resin composition

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

[0001] The present invention relates to a resin composition, and more particularly to a resin composition containing a polyphenylene sulfide resin, having excellent heat resistance and high flatness, and exhibiting excellent strength.

Background Art

[0002] Polyphenylene sulfide resin (hereinafter sometimes referred to as PPS resin) has excellent heat resistance, chemical resistance, electrical insulation, etc., and is therefore widely used in electrical and electronic equipment parts, automotive parts and other electrical parts, mechanical parts, etc.

[0003] However, since the PPS resin is a crystalline resin, the molding shrinkage rate is large, and warpage of the molded product tends to be a problem. In order to improve the warpage of the PPS resin, a plate-like filler such as talc is blended to reduce the warpage, but the strength and toughness tend to be inferior. In addition, a technique for achieving low warpage by alloying the PPS resin with a polyphenylene ether resin (hereinafter sometimes referred to as PPE resin) has also been proposed (for example, Patent Document 1), but it has not achieved the high degree of low warpage required for large-sized molded products.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object (problem) of the present invention is to provide a resin composition containing a PPS resin, having excellent heat resistance and a high degree of low warpage suitable for large-sized molded products, and excellent strength.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventor has found that by combining a high-flow PPS resin with a large amount of amorphous polystyrene or rubber-reinforced polystyrene and / or an amorphous PPE resin, and further blending a fibrous filler and a specific epoxy compound, the above problems can be solved, and the present invention has been achieved. The present invention relates to the following resin compositions and molded articles.

[0007] 1. 25 to 48 parts by mass of polyphenylene sulfide resin (A) having an MVR measured at 295 °C and a load of 1.00 kgf of 60 to 500 cm 3 / 10 min, 52 to 75 parts by mass in total of amorphous rubber-reinforced polystyrene or polystyrene (B) and / or polyphenylene ether resin (C), 5 to 150 parts by mass of fibrous filler (D), and 0.1 to 5 parts by mass of epoxy compound (E) are contained with respect to a total of 100 parts by mass of (A) to (C), and the epoxy equivalent of the epoxy group-containing compound (E) is 150 to 1500 g / eq. A resin composition characterized by the above. 2. The resin composition according to 1 above, wherein the epoxy equivalent of the epoxy compound (E) is 150 to 500 g / eq. 3. The resin composition according to 1 or 2 above, wherein the weight average molecular weight of the epoxy compound (E) is 300 to 9000. 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 comprising the resin composition according to any one of 1 to 4 above. 6. The molded article according to 5 above, which is a housing part for vehicle use.

Advantages of the Invention

[0008] The resin composition of the present invention exhibits extremely excellent low warpage properties, excellent heat resistance, and further excellent mechanical strength.

Modes for Carrying Out the Invention

[0009] The resin composition of the present invention has an MVR of 60-500 cm² measured at 295°C and a load of 1.00 kgf. 3 The product contains 25 to 48 parts by mass of polyphenylene sulfide resin (A) with a concentration of 10 min, 52 to 75 parts by mass of amorphous rubber-reinforced polystyrene or polystyrene (B) and / or polyphenylene ether resin (C) in total, with 5 to 150 parts by mass of fibrous filler (D) and 0.1 to 5 parts by mass of epoxy compound (E) per 100 parts by mass of (A) to (C), wherein the epoxy equivalent of epoxy group-containing compound (E) is 150 to 1500 g / eq.

[0010] By adopting this configuration, even in a system with a low PPS resin (A) content and a high rubber-reinforced polystyrene or polystyrene (B) and / or PPE resin (C) content, the high-flow PPS resin (A) forms a sea (matrix) in a sea-island structure or a sea in a co-continuous structure, the amorphous rubber-reinforced polystyrene or polystyrene (B) and / or PPE resin (C) form islands, and the PPS resin (A) becomes continuous via fibrous filler (D), making it easier to form a matrix (sea). Furthermore, the inclusion of epoxy compound (E) results in a resin composition that exhibits extremely low warping, excellent heat resistance, and high mechanical strength.

