JP2023024329A - resin composition - Google Patents

Abstract

To provide a resin composition containing a polyphenylene sulfide resin excellent in low warpage and heat resistance.SOLUTION: There is provided a resin composition which contains 25 to 48 pts.mass of a polyphenylene sulfide resin (A) having an MVR of 60 to 500 cm3/10 min, as measured at 295°C under a load of 1.00 kgf, an amorphous rubber-reinforced polystyrene or a polystyrene (B) having an MVR of 0.3 to 16 cm3/10 min, as measured at 200°C under a load of 5 kgf and/or a polyphenylene ether resin (C), based on 100 pts.mass of the total of (A) to (C), wherein the total content of the (B) and (C) is 52 to 75 pts.mass and the resin composition contains 5 to 150 pts.mass of a fibrous filler.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin composition containing a polyphenylene sulfide resin and exhibiting excellent heat resistance and low warpage.

Polyphenylene sulfide resin (hereinafter also referred to as PPS resin) has excellent heat resistance, chemical resistance, electrical insulation, etc., so it is used in electrical and electronic equipment parts, automotive parts, other electrical parts, machine parts, etc. widely used in

However, since the PPS resin is a crystalline resin, it has a large molding shrinkage rate, and warping of the molded product tends to be a problem. In order to improve the warpage of PPS resin, it has been attempted to reduce the warpage by blending plate-like fillers such as talc, but this tends to result in poor strength and toughness.
In addition, a technique for reducing warpage by alloying PPS resin with polyphenylene ether resin (hereinafter sometimes referred to as PPE resin) has also been proposed (for example, Patent Document 1). However, the required high degree of low warpage has not yet been achieved.

JP-A-2004-269664

An object (subject) of the present invention is to provide a resin composition containing a PPS resin and having excellent heat resistance and a high degree of low warpage suitable for large-sized molded products.

As a result of intensive studies to solve the above-described problems, the present inventors have found that a high-flow PPS resin is added with amorphous polystyrene or rubber-reinforced polystyrene with a high molecular weight and a low MVR, and/or an amorphous PPE resin. The present inventors have found that the above problems can be solved by combining a large amount and further blending a fibrous filler, and have arrived at the present invention.
The present invention relates to the following resin composition and molded article.

1. 25 to 48 parts by mass of a polyphenylene sulfide resin (A) having an MVR of 60 to 500 cm ³ /10 min measured at 295° C. under a load of 1.00 kgf based on a total of 100 parts by mass of the following (A) to (C), and Amorphous rubber-reinforced polystyrene or polystyrene (B) and/or polyphenylene ether resin (C) having an MVR measured at 200° C. and a 5 kgf load of 0.3 to 16 cm ³ /10 min, containing (B) and ( A resin composition characterized by having a total content of C) of 52 to 75 parts by mass and further containing 5 to 150 parts by mass of a fibrous filler (D).
2. 2. The resin composition according to 1 above, which contains both (B) and (C), and the total content thereof is 52 to 75 parts by mass based on 100 parts by mass of (A) to (C). thing.
3. 2. The resin composition according to 1 above, wherein the mass ratio (B)/(C) of the contents of (B) and (C) is 0.1 or more.
4. 2. The resin composition according to 1 above, wherein the mass ratio (B)/(C) of the contents of (B) and (C) is 0.5 or more.
5. 2. The resin composition according to 1 above, wherein the polyphenylene ether resin (C) has an intrinsic viscosity measured in chloroform at 30° C. of 0.4 dl/g or more.
6. 2. The resin composition as described in 1 above, wherein the polyphenylene sulfide resin (A) is a linear polyphenylene sulfide resin.
7. 2. The resin composition as described in 1 above, wherein the fibrous filler (D) is present in a state surrounded by the polyphenylene sulfide resin (A).
8. A molded article made of the resin composition according to any one of 1 to 7 above.
9. 8. The molded article according to 8 above, which is an in-vehicle housing component.

INDUSTRIAL APPLICABILITY The resin composition of the present invention exhibits an effect of being extremely excellent in low warpage property and excellent in heat resistance.

It is a photograph of an SEM image showing the morphology of a resin composition obtained in an example.

