JP2023075003A - resin composition - Google Patents

Abstract

To provide a resin composition which contains a polyphenylene sulfide resin and is excellent in low warpage properties, heat resistance and mechanical strength.SOLUTION: The resin composition contains 5-150 pts.mass of a fibrous filler (D) and 0.1-5 pts.mass of an epoxy compound (E) based on 100 pts.mass of the total of (A)-(C) containing: 25-48 pts.mass of a polyphenylene sulfide resin (A) having an MVR of 60-500 cm3/10 min; and 52-75 pts.mass of the total of amorphous rubber-reinforced polystyrene or polystyrene (B) and/or a polyphenylene ether resin (C). The epoxy group-containing compound (E) has an epoxy equivalent of 150-1,500 g/eq.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin composition that contains a polyphenylene sulfide resin, has excellent heat resistance and a high degree of low warpage, and exhibits excellent strength.

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 that contains a PPS resin, has excellent heat resistance and a high degree of low warpage suitable for large-sized molded products, and has excellent strength. .

As a result of intensive studies to solve the above problems, the present inventors have found that high-flow PPS resin is combined with a large amount of amorphous polystyrene or rubber-reinforced polystyrene, and/or amorphous PPE resin. In addition, the present inventors have found that the above problems can be solved by blending a fibrous filler and a specific epoxy compound, and have arrived at the present invention.
The present invention relates to the following resin composition and molded article.

25 to 48 parts by mass of polyphenylene sulfide resin (A) having an MVR of 60 to 500 cm ³ /10 min measured at 1.295° C. under a load of 1.00 kgf, amorphous rubber-reinforced polystyrene or polystyrene (B) and/or polyphenylene The ether resin (C) contains 52 to 75 parts by mass of (B) and (C) in total, with respect to a total of 100 parts by mass of (A) to (C), and 5 to 150 parts by mass of the fibrous filler (D). A resin composition containing 0.1 to 5 parts by mass of an epoxy compound (E), wherein the epoxy equivalent of the epoxy group-containing compound (E) is 150 to 1500 g/eq.
2. 2. The resin composition as described in 1 above, wherein the epoxy compound (E) has an epoxy equivalent weight of 150 to 500 g/eq.
3. 3. The resin composition as described in 1 or 2 above, wherein the epoxy compound (E) has a weight average molecular weight of 300 to 9,000.
4. 4. The resin composition according to any one of 1 to 3 above, wherein the mass ratio (B)/(C) of the contents of (B) and (C) is 0.5 or more.
5. A molded article made of the resin composition according to any one of 1 to 4 above.
6. 5. The molded article as described in 5 above, which is an in-vehicle housing component.

INDUSTRIAL APPLICABILITY The resin composition of the present invention exhibits excellent effects such as excellent low warpage property, excellent heat resistance, and excellent mechanical strength.

The resin composition of the present invention comprises 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 1.00 kgf load, and amorphous rubber-reinforced polystyrene or polystyrene ( B) and / or polyphenylene ether resin (C), with respect to a total of 100 parts by mass of (A) to (C) containing 52 to 75 parts by mass in total of (B) and (C), a fibrous filler ( 5 to 150 parts by mass of D), 0.1 to 5 parts by mass of the epoxy compound (E), and the epoxy equivalent of the epoxy group-containing compound (E) is 150 to 1500 g/eq.

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, amorphous rubber-reinforced polystyrene or polystyrene (B) and/or PPE resin (C) serving as islands, and PPS resin (A) serving as a fibrous filler ( By becoming continuous through D), it becomes easy to become a matrix (sea), and as a result of containing the epoxy compound (E), it has extremely excellent low warpage, excellent heat resistance, and high mechanical strength. A composition is 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 load of 1.00 kgf.
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 PPE resin (C), it has a high degree of low warpage, excellent heat resistance, and mechanical strength. It becomes a resin composition excellent also in chemical resistance.
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 the thickness is higher than 500 cm ³ /10 min, it becomes difficult to form the sea-island structure described above, and the rubber-reinforced polystyrene or polystyrene (B) and the PPE 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 uses amorphous rubber-reinforced polystyrene or polystyrene (B).

Amorphous rubber-reinforced polystyrene or polystyrene (B) is amorphous, which means that when a sample is measured using a differential scanning calorimeter (DSC), a clear melting point and melting peak are not detected. say. 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 and the like in which benzene rings are regularly arranged alternately with respect to the polymer main chain are crystalline and excluded from 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.

Rubber reinforced polystyrene or polystyrene (B), 25 to 48 parts by mass of PPS resin (A), rubber reinforced polystyrene or polystyrene (B) and/or PPE resin (C), total 100 mass of (A) to (C) By containing 52 to 75 parts by mass on a part basis, 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 can be achieved.