[0011] The embodiments of the present invention will be described in detail below. The following description may be based on embodiments and specific examples, but the present invention is not limited to such embodiments or specific examples. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0012] [Polyphenylene sulfide resin (A)] The resin composition of the present invention has an MVR of 60-500 cm² measured at 295°C and a load of 1.00 kgf. 3 It contains polyphenylene sulfide resin (A) at 10 min. MVR is 60-500cm 3By using the PPS resin with a melt volume rate (MVR) of 60 cm³ / 10 min in combination with rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C), a resin composition excellent in high flatness and heat resistance and also excellent in mechanical strength and chemical resistance can be obtained. An MVR lower than 60 cm³ / 10 min 3 When used, the amount of warpage becomes large, making it difficult to achieve low warpage, and in addition to the heat resistance of the PPS resin not being exhibited, the mechanical strength tends to be low. Also, when the MVR is higher than 500 cm³ / 10 min 3 it becomes difficult to form the above-mentioned sea-island structure, and rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C) tend to become the continuous phase, and the low warpage and heat resistance tend to deteriorate. The MVR is preferably 70 cm³ / 10 min or more, 3 more preferably 75 cm³ / 10 min or more, 3 even more preferably 80 cm³ / 10 min or more, 3 particularly preferably 85 cm³ / 10 min or more, 3 and most preferably 85 cm³ / 10 min or more. Also, it is preferably 300 cm³ / 10 min or less, 3 more preferably 250 cm³ / 10 min or less, 3 and most preferably 250 cm³ / 10 min or less.

[0013] In the present invention, the MVR of the PPS resin (A) is a value measured at a temperature of 295 °C and a load of 1.00 kgf.

[0014] The PPS resin (A) contains a p-phenylene sulfide unit as a constituent unit, and preferably contains more than 50 mol% of the p-phenylene sulfide unit, more preferably 70 mol% or more, and even more preferably 90 mol% or more. Other constituent units include m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfone units, phenylene ketone units, phenylene ether units, substituted group-containing phenylene sulfide units, etc. In particular, a resin composition containing 70 mol% or more, more preferably 90 mol% or more, of p-phenylene sulfide units, and especially a poly(p-phenylene sulfide) containing only p-phenylene sulfide units, is preferred because it results in a resin composition with excellent strength, toughness, heat resistance, chemical resistance, and mechanical properties.

[0015] The method for producing PPS resin (A) is not particularly limited and can be produced by a method generally known as a method for producing PPS resin. Specifically, it is obtained by polycondensation reaction of paradichlorobenzene and sodium sulfide in a polar solvent, and the reaction proceeds under high temperature and high pressure, polymerizing through dehydration and desalting reactions, and the MVR can be adjusted by adjusting the polymerization time and catalyst amount, as well as by introducing a branching agent.

[0016] The PPS resin (A) may be a linear type that maintains a linear structure because no special heat treatment is performed, or it may be a crosslinked type that is crosslinked by treatment at high temperature in the presence of oxygen. However, from the viewpoint of fully obtaining the effects of the present invention, a linear type of PPS resin is preferred over a crosslinked type.

[0017] [Rubber-reinforced polystyrene or polystyrene (B)] The resin composition of the present invention uses amorphous rubber-reinforced polystyrene or polystyrene (B).

[0018] Amorphous rubber-reinforced polystyrene or polystyrene (B) refers to the property that, when a sample is measured using a differential scanning calorimeter (DSC), no clear melting point or melting peak is detected. Conversely, crystalline refers to the property that molecules tend to form a regularly arranged crystalline structure and have a melting point and melting peak when measured using a differential scanning calorimeter (DSC). Syndiotactic polystyrene, in which benzene rings are regularly and alternately arranged on the polymer main chain, is crystalline and is therefore excluded from being classified as rubber-reinforced polystyrene or polystyrene (B).

[0019] The polystyrene may be a homopolymer of styrene, or a copolymer of other aromatic vinyl monomers, such as α-methylstyrene, para-methylstyrene, vinyltoluene, vinylxylene, etc., in an amount of 50% by mass or less.

[0020] The rubber-reinforced polystyrene is preferably copolymerized or blended with 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% by mass, and even more preferably 5 to 20% by mass. High-impact polystyrene (HIPS) is particularly preferred as the rubber-reinforced polystyrene.

[0021] By incorporating rubber-reinforced polystyrene or polystyrene (B) in an amount of 52 to 75 parts by mass, based on a total of 100 parts by mass of (A) to (C), as 25 to 48 parts by mass of PPS resin (A) and rubber-reinforced polystyrene or polystyrene (B) and / or PPE resin (C), the PPS resin (A) becomes dominant in terms of physical properties, resulting in high heat resistance and a high degree of low warping.

