by Petrochemical Co., Ltd., trade name "CT60") and homopolystyrene (manufactured by PS Japan Co., Ltd., trade name "PSJ-Polystyrene 685") in a mass ratio of 1:1.4.

[0146] [d. Emulsifying dispersant] For compositions using PPS as the base material for crystalline resin, styrene-glycidyl methacrylate (d-1) was used.

[0147] [e. Coloring agents] (e-1) Laser-transmitting colorant: LTW dye masterbatch manufactured by Orient Chemical Industries, Ltd.: A dye that transmits laser light with a wavelength of 800 nm or more. (e-2) Laser-absorbing coloring agent: Nigrosine, manufactured by Orient Chemical Industries Co., Ltd., NUBIAN® BLACK PA9801: a black coloring agent. (e-3) Laser-absorbing coloring agent: Carbon black W26 / 679 / Mitsubishi CB#960B: This is a black coloring agent.

[0148] [f Inorganic fillers] (f-1) Glass fiber, manufactured by Nippon Electric Glass Co., Ltd., E Glass Fiber, Chopped Strand T-249 (f-2) Glass fiber / mica weight ratio 1:1 mixture. Nippon Electric Glass Co., Ltd. E Glass Fiber Chopped Strand T-249 and Suzolite Mica 200HK

[0149] [g Flame retardant] (g-1) Phosphorus-based flame retardant, manufactured by ADEKA Corporation, ADEKA Stab FP600(A) (g-2) Exolit OP1230

[0150] [evaluation] (1) Preparation of test specimens for evaluation The obtained thermoplastic resin composition pellets were supplied to a screw-in-line injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name "EC75SXII injection molding machine") set to 240°C to 330°C. Rectangular parallelepiped test pieces (molded body 1 and molded body 2) measuring 20 mm wide x 60 mm long x 2 mm thick were injection molded with the cylinder temperature and mold temperature set to the conditions listed in Table 1. During the production of the molded products, the injection speed was 50 mm / sec, and a surface-treated mold containing titanium nitride was used.

[0151] (2) Measurement of laser transmittance The obtained test specimens for measuring welding strength, measuring 20 mm in width, 60 mm in length, and 2 mm in thickness, were used to measure wavelength transmittance in the measurement range of 400 to 1100 nm using a spectrophotometer (manufactured by JASCO Corporation, product name "Spectrophotometer V-630"). The transmittance at 940 nm (transmitting laser transmittance) and the transmittance at 800 nm (absorbing laser transmittance) are shown in Table 1.

[0152] (3) Fabrication of the joint The obtained molded body 1 and molded body 2 were placed facing each other with surfaces measuring 20 mm in width and 60 mm in length, and overlapped so that portions measuring 20 mm in width and 2.5 cm in length were in contact with each other. A 940 nm laser was then irradiated under the conditions shown in Table 1 to create a joined body.

[0153] (4) Welding strength The welding strength (MPa) of the obtained joints was measured by clamping both ends of the joint in a chuck with a support distance of 55 mm and fixing it, then using an INSTRON tensile testing machine along the longitudinal direction of the joint at a tensile speed of 5 mm / sec. The point at which the test specimen fractured or yielding of the stress-strain curve was observed was determined as the welding strength (N). Discoloration and deformation of the test specimens were evaluated according to the following criteria. Comparative Examples 1-3 were marked with "-" because they did not weld. In all of these examples, the test specimen fractured at the interface between molded body 1 and molded body 2. (Criteria for evaluating welding tests) A (Excellent): Sufficient welding strength (welding strength of 650N or higher) is observed. B (Good): Welding between materials is observed (welding strength is between 400N and 650N) C (Defective): No welding was observed (welding strength was less than 50N, or molded body 1 and molded body 2 did not join).

[0154] (5) Presence or absence of discoloration The joint was fabricated in the same manner as in (3) above. The presence or absence of discoloration at the laser-irradiated joint was visually checked and evaluated according to the following criteria. Good: No discoloration at the joints. Defect: Discoloration at the joint.

[0155] (6) Presence or absence of deformation The joint was fabricated in the same manner as in (3) above. The presence or absence of deformation of the test specimen at the joint irradiated with the laser was visually checked and evaluated according to the following criteria. Good: No deformation at the joint. Defect: Deformed joint.

[0156] [Examples, Comparative Examples] (Preparation of thermoplastic resin composition pellets) According to the formulation shown in Table 1 below, each component was melt-kneaded using a twin-screw extruder ("ZSK-40", manufactured by WERNER & PFLEIDERE) set to a temperature of 290-320°C and a screw rotation speed of 500 rpm to obtain thermoplastic resin composition (A) pellets and thermoplastic resin composition (B) pellets. Then, a joint was fabricated using the method described above and evaluated. Table 1 below shows the evaluation results for the examples and comparative examples.

[0157] [Table 1] [Industrial applicability]

[0158] The above-described joint achieves welding without an adhesive layer, thereby suppressing the risk of dust contamination between processes and achieving welding of thermoplastic resins between dissimilar materials with minimal thermal deformation of components and high joint strength. This makes it particularly suitable for industrial applications in high-capacity storage batteries, especially alkaline storage batteries and other battery case applications.

Claims

1. Molded body 1 and molded body 2 are joined together. The molded body 1 is made of a thermoplastic resin composition (A), The thermoplastic resin composition (A) contains polyphenylene ether, and contains 50 to 78 parts by mass of the polyphenylene ether per 100 parts by mass of the thermoplastic resin composition (A). The molded body 2 is made of a thermoplastic resin composition (B), The thermoplastic resin composition (B) contains a crystalline thermoplastic resin, and the crystalline thermoplastic resin is contained in an amount of 20 to 90 parts by mass per 100 parts by mass of the thermoplastic resin composition (B). The thermoplastic resin composition (B) further comprises an amorphous component, The amorphous component is selected from the group consisting of polyphenylene ether and semi-aromatic polyamide. The molded body 1 and the molded body 2 are joined by welding at least a portion of the interface between the molded body 1 and the molded body 2. The laser transmittance of the molded body 1 at a wavelength of 940 nm is 20% or more. Characterized by, zygote.

2. The bonded body according to claim 1, wherein the thermoplastic resin composition (A) contains a dye that transmits laser light with a wavelength of 800 nm or more.

3. The joint according to claim 1 or 2, wherein the thermoplastic resin composition (B) comprises a black coloring agent.

4. The bonded body according to any one of claims 1 to 3, wherein the molded body 2 has a laser transmittance of 3% or less at a wavelength of 800 nm.

5. The joint according to any one of claims 1 to 4, wherein the thermoplastic resin composition (A) and / or the thermoplastic resin composition (B) contains 0.1 to 60 parts by mass of an inorganic filler per 100 parts by weight of the thermoplastic resin composition.

6. The joint according to any one of claims 1 to 5, wherein the thermoplastic resin composition (B) contains 20 parts by mass or more of at least one selected from the group consisting of polyamide and polyphenylene sulfide, per 100 parts by mass of the thermoplastic resin composition (B).

7. The joint according to any one of claims 1 to 6, wherein the type of thermoplastic resin most abundantly contained in the molded body 1 and the molded body 2 is different.

8. The joint according to any one of claims 1 to 7, wherein the ratio of the amount of amorphous component to the amount of crystalline thermoplastic resin contained in the thermoplastic resin composition (B) is 5:5 to 2:

8.

9. The joint according to any one of claims 1 to 8, wherein the joint is a sealed battery case used as a power source for mobile devices.

10. The bonding body according to any one of claims 1 to 8, wherein the bonding body is an insulating component for a solar cell module.

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