The resin composition of the present invention is a polyphenylene sulfide resin (A) having an MVR of 60 to 500 cm ³ /10 min measured at 295° C. under a load of 1.00 kgf based on a total of 100 parts by mass of (A) to (C). up to 48 parts by mass, and amorphous rubber-reinforced polystyrene or polystyrene (B) and/or polyphenylene ether resin (C) having an MVR of 0.3 to 16 cm ³ /10 min measured at 200° C. under a 5 kgf load, The total content of (B) and (C) is from 52 to 75 parts by mass, and the fibrous filler (D) is further contained from 5 to 150 parts by mass.
By adopting such a structure, even in a system rich in rubber-reinforced polystyrene or polystyrene (B) and/or PPE resin (C), which has a small amount of PPS resin (A), a high-flow PPS resin (A) can be obtained. A sea (matrix) having a sea-island structure or a sea having a co-continuous structure, rubber-reinforced polystyrene or polystyrene (B) having a low melt viscosity and/or PPE resin (C) serving as islands, and further PPS resin (A) serving as a fibrous filler ( By becoming continuous via D), it becomes easy to form a matrix (sea), and as a result, a resin composition having extremely excellent low warpage properties and excellent heat resistance can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. Although the explanations described below may be made based on embodiments and specific examples, the present invention should not be construed as being limited to such embodiments and specific examples.
In this specification, the term "~" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

[Polyphenylene sulfide resin (A)]
The resin composition of the present invention contains a polyphenylene sulfide resin (A) having an MVR of 60 to 500 cm ³ /10 min measured at 295° C. under a 1.00 kgf load.
By using a high-flow PPS resin with an MVR of 60 to 500 cm ³ /10 min in combination with rubber-reinforced polystyrene or polystyrene (B) and polyphenylene ether resin (C), it has a high degree of low warpage and excellent heat resistance. A resin composition having excellent mechanical strength and chemical resistance is obtained.
If the MVR is lower than 60 cm ³ /10 min, the amount of warpage increases, making it difficult to achieve low warpage, and the heat resistance of the PPS resin does not develop, and the mechanical strength tends to be low. On the other hand, if it is higher than 500 cm ³ /10 min, it becomes difficult to form the above-mentioned sea-island structure, and rubber-reinforced polystyrene or polystyrene (B) and polyphenylene ether resin (C) tend to form a sea, and low warpage and heat resistance tend to deteriorate. . The MVR is preferably 70 cm ³ /10 min or more, more preferably 75 cm ³ /10 min or more, even more preferably 80 cm ³ /10 min or more, more preferably 85 cm ³ /10 min or more, more preferably 300 cm 3 /10 min or more, more preferably 300 cm ³ /10 min or more. 250 cm ³ /10 min or less.

In the present invention, the MVR of PPS resin (A) is a value measured at a temperature of 295° C. and a load of 1.00 kgf.

The PPS resin (A) contains a p-phenylene sulfide unit as a structural unit, and preferably contains more than 50 mol%, more preferably 70 mol% or more, and still more preferably 90 mol% or more of the p-phenylene sulfide unit. It is a thing. Other structural units include m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfone units, phenylene ketone units, phenylene ether units, and substituent-containing phenylene sulfide units.
Among them, since it becomes a resin composition excellent in strength, toughness, heat resistance, chemical resistance, and mechanical properties, the p-phenylene sulfide unit is preferably 70 mol% or more, more preferably 90 mol% or more, especially is preferably poly(p-phenylene sulfide) containing only p-phenylene sulfide units.

The method for producing the PPS resin (A) is not particularly limited, and it may be produced by a method generally known as a method for producing a PPS resin. Specifically, it is obtained by subjecting paradichlorobenzene and sodium sulfide to a polycondensation reaction in a polar solvent. The MVR can also be adjusted by adjusting the or introducing a branching agent.

The PPS resin (A) may be a linear type that maintains a linear structure because no special heat treatment is performed, or a crosslinked type that is crosslinked by treatment at a high temperature in the presence of oxygen. Although it may be present, from the viewpoint of sufficiently obtaining the effects of the present invention, a straight-chain PPS resin is preferable to a cross-linked PPS resin.

[Rubber-reinforced polystyrene or polystyrene (B)]
The resin composition of the present invention contains ^rubber -reinforced polystyrene or polystyrene, and is amorphous rubber-reinforced polystyrene or polystyrene (B ) is used.

The rubber-reinforced polystyrene or polystyrene (B) is preferably amorphous. Here, the term "amorphous" refers to a property in which a clear melting point and melting peak are not detected when a sample is measured using a differential scanning calorimeter (DSC) or the like. Conversely, crystallinity refers to the property of having a crystalline structure in which molecules are regularly arranged and having a melting point and a melting peak measured by a differential scanning calorimeter (DSC) or the like. Syndiotactic polystyrene or the like in which benzene rings are regularly arranged alternately with respect to the polymer main chain is crystalline and is preferably excluded as rubber-reinforced polystyrene or polystyrene (B).

The polystyrene is a homopolymer of styrene, or copolymerized with other aromatic vinyl monomers such as α-methylstyrene, paramethylstyrene, vinyltoluene, vinylxylene, etc., in a range of 50% by mass or less. may

The rubber-reinforced polystyrene is preferably obtained by copolymerizing or blending a butadiene-based rubber component, and the amount of the butadiene-based rubber component is usually 1% by mass or more and less than 50% by mass, preferably 3 to 40% by mass, More preferably 5 to 30 mass %, still more preferably 5 to 20 mass %. High impact polystyrene (HIPS) is particularly preferred as rubber-reinforced polystyrene.