[0022] For rubber-reinforced polystyrene or polystyrene (B), the MVR measured at 200°C with a 5kgf load is 0.3 to 16 cm. 3 It is preferable to use one that is 10 min, and more preferably 0.4 cm. 3 / 10 min or more, and also 0.8 cm 3 / 10 min or more, especially 1.0 cm 3 / 10 min or more, especially 1.1 cm 3 It is preferable that the interval be 10 min or longer. More preferably, it is 11 cm. 3 / 10 min or less, more preferably 8 cm 3 / 10 min or less, especially 6 cm 3 / 10 min or less, particularly preferably 4 cm 3 / 10min or less. MVR is 16cm 3 If the duration is 10 min or less, heat resistance and chemical resistance can be improved, and 0.3 cm 3If the time is 10 min or more, it can be provided with excellent production stability and fluidity.

[0023] [Polyphenylene ether resin (C)] The polyphenylene ether resin (C) used in the resin composition of the present invention is a polymer having a main chain of structural units represented by the following general formula, and may be either a homopolymer or a copolymer.

[0024] [ka] (In the formula, two R a Each of these independently represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbon oxy group, or a halohydrocarbon oxy group, and the two R b Each of these independently represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group, or a halohydrocarbon oxy group. However, two R a (They cannot both become hydrogen atoms.)

[0025] R a and R b Preferred members include hydrogen atoms, primary or secondary alkyl groups, and aryl groups. Suitable 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, or heptyl groups. Suitable examples of secondary alkyl groups include, for example, isopropyl, sec-butyl, or 1-ethylpropyl groups. In particular, R a It is preferable that the group is a primary or secondary alkyl group or phenyl group having 1 to 4 carbon atoms. b It is preferable that it is a hydrogen atom.

[0026] Suitable homopolymers of PPE resin (C) include, for example, polymers of 2,6-dialkylphenylene ethers such as 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), and poly(2-methyl-6-propyl-1,4-phenylene ether). Examples of copolymers include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymers, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymers, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymers, and other 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers; graft copolymers obtained by graft polymerization of styrene onto poly(2,6-dimethyl-1,4-phenylene ether); and graft copolymers obtained by graft polymerization of styrene onto 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers.

[0027] 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.

[0028] The PPE resin (C) preferably has an intrinsic viscosity of 0.4 dl / g or higher, measured in chloroform at 30°C, and more preferably 0.42 dl / g or higher. Achieving an intrinsic viscosity of 0.4 dl / g or higher tends to improve the mechanical strength of the resin composition and further enhance its chemical resistance and heat resistance. A preferred upper limit for the intrinsic viscosity is 0.8 dl / g; achieving a viscosity of 0.8 dl / g or lower tends to improve fluidity and facilitate molding. Alternatively, two or more PPE resins with different intrinsic viscosities may be used in combination to achieve this viscosity range.

[0029] The method for producing PPE resin (C) is not particularly limited, and a known method can be employed, for example, by oxidative polymerization of a monomer such as 2,6-dimethylphenol in the presence of an amine copper catalyst. In this case, the intrinsic viscosity can be controlled to a desired range by selecting the reaction conditions. Control of intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.

[0030] The resin composition of the present invention contains PPE resin (C) and / or the aforementioned rubber-reinforced polystyrene or polystyrene (B) in an amount of 52 to 75 parts by mass in total, based on a total of 100 parts by mass of (A) to (C), together with 25 to 48 parts by mass of PPS resin (A). As a result, PPS resin (A) becomes dominant in terms of physical properties, and as a result, high heat resistance and a high degree of low warping can be achieved. The preferred content of (A) to (C) is 30 to 48 parts by mass, particularly 35 to 48 parts by mass, of component (A) based on a total of 100 parts by mass of (A) to (C). The preferred content of component (B) and / or (C) is the amount obtained by subtracting the amount of (A) above from 100 parts by mass. It is preferable that both rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C) are included, and based on a total of 100 parts by mass of (A) to (C), it is preferable that (B) is 15 to 40 parts by mass, of which 15 to 35 parts by mass and (C) is 15 to 40 parts by mass, of which 15 to 35 parts by mass. Furthermore, from the viewpoint of load deflection temperature, the mass ratio (B) / (C) of the content of (B) to (C) is preferably 0.5 or more, more preferably 0.7 or more, even more preferably 0.8 or more, preferably 3 or less, more preferably 2 or less, and most preferably 1.5 or less.

[0031] [Fibrous filler (D)] The resin composition of the present invention contains a fibrous filler (D). Examples of fibrous fillers (D) include glass fibers, carbon fibers, and mineral fibers, but glass fibers are preferred among them.

[0032] Any known glass fiber can be used, regardless of its form when compounded, such as A glass, E glass, alkali-resistant glass compositions containing zirconia components, chopped strand, roving glass, or masterbatches of thermoplastic resin and glass fiber. Among these, alkali-free glass (E glass) is preferred for the purpose of improving the thermal stability of the resin composition.