As the rubber-reinforced polystyrene or polystyrene (B), it is preferable to use one having an MVR of 0.3 to 16 cm ³ /10 min, more preferably 0.4 cm ³ /10 min or more, as measured at 200° C. under a load of 5 kgf. is preferably 0.8 cm ³ /10 min or more, more preferably 1.0 cm ³ /10 min or more, particularly 1.1 cm ³ /10 min or more. Further, it is more preferably 11 cm ³ /10 min or less, still more preferably 8 cm ³ /10 min or less, especially 6 cm ³ /10 min or less, and particularly preferably 4 cm ³ /10 min or less. 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.

[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 graft-polymerizing 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.

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

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 the PPE resin (C) and/or the rubber-reinforced polystyrene or polystyrene (B) described above, based on a total of 100 parts by mass of (A) to (C), in a total of 52 to 75 parts by mass. 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.
A preferable content of (A) to (C) is 30 to 48 parts by mass, particularly preferably 35 to 48 parts by mass, based on 100 parts by mass of (A) to (C) in total. A preferable content of components (B) and/or (C) is the amount obtained by subtracting the amount of (A) from 100 parts by mass.
Rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C) are both preferably contained, and based on 100 parts by mass of (A) to (C) in total, (B) is 15 to 40 parts by mass, especially 15 parts by mass. 15 to 40 parts by mass, preferably 15 to 35 parts by mass of (C).
From the standpoint of deflection temperature under load, the mass ratio (B)/(C) of the contents of (B) and (C) is preferably 0.5 or more, more preferably 0.7 or more, further preferably 0.5. It is preferably 8 or more, preferably 3 or less, more preferably 2 or less, and most preferably 1.5 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, mineral fiber, etc. Among them, glass fiber is preferable.

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, 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 content of the fibrous filler (D) is 5 to 150 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), preferably 10 parts by mass or more, more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, preferably 120 parts by mass or less, more preferably 100 parts by mass or less, especially 80 parts by mass or less , and 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.
The fibrous filler (D) may be used in combination of two or more depending on the properties required.

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.

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.

[Epoxy compound (E)]
The resin composition of the present invention also preferably contains an epoxy compound (E).
By containing the epoxy compound (E), although the PPS resin (A) itself does not have a chemical structure that reacts with the epoxy compound (E), the epoxy compound (E) reacts with the PPS resin ( By being unevenly distributed at the interface between A) and the fibrous filler (D), the interfacial strength between the PPS resin (A) and the fibrous filler (D) is increased, and as a result, the mechanical strength of the resin composition, particularly the toughness, is improved. can be made
The preferred content when containing the epoxy compound (E) is 0.01 to 5 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). Department. By setting it as such content, mechanical strength, especially toughness can be improved. If the content is less than 0.01 parts by mass, the above-mentioned improvement effect is reduced, and if it exceeds 5 parts by mass, the viscosity increases significantly during retention, and molding stability tends to decrease. The content of the epoxy compound (E) is more preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, particularly 0.3 parts by mass or more, more preferably 4 parts by mass or less, and further It is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, 1.5 parts by mass or less, and particularly 1 part by mass or less.

The epoxy compound (E) may have one or more epoxy groups in one molecule. Examples thereof include novolac epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, and alicyclic epoxy compounds , glycidyl ethers, glycidyl esters, epoxidized butadiene polymers, resorcinol-type epoxy compounds, and the like.
In addition, the brominated epoxy compound mentioned in the brominated flame retardant (E) is excluded from this epoxy compound (E).

Examples of the novolak-type epoxy compounds include phenol novolak-type epoxy compounds and cresol novolak-type epoxy compounds.
Examples of bisphenol A type epoxy compounds include bisphenol A-diglycidyl ether, hydrogenated bisphenol A-diglycidyl ether, etc. Examples of bisphenol F type epoxy compounds include bisphenol F-diglycidyl ether and hydrogenated bisphenol F-diglycidyl. ether and the like.

Examples of cycloaliphatic epoxy compounds include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxycyclohexyl-3,4-cyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, epoxide, 3,4-epoxycyclohexyl glycidyl ether and the like.

Specific examples of glycidyl ethers include monoglycidyl ethers such as methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, and allyl glycidyl ether; Diglycidyl ethers such as pentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerol diglycidyl ether, propylene glycol diglycidyl ether and bisphenol A diglycidyl ether can be mentioned.
Glycidyl esters include monoglycidyl esters such as glycidyl benzoate and glycidyl sorbate; and diglycidyl esters such as diglycidyl adipate, diglycidyl terephthalate and diglycidyl orthophthalate.

Examples of epoxidized butadiene polymers include epoxidized polybutadiene, epoxidized styrene-butadiene copolymers, and epoxidized hydrogenated styrene-butadiene copolymers.
Examples of resorcin type epoxy compounds include resorcin diglycidyl ether and the like.