In the present invention, rubber-reinforced polystyrene or polystyrene (B) having an MVR of 0.3 to 16 cm ³ /10 min measured at 200° C. under a load of 5 kgf is used. Such MVR rubber-reinforced polystyrene or polystyrene (B) is used as PPS resin (A) 25 to 48 parts by mass, rubber-reinforced polystyrene or polystyrene (B) and / or PPE resin (C), (A) to (C ) in an amount of 52 to 75 parts by mass based on a total of 100 parts by mass of ), the PPS resin (A) becomes dominant in terms of physical properties, and as a result, high heat resistance and high degree of low warpage are achieved. be able to. If the MVR is 16 cm ³ /10 min or less, heat resistance and chemical resistance can be improved, and if it is 0.3 cm ³ /10 min or more, excellent production stability and fluidity can be provided.

MVR of rubber-reinforced polystyrene or polystyrene (B) is preferably 0.4 cm ³ /10 min or more, more preferably 0.8 cm ³ /10 min or more, still more preferably 1.0 cm ³ /10 min or more, especially 1.1 cm ³ / It is preferably 10 min or longer. The upper limit is preferably 11 cm ³ /10 min or less, more preferably 8 cm ³ /10 min or less, further preferably 6 cm ³ /10 min or less, and particularly preferably 4 cm ³ /10 min or less.

[Polyphenylene ether resin (C)]
The polyphenylene ether resin (C) used in the resin composition of the present invention is a polymer having a structural unit represented by the following general formula in its main chain, and may be either a homopolymer or a copolymer. good.

（式中、２つのＲ^ａは、それぞれ独立に、水素原子、ハロゲン原子、第１級若しくは第２級アルキル基、アリール基、アミノアルキル基、ハロアルキル基、炭化水素オキシ基、またはハロ炭化水素オキシ基を表し、２つのＲ^ｂは、それぞれ独立に、水素原子、ハロゲン原子、第１級若しくは第２級アルキル基、アリール基、ハロアルキル基、炭化水素オキシ基、またはハロ炭化水素オキシ基を表す。ただし、２つのＲ^ａがともに水素原子になることはない。）

(In the formula, two R ^a are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy and two R ^b each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group. However, two R ^a are not both hydrogen atoms.)

R ^a and R ^b are preferably a hydrogen atom, a primary or secondary alkyl group, or an aryl group. Preferred examples of primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, 2,3-dimethylbutyl, 2 -, 3- or 4-methylpentyl groups or heptyl groups. Suitable examples of secondary alkyl groups include, for example, isopropyl, sec-butyl and 1-ethylpropyl groups. In particular, R ^a is preferably a primary or secondary alkyl group having 1 to 4 carbon atoms or a phenyl group. ^Rb is preferably a hydrogen atom.

Suitable homopolymers of PPE resin (C) include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly( 2,6-dipropyl-1,4-phenylene ether), poly(2-ethyl-6-methyl-1,4-phenylene ether), poly(2-methyl-6-propyl-1,4-phenylene ether), etc. and polymers of 2,6-dialkylphenylene ethers. Copolymers include 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol/2,3,6-triethylphenol copolymer, 2,6-diethylphenol /2,3,6-trimethylphenol copolymer, 2,6-dialkylphenol/2,3,6-trialkylphenol copolymer such as 2,6-dipropylphenol/2,3,6-trimethylphenol copolymer Polymer, graft copolymer obtained by grafting styrene to poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer to styrene and a graft copolymer obtained by graft polymerization.

As the PPE resin (C), poly(2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol/2,3,6-trimethylphenol random copolymer are particularly preferred.

The PPE resin (C) preferably has an intrinsic viscosity of 0.4 dl/g or more, more preferably 0.42 dl/g or more, measured in chloroform at 30°C. By setting the intrinsic viscosity to 0.4 dl/g or more, the mechanical strength of the resin composition is further improved, and the chemical resistance and heat resistance of the resin composition tend to develop. A preferable upper limit of the intrinsic viscosity is 0.8 dl/g, and by setting it to 0.8 dl/g or less, there is a tendency that the fluidity is further improved and the molding process becomes easier. In addition, two or more PPE resins having different intrinsic viscosities may be used together to set the intrinsic viscosity within this range.

The method for producing the PPE resin (C) is not particularly limited, and according to a known method, for example, a method of oxidatively polymerizing a monomer such as 2,6-dimethylphenol in the presence of an amine copper catalyst can be adopted. At that time, the intrinsic viscosity can be controlled within a desired range by selecting the reaction conditions. Control of intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, amount of catalyst, and the like.