[0033] The glass fibers may have a round cross-section in the longitudinal direction, and glass fibers with a cross-sectional area ratio of 2 to 6 in the longitudinal direction are also preferred. The cross-sectional area ratio in the longitudinal direction is the ratio of the major axis to the minor axis when a rectangle with the smallest area circumscribed around a cross-section perpendicular to the longitudinal direction of the glass fiber is assumed, and the length of the long side of this rectangle is defined as the major axis and the length of the short side as the minor axis. By including glass fibers with a cross-sectional area ratio of 2 to 6, the glass fibers exhibit a bridging function that connects the phases of the oriented PPS resin (A), making it easier for the PPS resin (A) to become a matrix (sea), which can result in a particularly improved heat resistance, as well as low warping and excellent appearance. Furthermore, when the glass fibers are surrounded by a phase of PPS resin (A), the bridging effect between the PPS resin (A) phases by the glass fibers is enhanced, and in addition, the bulky glass fibers act as a bulking agent for the PPS resin (A), which further improves heat resistance.

[0034] In the case of glass fibers with irregular cross-sections, the ratio of irregularity is more preferably 2.5 or more, even more preferably 3 or more, more preferably 5.5 or less, and even more preferably 5 or less. The shape of the longitudinal cross-section is particularly preferably substantially rectangular. The cross-sectional area of ​​the glass fiber in the longitudinal direction is 180 μm². 2 Ultra 300μm 2 The following is preferable, as such a cross-sectional area makes it easier for the PPS resin (A) to form the matrix, resulting in improved heat resistance. The cross-sectional area is more preferably 180 μm². 2 Super 250μm 2 More preferably 180 μm 2 Super 200μm 2The following applies: The thickness of the glass fibers is not particularly limited, but it is preferable that the short diameter is 2 to 20 μm and the long diameter is 5 to 50 μm.

[0035] The glass fibers may be treated with a sizing agent or a surface treatment agent. Alternatively, during the production of the resin composition of the present invention, a sizing agent or a surface treatment agent may be added separately from the untreated glass fibers to perform surface treatment.

[0036] Examples of sizing agents include resin emulsions such as vinyl acetate resin, ethylene / vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane resin, and polyester resin. Examples of surface treatment agents include aminosilane compounds such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropyltrimethoxysilane; chlorosilane compounds such as vinyltrichlorosilane and methylvinyldichlorosilane; alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloxypropyltrimethoxysilane; epoxysilane compounds such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane; acrylic compounds; isocyanate compounds; titanate compounds; and epoxy compounds. These sizing agents and surface treatment agents may be used in combination of two or more types, and the amount used (amount applied) is usually 10% by mass or less, preferably 0.05 to 5% by mass, relative to the mass of the glass fibers. By limiting the amount applied to 10% by mass or less, a necessary and sufficient effect can be obtained.

[0037] The content of fibrous filler (D) is 5 to 150 parts by mass per 100 parts by mass of the total of 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, even 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, and most preferably 80 parts by mass or less, particularly preferably 60 parts by mass or less. By including it within this range, high heat resistance can be achieved, and the strength and shrinkage reduction effect of the resulting molded article can be enhanced. The fibrous filler (D) may be used in combination of two or more types depending on the required properties.

[0038] In the present invention, it is preferable that the fibrous filler (D) is surrounded by a phase of PPS resin (A) in the cross-sectional structure of the molded article of the resin composition as observed by an electron microscope. Furthermore, it is preferable that the PPS resin (A) forms a sea (matrix) in a sea-island structure, or a co-continuous phase with rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C). Having such a morphological structure specifically improves heat resistance, further enhances low warping, and tends to result in a superior appearance.

[0039] The resin composition of the present invention may contain other inorganic fillers in the form of plates, granules, or amorphous materials, in addition to the fibrous filler (D) described above. Examples of plate-shaped inorganic fillers include talc, glass flakes, mica, kaolin, expanded graphite, flaky graphite, and metal foil. Other granular or amorphous inorganic fillers include ceramic beads, clay, zeolite, barium sulfate, titanium dioxide, silicon dioxide, aluminum oxide, magnesium hydroxide, and zinc sulfide.

[0040] While inorganic fillers other than fibrous filler (D) are effective in reducing warping by reducing anisotropy, they tend to decrease the strength and toughness of the resin composition, so excessive addition is undesirable. When other inorganic fillers are included, the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and among these, 10 parts by mass or less, 7 parts by mass or less, and especially 5 parts by mass or less, based on 100 parts by mass of the total of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C).