Further, the epoxy compound (E) may be a copolymer containing a glycidyl group-containing compound as one component. For example, a copolymer of an α,β-unsaturated acid glycidyl ester and one or more monomers selected from the group consisting of α-olefins, acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. For example, an epoxy group-containing acrylic (co)polymer can be mentioned as a preferable one.
General-purpose epoxy compounds, such as epoxy group-containing olefin-based elastomers, are themselves flexible, so while they have excellent toughness, they do not improve mechanical strength sufficiently, and rigidity also decreases. , these elastomers are less preferred.

In the present invention, as the epoxy compound (E), one having an epoxy equivalent of 150 to 1500 g/eq is used. If the epoxy equivalent is less than 150 g/eq, the amount of epoxy groups is too large, resulting in an increase in the viscosity of the resin composition. The effect of improving the mechanical strength of the resin composition tends to be insufficient. The epoxy equivalent is preferably 150-1000 g/eq, more preferably 150-500 g/eq.
The epoxy compound (E) preferably has a weight average molecular weight of 300 to 9,000. If the weight average molecular weight exceeds 9000, the compatibility with the PPS resin (A), the rubber-reinforced polystyrene or polystyrene (B), and the PPE resin (C) is lowered, and the mechanical strength of the molded article of the resin composition is lowered. tend to The weight average molecular weight is more preferably 7,000 or less, and even more preferably 6,000 or less.
The weight average molecular weight of the epoxy compound (E) is the polystyrene equivalent weight average molecular weight Mw by GPC.

As the epoxy compound (E), a bisphenol A-type epoxy compound or a novolac-type epoxy compound obtained by reacting bisphenol A or novolac with epichlorohydrin, or an epoxy group-containing acrylic (co)polymer can be used. It is particularly preferable from the point of view of properties.

[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. Phosphorus-based stabilizers, sulfur-based stabilizers and phenol-based stabilizers are preferred as stabilizers.

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'-biphenylene diphosphonite, tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite, 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.

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, and styrene resins, particularly acrylonitrile-styrene resins (AS resins) are 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 may 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 PPE resin (C). It is preferably 10 parts by mass or less, more preferably 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 PPE resin (C), and other resin components and various additives added as desired are combined. and then melt-kneaded in 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.

The resulting molded product has low warpage, excellent heat resistance, toughness and strength, and excellent chemical resistance. It is particularly suitable for use.
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 4, Comparative Examples 1 to 4)
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 shown in Table 2 below (all parts by mass), and then mixed with a twin-screw extruder ( Using "TEX30α" manufactured by Japan Steel Works, Ltd., L / D = 42), while feeding the fibrous filler (D) using a side feeder, cylinder setting temperature 310 ° C., discharge amount 30 kg / h, screw rotation The resin composition melted and kneaded under conditions of several 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.

[Mechanical strength determination]
Based on the above results, the mechanical strength was evaluated and determined according to the following criteria.
○: Satisfy both tensile strength of 130 MPa or more and bending strength of 175 MPa or more △: Satisfy both of tensile strength of 120 MPa or more and bending strength of 170 MPa or more ×: None of the conditions of ○ and △ are satisfied

[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.
○: Deflection temperature under load is 175 ° C. or higher ×: Deflection temperature under load is less than 175 ° 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.
◯: No abnormality in shape and appearance was observed. △: Shape was maintained, but abnormality in appearance such as swelling was observed.
x: The shape is not retained.

[Warpage amount and warpage determination]
Using an injection molding machine ("NEX80" manufactured by Nissei Plastic Industry Co., Ltd.), a cylinder temperature of 310°C, a mold temperature of 130°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 determined.
Evaluation of warpage was performed according to the following criteria.
O: The amount of warp is less than 3 mm △: The amount of warp is 3 mm or more and less than 5 mm ×: The amount of warp is 5 mm or more The results are shown in Table 2 below.

The resin composition of the present invention has low warpage, excellent heat resistance and strength, and excellent chemical resistance. can be suitably used.

Claims (6)

25 to 48 parts by mass of 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, amorphous rubber-reinforced polystyrene or polystyrene (B) and/or polyphenylene ether resin 5 to 150 parts by mass of the fibrous filler (D) with respect to a total of 100 parts by mass of (A) to (C) containing 52 to 75 parts by mass of (B) and (C) in total of (C) and 0.1 to 5 parts by mass of an epoxy compound (E), wherein the epoxy equivalent of the epoxy group-containing compound (E) is 150 to 1500 g/eq. 2. The resin composition according to claim 1, wherein the epoxy compound (E) has an epoxy equivalent of 150 to 500 g/eq. 3. The resin composition according to claim 1, wherein the epoxy compound (E) has a weight average molecular weight of 300 to 9,000. The resin composition according to any one of claims 1 to 3, wherein the mass ratio (B)/(C) of the contents of (B) and (C) is 0.5 or more. A molded article made of the resin composition according to any one of claims 1 to 4. 6. The molded article according to claim 5, which is an in-vehicle housing component.