The resin composition of the present invention contains 52 to 75 parts by mass of the PPE resin (C) and/or the above-described MVR rubber-reinforced polystyrene or polystyrene (B) based on a total of 100 parts by mass of (A) to (C). By containing 25 to 48 parts by mass of the PPS resin (A) together with the PPS resin (A), the PPS resin (A) becomes dominant in terms of physical properties, and as a result, high heat resistance and a high degree of low warpage are achieved. be able to.
Preferred contents of (A) to (C) are 30 to 48 parts by mass, especially 35 to 48 parts by mass of component (A) based on 100 parts by mass of (A) to (C) in total, (B) and/or Component (C) is 52 to 70 parts by mass, especially 52 to 65 parts by mass.
Rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C) preferably contain both, and the total of (B) and (C) is 52 to 100 parts by mass based on the total of (A) to (C) It is preferably 75 parts by mass, preferably 20 to 60 parts by mass for (B) and 15 to 40 parts by mass for (C).
From the viewpoint of deflection temperature under load, the mass ratio (B)/(C) of the contents of (B) and (C) is preferably 0.1 or more, more preferably 0.3 or more, especially 0.1. 4 or more, 0.5 or more, 0.7 or more, and more preferably 0.8 or more. From the viewpoint of improving moldability, the mass ratio (B)/(C) of the contents of (B) and (C) is preferably 15 or less, more preferably 10 or less, especially 8 or less, 6 or less, and 5 or less. , 4 or less, particularly preferably 2 or less.

[Fibrous filler (D)]
The resin composition of the present invention contains a fibrous filler (D).
Examples of the fibrous filler (D) include fibrous fillers such as glass fiber, carbon fiber and mineral fiber, among which glass fiber is preferred.

The glass fiber may be A glass, E glass, alkali resistant glass composition containing zirconia component, chopped strand, roving glass, masterbatch of thermoplastic resin and glass fiber, etc. , any known glass fiber can be used. Among them, as the glass fiber, alkali-free glass (E glass) is preferable for the purpose of improving the thermal stability of the resin composition.

The glass fiber may have a circular cross section in the longitudinal direction, and a glass fiber having an irregularity ratio of 2 to 6 in the cross section in the longitudinal direction is also preferable. The shape ratio of the cross section in the longitudinal direction is assumed to be a rectangle with the smallest area that circumscribes the cross section perpendicular to the length direction of the glass fiber. is the ratio of the major axis/minor axis, where is the minor axis. By containing glass fibers having an irregular shape ratio of 2 to 6, the function of bridging between the phases of the PPS resin (A) in which the glass fibers are oriented is exhibited, and the PPS resin (A) becomes a matrix (sea). Since it becomes easier, the heat resistance is specifically improved, and it is also possible to make it excellent in low warpage and appearance.
Furthermore, when the glass fibers are present in a state surrounded by the PPS resin (A) phase, the glass fibers have a higher bridging effect between the PPS resin (A) phases. Since the bulky glass fiber serves as an extender for the PPS resin (A), the heat resistance is likely to be further improved.

In the case of a glass fiber with a modified cross section, the deformation ratio is more preferably 2.5 or more, still more preferably 3 or more, and more preferably 5.5 or less, still more preferably 5 or less. It is particularly preferred that the shape of the longitudinal cross-section is substantially rectangular.
The cross-sectional area in the length direction of the glass fiber is preferably more than 180 μm ² and 300 μm ² or less. With such a cross-sectional area, the PPS resin (A) easily becomes a matrix, resulting in improved heat resistance. easy to do The cross-sectional area is more preferably more than 180 μm ² and 250 μm ² or less, and still more preferably more than 180 μm ² and 200 μm ² or less.
Although the thickness of the glass fiber is not particularly limited, it is preferable that the minor axis is about 2 to 20 μm and the major axis is about 5 to 50 μm.

The glass fibers may be treated with a sizing agent or a surface treatment agent. In addition to the untreated glass fibers, a sizing agent or a surface treatment agent may be added for surface treatment during the production of the resin composition of the present invention.

Examples of the sizing agent include resin emulsions such as vinyl acetate resins, ethylene/vinyl acetate copolymers, acrylic resins, epoxy resins, polyurethane resins and polyester resins.
Examples of surface treatment agents include aminosilane compounds such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropyltrimethoxysilane; vinyltrichlorosilane; Chlorosilane compounds such as chlorosilane, alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy Epoxysilane-based compounds such as silane, γ-glycidoxypropyltrimethoxysilane, acrylic compounds, isocyanate-based compounds, titanate-based compounds, and epoxy-based compounds are included.
Two or more of these sizing agents and surface treatment agents may be used in combination, and the amount (attachment amount) thereof used is usually 10% by mass or less, preferably 0.05 to 5% by mass, based on the mass of the glass fiber. is. A necessary and sufficient effect can be obtained by setting the adhesion amount to 10% by mass or less.