[0041] [Epoxy compound (E)] The resin composition of the present invention may also preferably contain an 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) is unevenly distributed at the interface between the PPS resin (A) and the fibrous filler (D) due to its polar affinity. This increases the interfacial strength between the PPS resin (A) and the fibrous filler (D), and consequently improves the mechanical strength, particularly the toughness, of the resin composition. When epoxy compound (E) is included, the preferred content is 0.01 to 5 parts by mass per 100 parts by mass of the total of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). This content improves mechanical strength, particularly toughness. Below 0.01 parts by mass, the above improvement effect is reduced, while above 5 parts by mass, viscosity increases significantly during retention, leading to a decrease in molding stability. The content of epoxy compound (E) is more preferably 0.1 parts by mass or more, even 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, even more preferably 3 parts by mass or less, and among these, 2 parts by mass or less, 1.5 parts by mass or less, and particularly 1 part by mass or less.

[0042] The epoxy compound (E) can be any compound having one or more epoxy groups in one molecule, such as novolac-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, alicyclic epoxy compounds, glycidyl ethers, glycidyl esters, epoxidized butadiene polymers, resorcinol-type epoxy compounds, and the like. Note that the brominated epoxy compounds listed under brominated flame retardants (E) are excluded from this epoxy compound (E) category.

[0043] Examples of novolac-type epoxy compounds include phenol novolac-type epoxy compounds and cresol novolac-type epoxy compounds. Examples of bisphenol A type epoxy compounds include bisphenol A-diglycidyl ether and hydrogenated bisphenol A-diglycidyl ether, while examples of bisphenol F type epoxy compounds include bisphenol F-diglycidyl ether and hydrogenated bisphenol F-diglycidyl ether.

[0044] Examples of alicyclic epoxy compounds include vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxycyclohexyl-3,4-cyclohexyl carboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, and 3,4-epoxycyclohexyl glycidyl ether.

[0045] 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; and diglycidyl ethers such as neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and bisphenol A diglycidyl ether. Examples of glycidyl esters include monoglycidyl esters such as glycidyl benzoate and glycidyl sorbate; and diglycidyl esters such as diglycidyl adipic acid, diglycidyl terephthalate, and diglycidyl orthophthalate.

[0046] Examples of epoxidized butadiene polymers include epoxidized polybutadiene, epoxidized styrene-butadiene copolymers, and epoxidized hydrogenated styrene-butadiene copolymers. Examples of resorcinol-type epoxy compounds include resorcinol diglycidyl ether.

[0047] Furthermore, the epoxy compound (E) may be a copolymer in which a glycidyl group-containing compound is one of the components. For example, a copolymer of a glycidyl ester of an α,β-unsaturated acid and one or more monomers selected from the group consisting of α-olefins, acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters can be mentioned. For example, a preferred example is an epoxy group-containing acrylic (co)polymer. Common epoxy compounds, such as epoxy group-containing olefin elastomers, are inherently flexible and therefore offer excellent toughness, but their mechanical strength improvement is insufficient, and their rigidity is reduced. For these reasons, these elastomer-based materials are not very desirable.

[0048] In this invention, the epoxy compound (E) used has an epoxy equivalent of 150 to 1500 g / eq. If the epoxy equivalent is less than 150 g / eq, the viscosity of the resin composition will be high due to the excessive amount of epoxy groups, and conversely, if the epoxy equivalent is greater than 1500 g / eq, the amount of epoxy groups will be low, making it difficult to sufficiently improve the mechanical strength of the resin composition. The epoxy equivalent is preferably 150 to 1000 g / eq, and more preferably 150 to 500 g / eq. The weight-average molecular weight of the epoxy compound (E) is preferably 300 to 9000. If the weight-average molecular weight exceeds 9000, the compatibility with PPS resin (A), rubber-reinforced polystyrene or polystyrene (B) and PPE resin (C) decreases, and the mechanical strength of the molded article of the resin composition tends to decrease. The weight-average molecular weight is more preferably 7000 or less, and even more preferably 6000 or less. The weight-average molecular weight of epoxy compound (E) is the weight-average molecular weight Mw calculated on a polystyrene basis using GPC.

[0049] As the epoxy compound (E), bisphenol A-type epoxy compounds or novolac-type epoxy compounds obtained from the reaction of bisphenol A or novolac with epichlorohydrin, or epoxy group-containing acrylic (co)polymers are particularly preferred in terms of heat resistance and handling properties.

[0050] [Stabilizer] The resin composition of the present invention is preferably composed of a stabilizer, as this has the effect 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.