The fibrous filler (D) may be used in combination of two or more depending on the properties required, and the content thereof is PPS resin (A), rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C). 5 to 150 parts by mass, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more. is 120 parts by mass or less, more preferably 100 parts by mass or less, more preferably 80 parts by mass or less, particularly preferably 60 parts by mass or less. By containing it in such a range, high heat resistance can be achieved, and the effect of reducing the strength and shrinkage of the resulting molded article can be enhanced.

In the resin composition of the present invention, the fibrous filler (D) is present in a state surrounded by the phase of the PPS resin (A) in the cross-sectional structure of the molded article of the resin composition observed with an electron microscope. is preferred. Further, it is preferable that the PPS resin (A) forms a co-continuous phase with a sea (matrix) having a sea-island structure, or rubber-reinforced polystyrene or polystyrene (B) and the PPE resin (C). By having such a morphological structure, the heat resistance is specifically improved, and furthermore, it tends to be excellent in low warpage property and excellent in appearance.
FIG. 1 is a photograph of an SEM image showing the morphology of a molded product of the resin composition obtained in Example 2. FIG. In the figure, the light gray part is a co-continuous phase composed of polystyrene and PPE resin, the dark gray part forms the matrix phase (sea) of the PPS resin, and the black circles are glass fibers, and the glass fibers are PPS. It can be seen that they exist in a state surrounded by a resin phase.

The resin composition of the present invention may contain other plate-like, granular or amorphous inorganic fillers in addition to the fibrous filler (D) described above. Plate-like inorganic fillers include talc, glass flakes, mica, mica, kaolin, expanded graphite, scale-like graphite, metal foil and the like.
Other particulate or amorphous inorganic fillers include ceramic beads, clays, zeolites, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, zinc sulfide, and the like.

Inorganic fillers other than the fibrous filler (D) are effective in reducing warpage by reducing anisotropy, but tend to lower the strength and toughness of the resin composition, so excessive addition is not preferred.
The content when other inorganic fillers are contained is preferably 30 parts by mass or less with respect to a total of 100 parts by mass of the PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). , more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, especially 10 parts by mass or less, 7 parts by mass or less, and particularly 5 parts by mass or less.

[Elastomer (E)]
The resin composition of the present invention may contain an elastomer (E) from the viewpoint of improving toughness and heat shock resistance of the resin composition. From the viewpoint of compatibility with the PPS resin (A), the elastomer (E) is preferably an epoxy group-containing olefin elastomer or an epoxy group-containing acrylic elastomer.

The olefinic elastomer or acrylic elastomer containing an epoxy group is preferably an elastomer obtained by introducing a glycidyl group into an olefinic elastomer or acrylic elastomer. The method for introducing a glycidyl group is not limited, and any known method can be adopted. Specifically, vinyl-based monomers having an epoxy group such as glycidyl ester compounds of α,β-unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate are used as raw materials for elastomers. Examples include a method of copolymerizing with a certain olefinic or acrylic monomer, a method of polymerizing an elastomer polymer using a polymerization initiator or chain transfer agent having an epoxy group, a method of grafting an epoxy compound onto an elastomer, and the like.

The content of the glycidyl group is usually 1 to 20% by mass in the case of a glycidyl methacrylate group, preferably 3 to 15% by mass, more preferably 3 to 12% by mass, particularly preferably 4 to 8% by mass. .

Examples of olefinic elastomers include polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, diene elastomers such as butadiene-isoprene copolymers, and ethylene. - Ethylene such as random and block copolymers of propylene, random and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins, ethylene-propylene-hexadiene copolymers- Preferred examples include a propylene non-conjugated diene terpolymer and a butylene-isoprene copolymer.

Acrylate-based elastomers are rubber-like elastomers obtained by polymerization of acrylic acid esters or copolymerization based on acrylic acid esters. Polymers obtained by polymerizing monomers include rubber-like polymers obtained by graft-polymerizing graft-polymerizable monomers such as methyl methacrylate.

Examples of the acrylate include butyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like. In addition to butylene diacrylate, the crosslinkable monomers include esters of polyols such as butylene dimethacrylate and trimethylolpropane trimethacrylate and acrylic acid or methacrylic acid; vinyl compounds such as vinyl acrylate and vinyl methacrylate; Acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate and the like.

In addition to methyl methacrylate, examples of graft-polymerizable monomers include methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate, styrene, and acrylonitrile. Furthermore, acrylates having a glycidyl group such as glycidyl methacrylate and the like are included. A part of this graft-polymerizable monomer can be co-polymerized when the acrylic acid ester and the crosslinkable monomer are polymerized to produce a polymer.

As the olefin-based elastomer or acrylic elastomer, a copolymer obtained by combining the above-described olefin-based monomer and the above-described acrylate-based monomer is also preferable.

The epoxy group-containing olefin elastomer or epoxy group-containing acrylic elastomer is preferably copolymerized with glycidyl methacrylate, and particularly preferably contains 3 to 15% by mass of constituent units derived from glycidyl methacrylate.

[Stabilizer]
It is preferable that the resin composition of the present invention contains a stabilizer because it has effects of improving thermal stability and preventing deterioration of mechanical strength, transparency and hue. The stabilizer is preferably a heat stabilizer or an antioxidant such as a phosphorus stabilizer, a sulfur stabilizer, and a phenol stabilizer.

Phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphites (phosphites), trivalent phosphates (phosphonites), pentavalent phosphates (phosphates) and the like. Phyto compounds, organic phosphonite compounds and organic phosphate compounds are preferred.

The organic phosphate compound preferably has the following general formula:
(R ¹ O) _3-n P(=O)OH _n
(In the formula, R ¹ is an alkyl group or an aryl group, which may be the same or different. n represents an integer of 0 to 2.)
It is a compound represented by More preferably, R ¹ is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of alkyl groups having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group and the like can be mentioned.

Examples of long-chain alkyl acid phosphate compounds include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate and the like. Among these, octadecyl acid phosphate is preferred, and this product is commercially available from ADEKA under the trade name "ADEKA STAB AX-71".

The organic phosphite compound preferably has the following general formula:
R ² OP(OR ³ )(OR ⁴ )
(wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ² , R ³ and R ⁴ is an aryl group having 6 to 30 carbon atoms.)
The compound represented by is mentioned.

Examples of organic phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, dilaurylhydrogenphosphite, triethylphosphite, tridecylphosphite, tris(2-ethylhexyl)phosphite, tris(tridecyl ) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite , hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis(3-methyl-6-tert-butylphenyl di(tridecyl)phosphite), tetra(tridecyl) 4,4 '-isopropylidene diphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris(4- tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis(2,4-di-tert-butylphenyl)pentaerythritol di Phosphites, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis( 2,4-dicumylphenyl)pentaerythritol diphosphite and the like. Among these, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is preferred.

The organic phosphonite compound preferably has the following general formula:
R ⁵ -P(OR ⁶ )(OR ⁷ )
(wherein R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and among R ⁵ , R ⁶ and R ⁷ is an aryl group having 6 to 30 carbon atoms.)
The compound represented by is mentioned.

Examples of organic phosphonite compounds include tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-n-butylphenyl)-4,4'-biphenyl diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite night, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis ( 2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, and the like. .

As the sulfur-based stabilizer, any conventionally known sulfur atom-containing compound can be used, and thioethers are particularly preferable. Specific examples include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), thiobis(N-phenyl-β-naphthylamine ), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryltrithiophosphite. Among these, pentaerythritol tetrakis(3-dodecylthiopropionate) is preferred.

Phenolic stabilizers include, for example, pentaerythritol tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3,5-di-tert-butyl-4 -hydroxyphenyl)propionate, thiodiethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol tetrakis(3-(3,5-di-neopentyl-4-hydroxyphenyl) ) propionate) and the like. Among these, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is preferred.

One stabilizer may be contained, or two or more stabilizers may be contained in any combination and ratio.

The content of the stabilizer is preferably 0.001 to 2 parts by mass with respect to a total of 100 parts by mass of the PPS resin (A), rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C). If the content of the stabilizer is less than 0.001 parts by mass, the thermal stability of the resin composition tends to decrease, and the molecular weight and hue are likely to deteriorate during molding. As a result, there is a tendency that the generation of silver and the deterioration of hue are more likely to occur. The stabilizer content is more preferably 0.01 to 1.5 parts by mass, and still more preferably 0.1 to 1 part by mass.

[Release agent]
The resin composition of the present invention preferably contains a release agent (or lubricant).
Release agents (lubricants) include, for example, hydrocarbon release agents such as liquid paraffin, paraffin wax, polyethylene wax and polypropylene wax; aliphatic release agents such as stearyl alcohol, stearic acid and 12-hydroxystearic acid. ; amide compounds such as stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, methylene bis stearic acid amide, ethylene stearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, ethylene bis lauric acid amide Molding agents: metallic soap-based releasing agents such as calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, barium stearate; hydrogenated fats and oils, glycerin monostearate, butyl stearate, pentaerythritol stearate and ester release agents such as stearyl stearate.

Among these, amide-based mold release agents are preferable because they have a high softening point, improve the fluidity and heat resistance of the resin composition, and have a high mold release effect. Amides are preferred.

The content of the release agent (lubricant) is preferably 0.1 to 3 parts by mass with respect to a total of 100 parts by mass of the PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). is more preferably 0.2 to 2.5 parts by mass, more preferably 0.3 to 2 parts by mass. If the amount is less than 0.1 parts by mass, the surface property tends to be deteriorated due to poor mold release during melt molding. The surface tends to become cloudy.