[0051] Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphorous acid esters (phosphites), trivalent phosphate esters (phosphonites), and pentavalent phosphate esters (phosphates), with organic phosphite compounds, organic phosphonite compounds, and organic phosphate compounds being preferred.

[0052] Preferably, the organic phosphate compound is one of the following general formulas: (R 1 O) 3-n P(=O)OH n (In the formula, R 1 (where n is an alkyl group or an aryl group, which may be the same or different; n is an integer between 0 and 2.) It is a compound represented by . More preferably, R 1 Examples include long-chain alkyl acid phosphate compounds 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, hexadecyl group, octadecyl group, eicosyl group, and triacontyl group.

[0053] 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, and alkoxypolyethylene glycol acid phosphate. Examples include 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, and bisnonylphenyl acid phosphate. Among these, octadecyl acid phosphate is preferred, and this is commercially available under the trade name "ADEKA Stab AX-71" from ADEKA Corporation.

[0054] Preferably, the organophosphite compound is one of the following general formulas: R 2 OP(OR 3 )(OR 4 ) (In the formula, R 2 , R 3 and R 4 These are a hydrogen atom, an alkyl group with 1 to 30 carbon atoms, or an aryl group with 6 to 30 carbon atoms, and R 2 , R 3 and R 4 At least one of them is an aryl group with 6 to 30 carbon atoms. Examples of compounds represented by [the formula shown] are given.

[0055] Examples of organic phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono(tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenyl di(tridecyl) phosphite), and tetra(tridecyl)4,4'-iso Examples include propyridene 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 diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite. Among these, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is preferred.

[0056] Preferably, the organic phosphonite compound is one of the following general formulas: R 5 -P(OR 6 )(OR 7 ) (In the formula, R 5 , R 6 and R7 Each of these is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and R 5 , R 6 and R 7 At least one of them is an aryl group with 6 to 30 carbon atoms. Examples of compounds represented by [the formula shown] are given.

[0057] Examples of organic phosphonite compounds include tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-n-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, and tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphona Examples include tetrakis(2,6-di-iso-propylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-n-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, and tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite.

[0058] As sulfur-based stabilizers, any conventionally known sulfur atom-containing compound can be used, with thioethers being particularly preferred. Specifically, 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, and trilauryl trithiophosphite. Among these, pentaerythritol tetrakis(3-dodecylthiopropionate) is preferred.

[0059] Examples of phenolic stabilizers include 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), and pentaerythritol tetrakis(3-(3,5-di-neopentyl-4-hydroxyphenyl)propionate). Among these, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred.

[0060] The stabilizer may contain one type, or two or more types in any combination and ratio.

[0061] The stabilizer content is preferably 0.001 to 2 parts by mass per 100 parts by mass of the total of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). If the stabilizer content is less than 0.001 parts by mass, the thermal stability of the resin composition tends to decrease, leading to a decrease in molecular weight and deterioration of color during molding. If it exceeds 2 parts by mass, it becomes an excess, and the occurrence of silver and deterioration of color tend to occur even more easily. The stabilizer content is more preferably 0.01 to 1.5 parts by mass, and even more preferably 0.1 to 1 part by mass.

[0062] [Release agent] The resin composition of the present invention preferably contains a mold release agent (or lubricant). Examples of release agents (lubricants) include hydrocarbon-based 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-based release agents such as stearamide, oleamide, erucamide, behenamide, methylenebisstearate, ethylenestearate, ethylenebisoleamide, ethylenebiserucamide, and ethylenebislauramide; metal soap-based release agents such as calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, and barium stearate; and ester-based release agents such as hydrogenated oils and fats, glycerin monostearate, butyl stearate, pentaerythritol stearate, and stearyl stearate.

[0063] The content of the mold release agent (lubricant) is preferably 0.1 to 3 parts by mass, more preferably 0.2 to 2.5 parts by mass, and even more preferably 0.3 to 2 parts by mass, per 100 parts by mass of the total of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). If it is less than 0.1 parts by mass, surface quality tends to decrease due to poor mold release during melt molding. On the other hand, if it exceeds 3 parts by mass, the kneading workability of the resin composition tends to decrease, and clouding tends to occur on the surface of the molded article.

[0064] [Carbon Black] The resin composition of the present invention preferably contains carbon black. There are no restrictions on the type, raw material, or manufacturing method of carbon black; furnace black, channel black, acetylene black, Ketjen black, etc., can all be used. There are no particular restrictions on the number-average particle size, but it is preferably around 5 to 60 nm.