[Carbon black]
The resin composition of the present invention preferably contains carbon black.
Carbon black is not limited in its type, raw material type, and production method, and any of furnace black, channel black, acetylene black, ketjen black, etc. can be used. Although the number average particle diameter is not particularly limited, it is preferably about 5 to 60 nm.

It is preferable to use carbon black that has been masterbatched in advance with a thermoplastic resin. PPS resins, PPE resins, olefin resins, styrene resins and the like are preferably used as thermoplastic resins for masterbatching, with styrene resins, particularly acrylonitrile-styrene resins (AS resins) being preferred.

The content of carbon black is preferably 0.1 to 4 parts by mass, more preferably 0.1 to 4 parts by mass, with respect to a total of 100 parts by mass of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). 2 to 3 parts by mass. When the amount is 0.1 part by mass or more, the effect of obtaining a desired color is enhanced, and an effect of improving weather resistance and the like can be expected. If the amount is 4 parts by mass or less, it can be expected that deterioration of mechanical properties can be suppressed.

[Other ingredients]
The resin composition of the present invention contains a thermoplastic resin other than the above-described PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C) within a range that does not impair the effects of the present invention. be able to. Specific examples of other thermoplastic resins include polybutylene terephthalate resin, polyacetal resin, polyamide resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyetherketone resin, polyolefin resin, and the like. is mentioned.
However, if other resins are contained, the content shall be 20 parts by mass or less with respect to the total of 100 parts by mass of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and polyphenylene ether resin (C). is preferable, 10 parts by mass or less is more preferable, 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

In addition, the resin composition of the present invention may contain various additives other than those described above. Examples of such additives include flame retardants, flame retardant aids, drip inhibitors, ultraviolet absorbers, Examples include antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersants, antibacterial agents, coloring agents, dyes and pigments, and the like.

[Production of resin composition]
The resin composition of the present invention can be produced according to a conventional method for preparing a resin composition. That is, the PPS resin (A) excluding the fibrous filler (D), the rubber-reinforced polystyrene or polystyrene (B), the polyphenylene ether resin (C), and other resin components and various additives added as desired are combined together. and then melt-kneaded with a single-screw or twin-screw extruder. The resin composition can also be prepared without premixing the respective components, or premixing only a part of them, feeding them to an extruder using a feeder and melt-kneading them. Alternatively, a masterbatch of a part thereof may be blended and melt-kneaded. Furthermore, it is also possible to supply a mixture obtained by mixing each component in advance to a molding machine such as an injection molding machine as it is without melt-kneading to produce various moldings. The fibrous filler (D) is preferably side-fed using a side feeder.

The heating temperature for melt-kneading can be appropriately selected from the range of 280 to 350°C. If the temperature is too high, decomposition gas is likely to be generated, which may cause poor appearance. Therefore, it is desirable to select a screw structure in consideration of shear heat generation and the like. In order to suppress decomposition during kneading and subsequent molding, it is desirable to use antioxidants and heat stabilizers.

[Molded body]
The method for producing a molded article using the resin composition of the present invention is not particularly limited, and any molding method commonly used for resin compositions can be employed. Examples include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, hollow molding such as gas assist, molding using heat insulating molds, and rapid heating molds. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, A blow molding method and the like can be mentioned. Among these, injection molding and insert molding are particularly preferred. Further, in one embodiment of the present invention, the resin composition of the present invention is particularly suitable for insert molding because it hardly corrodes metal.

The resulting molded product has excellent low warpage, heat resistance, toughness, strength, other mechanical properties, chemical resistance, and resistance to metal corrosion. It is particularly suitable for use as equipment parts, interior and exterior parts for automobiles, and other electric parts.
Electrical and electronic device parts include connectors, coils, sensors, sensor covers, lamp sockets, resistors, relay cases, small switches, coil bobbins, capacitors, various terminal boards, plugs, housings for variable condensers, housing parts for IH cookers, Grill handles, coil peripheral materials, rice cooker protective frames, smart meter housings, industrial breaker housings, inverter cases, mobile phone housings, warming device housings, battery separators, battery cases, car charging equipment, etc. Specifically.
Automotive interior and exterior parts include automotive housing parts, automotive battery cases, automotive battery covers, automotive battery separators, various motor cases, sensor cases, various valves such as exhaust gas valves, fuel related / exhaust system / Intake system pipes, air intake nozzles, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, automotive camera brackets, exhaust gas sensors, holder parts, door mirror stays, head-up display housings for automobile interiors It can be particularly preferably used for a body, a housing for an engine control unit (ECU), or a connector part for electrical equipment of an automobile.
In particular, the resin composition of the present invention is suitable for vehicle housing parts and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention should not be construed as being limited to the following examples.

(Examples 1 to 10, Comparative Examples 1 to 7)
The ingredients used are shown in Table 1 below.