[0065] It is preferable to use carbon black that has been pre-master-batched with a thermoplastic resin. Preferred thermoplastic resins for master-batching include PPS resin, PPE resin, olefin resin, and styrene resin, with styrene resin being particularly preferred, and acrylonitrile-styrene resin (AS resin) being preferred.

[0066] The carbon black content is preferably 0.1 to 4 parts by mass, more preferably 0.2 to 3 parts by mass, per 100 parts by mass of the total of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C). A content of 0.1 parts by mass or more enhances the effect of obtaining the desired color and can be expected to improve weather resistance, etc. A content of 4 parts by mass or less can be expected to suppress the deterioration of mechanical properties, etc.

[0067] [Other ingredients] The resin composition of the present invention may contain other thermoplastic resins other than the above-mentioned PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C), to the extent that they do not impair the effects of the present invention. Specific examples of other thermoplastic resins include polybutylene terephthalate resin, polyacetal resin, polyamide resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyetherketone resin, and polyolefin resin. However, if other resins are included, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, based on 100 parts by mass of the total of PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C).

[0068] Furthermore, 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 enhancers, anti-dripping agents, ultraviolet absorbers, antistatic agents, anti-fogging agents, anti-blocking agents, plasticizers, dispersants, antibacterial agents, colorants, dyes, and pigments.

[0069] [Manufacturing of resin compositions] The resin composition of the present invention can be manufactured according to conventional methods for preparing resin compositions. Specifically, PPS resin (A), rubber-reinforced polystyrene or polystyrene (B), and PPE resin (C), excluding the fibrous filler (D), along with other resin components and various additives that may be added as desired, are thoroughly mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Alternatively, the resin composition can be prepared by pre-mixing the components, or by pre-mixing only a portion of them, supplying them to the extruder using a feeder, and melt-kneading them. Furthermore, a masterbatch of a portion of the components may be incorporated and melt-kneaded. Moreover, it is possible to manufacture various molded articles by supplying a pre-mixed mixture of the components directly to a molding machine such as an injection molding machine without melt-kneading. It is preferable to side-feed the fibrous filler (D) using a side feeder.

[0070] The heating temperature during melt mixing can usually be appropriately selected from the range of 280 to 350°C. If the temperature is too high, decomposition gases are likely to be generated, which may cause defects in appearance. Therefore, it is desirable to select a screw configuration that takes shear heating into consideration. To suppress decomposition during mixing and subsequent molding processes, it is desirable to use antioxidants and heat stabilizers.

[0071] [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 arbitrarily employed. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding using a heat-insulating mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, and the like. Among these, injection molding and insert molding are particularly preferred.

[0072] The resulting molded articles exhibit low warping, excellent heat resistance, toughness, and strength, as well as superior chemical resistance. Therefore, they are particularly suitable for use as electrical and electronic equipment components, automotive interior and exterior parts, and other electrical components where these properties are strictly required. Examples of electrical and electronic equipment components include connectors, coils, sensors, sensor covers, lamp sockets, resistors, relay cases, miniature switches, coil bobbins, capacitors, various terminal boards, plugs, variable capacitor housings, induction cooker housing components, grill handles, coil peripheral components, rice cooker protective frames, smart meter housings, industrial circuit breaker housings, inverter cases, mobile phone housings, heating equipment housings, battery separators, battery cases, and automotive charging equipment. For automotive interior and exterior parts, it can be particularly suitable for use in vehicle housing components, vehicle battery cases, vehicle battery covers, vehicle battery separators, various motor cases, sensor cases, various valves such as exhaust gas valves, various pipes for fuel, exhaust, and intake systems, air intake nozzles, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, vehicle camera brackets, exhaust gas sensors, holder components, door mirror stays, housings for automotive interior head-up displays, or housings for engine control units (ECUs), as well as for automotive electrical connector components. In particular, the resin composition of the present invention is suitable for automotive housing components and the like. [Examples]

[0073] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

[0074] (Examples 1-4, Comparative Examples 1-4) The ingredients used are as shown in Table 1 below.

[0075] [Table 1]

[0076] Of the components shown in Table 1 above, all components except the fibrous filler (D) were uniformly mixed in a tumbler mixer in the proportions (all parts by mass) shown in Table 2 below. Then, using a twin-screw extruder (TEX30α, manufactured by Japan Steel Works, Ltd., L / D=42), the fibrous filler (D) was added using a side feeder. The resin composition was melt-kneaded under the conditions of a cylinder temperature of 310°C, a discharge rate of 30 kg / h, and a screw rotation speed of 200 rpm. The mixture was rapidly cooled in a water bath and pelletized using a pelletizer to obtain pellets of the resin composition.