Among the components shown in Table 1 above, the components excluding the fibrous filler (D) are uniformly mixed in a tumbler mixer at the ratios (all parts by mass) shown in Table 2-3 below, and then biaxially extruded. Using a machine ("TEX30α" manufactured by Japan Steel Works, Ltd., L / D = 42), while feeding the fibrous filler (D) using a side feeder, the cylinder setting temperature is 310 ° C., the discharge amount is 30 kg / h, The resin composition melted and kneaded at a screw speed of 200 rpm was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of the resin composition.

[Tensile breaking strength, tensile breaking elongation]
After drying the pellets obtained above at 120 ° C. for 5 hours, using an injection molding machine manufactured by Japan Steel Works, Ltd. (clamping force 85 T), under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., ISO Multipurpose specimens (4 mm thick) were injection molded.
Based on ISO527, tensile strength at break (unit: MPa) and tensile elongation at break (unit: %) were measured using the above ISO multi-purpose test piece (4 mm thick).
[Maximum flexural strength, flexural modulus]
Using the ISO multi-purpose test piece (4 mm thick), the maximum flexural strength (unit: MPa) and flexural modulus (unit: MPa) were measured at a temperature of 23° C. in accordance with ISO178.
[Notched Charpy impact strength]
Notched Charpy impact strength (unit: kJ/m ² ) was measured at a temperature of 23° C. for a notched test piece obtained by notching the above ISO multipurpose test piece (4 mm thick) according to ISO179.

[Deformation temperature under load and judgment of heat resistance]
Using the above ISO multi-purpose test piece (4 mm thick), the load deflection temperature was measured under the condition of a load of 1.80 MPa in accordance with ISO75-1 and ISO75-2.
Heat resistance was determined according to the following criteria.
AA: Deflection temperature under load is over 250°C A: Deflection temperature under load is 150°C or more and 250°C or less C: Deflection temperature under load is less than 150°C

[Solder heat resistance test and determination of solder heat resistance]
Using an injection molding machine ("J50ADS" manufactured by Japan Steel Works, Ltd.), a combustion test piece of 12.5 mm x 125 mm x 1.5 mm thickness was injection molded under the conditions of a cylinder temperature of 310°C and a mold temperature of 130°C. Using tweezers, this test piece was immersed in a solder bath adjusted to 260° C. for 10 seconds, and the state of the test piece after taking it out was observed.
Evaluation of solder heat resistance was performed according to the following criteria.
A: No abnormality is observed in terms of shape and appearance.
B: Although the shape is maintained, an abnormality in appearance such as swelling is confirmed.
C: Does not retain shape.

[Warpage amount and warpage determination]
Using an injection molding machine ("NEX80" manufactured by Nissei Plastic Industry Co., Ltd.), a cylinder temperature of 260°C, a mold temperature of 80°C, and an injection time of 0.5 sec were used to form a disc with a diameter of 100 mm and a thickness of 1.6 mm. Molding was performed using a mold, and the warpage amount (unit: mm) of the disk was obtained.
Evaluation of warpage was performed according to the following criteria.
AA: less than 3 mm of warp B: more than 3 mm and less than 4 mm of warp C: more than 4 mm of warp The results are shown in Table 2-3 below.

The resin composition of the present invention is excellent in low warpage, heat resistance, mechanical strength and chemical resistance. It can be suitably used for parts and the like.

Claims (9)

25 to 48 parts by mass of a polyphenylene sulfide resin (A) having an MVR of 60 to 500 cm ³ /10 min measured at 295° C. under a load of 1.00 kgf based on a total of 100 parts by mass of the following (A) to (C), and Amorphous rubber-reinforced polystyrene or polystyrene (B) and/or polyphenylene ether resin (C) having an MVR measured at 200° C. and a 5 kgf load of 0.3 to 16 cm ³ /10 min, containing (B) and ( A resin composition characterized by having a total content of C) of 52 to 75 parts by mass and further containing 5 to 150 parts by mass of a fibrous filler (D). The resin according to claim 1, which contains both (B) and (C), and the total content is 52 to 75 parts by mass based on 100 parts by mass of (A) to (C). Composition. 2. The resin composition according to claim 1, wherein the mass ratio (B)/(C) of the contents of (B) and (C) is 0.1 or more. 2. The resin composition according to claim 1, wherein the mass ratio (B)/(C) of the contents of (B) and (C) is 0.5 or more. 2. The resin composition according to claim 1, wherein the polyphenylene ether resin (C) has an intrinsic viscosity of 0.4 dl/g or more measured in chloroform at 30°C. 2. The resin composition according to claim 1, wherein the polyphenylene sulfide resin (A) is a linear polyphenylene sulfide resin. 2. The resin composition according to claim 1, wherein the fibrous filler (D) is present surrounded by the polyphenylene sulfide resin (A). A molded article made of the resin composition according to any one of claims 1 to 7. 9. The molded article according to claim 8, which is an in-vehicle housing component.

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