[0077] [Tensile breaking strength, tensile elongation] After drying the pellets obtained above at 120°C for 5 hours, ISO multipurpose test specimens (4 mm thick) were injection molded using an injection molding machine manufactured by Japan Steel Works, Ltd. (clamping force 85T) under the conditions of cylinder temperature 320°C and mold temperature 140°C. In accordance with ISO 527, the tensile breaking strength (in MPa) and tensile elongation at breaking (in %) were measured using the above ISO multipurpose test specimen (4 mm thick). [Maximum bending strength, flexural modulus] In accordance with ISO 178, the maximum bending strength (in MPa) and flexural modulus (in MPa) were measured at a temperature of 23°C using the above ISO multipurpose test specimen (4 mm thick). [Charpy impact strength with notch] In accordance with ISO 179, the notched test specimens, which were prepared by notching the above ISO multipurpose test specimen (4 mm thick), were subjected to a notched test at a temperature of 23°C (unit: kJ / m²). 2 ) was measured.

[0078] [Mechanical strength judgment] Based on the above results, the mechanical strength was evaluated and determined according to the following criteria. ○: Meets both tensile strength of 130 MPa or higher and bending strength of 175 MPa or higher. △: Meets both tensile strength of 120 MPa or higher and bending strength of 170 MPa or higher. ×: Does not meet any of the conditions of ○ or △.

[0079] [Load deflection temperature and heat resistance assessment] Using the above ISO multipurpose test specimen (4 mm thick), the temperature of deflection under load was measured in accordance with ISO 75-1 and ISO 75-2 under conditions of a load of 1.80 MPa. The heat resistance was determined according to the following criteria. ○: Load deflection temperature is 175℃ or higher ×: Load deflection temperature is less than 175°C

[0080] [Solder heat resistance test and solder heat resistance judgment] A combustion test specimen measuring 12.5 mm × 125 mm × 1.5 mm in thickness was injection molded using an injection molding machine (Japan Steel Works, Ltd. "J50ADS") under the conditions of a cylinder temperature of 310°C and a mold temperature of 130°C. Using tweezers, the specimen was immersed in a solder bath adjusted to 260°C for 10 seconds, and the condition of the specimen after removal was observed. The solder heat resistance was evaluated and determined based on the following criteria. ○: No abnormalities are observed in terms of shape and appearance. △: The shape is maintained, but external abnormalities such as swelling are observed. ×: Does not retain its shape.

[0081] [Determination of warp amount and warp tendency] Using an injection molding machine (NEX80, manufactured by Nissei Plastic Industrial Co., Ltd.), a disc with a diameter of 100 mm and a thickness of 1.6 mm was molded using a side gate mold under the conditions of cylinder temperature 310°C, mold temperature 130°C, and injection time 0.5 sec, and the amount of warping of the disc (in mm) was determined. The warp resistance was evaluated based on the following criteria. ○: Curvature less than 3mm △: Curvature of 3mm or more, but less than 5mm ×: Curvature of 5mm or more The results are shown in Table 2 below.

[0082] [Table 2] [Industrial applicability]

[0083] The resin composition of the present invention exhibits excellent low warping, heat resistance, and strength, as well as excellent chemical resistance, making it suitable for use in electrical and electronic product components, automotive electronic components, automotive housing components, and the like, where these properties are strictly required.

Claims

1. The MVR measured at 295°C with a 1.00 kgf load was 60-500 cm. ３ A resin composition characterized by containing 25 to 48 parts by mass of polyphenylene sulfide resin (A) at 10 min / 10 min, 52 to 75 parts by mass of amorphous rubber-reinforced polystyrene or polystyrene (B) and / or polyphenylene ether resin (C) in total for (B) and (C), with a total of 100 parts by mass of (A) to (C), 5 to 150 parts by mass of fibrous filler (D), and 0.1 to 5 parts by mass of epoxy compound (E), wherein the epoxy equivalent of epoxy group-containing compound (E) is 150 to 1500 g / eq.

2. The resin composition according to claim 1, wherein the epoxy equivalent of epoxy compound (E) is 150 to 500 g / eq.

3. The resin composition according to claim 1 or 2, wherein the weight-average molecular weight of the epoxy compound (E) is 300 to 9000.

4. The resin composition according to any one of claims 1 to 3, wherein the mass ratio of the content of (B) and (C), (B) / (C), is 0.5 or more.

5. A molded article comprising the resin composition described in any one of claims 1 to 4.

6. A molded article according to claim 5, which is an in-vehicle housing component.

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