JP2014114421A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is used in precision molded articles such as optical instrument mechanism components, components around light source lamps, connector ferrules for optical fibers, printer components, copying machine components, automobile lamp components, automobile radiator tank components, and components in automobile engine rooms and water section pipes or casings as applications, which contains a polymer alloy comprising a polyphenylene sulfide resin and a polyphenylene ether resin, and which has toughness and rigidity well-balancedly and excellent vibration fatigue characteristics.SOLUTION: The resin composition is obtained by feeding a raw material component, which contains a specific amount of a linear type polyphenylene sulfide resin (a), a specific amount of a cross-linked type polyphenylene sulfide resin (b), a specific amount of the polyphenylene ether resin (c), a specific amount of a mixing agent (d) and a specific amount of an inorganic filler (e), to a melt-kneading machine by a specific method and melt-kneading the fed raw material component.

Description

  The present invention relates to a resin composition.

  Polyphenylene sulfide resin is one of crystalline resins with high heat resistance. Polyphenylene sulfide resin is blended with fillers such as glass fiber, and is used as a resin molding material with excellent heat resistance, chemical resistance, rigidity, and flame resistance. ing. In order to meet the further required characteristics of these parts, many improved resin compositions have been proposed.

  As such a resin composition, for example, by adding a specific filler to the polyphenylene sulfide resin, it maintains excellent heat resistance, rigidity, dimensional stability, flame retardancy, etc. In particular, a composition (see, for example, Patent Document 1) in which both excellent thermal rigidity (deflection temperature under load) and surface smoothness for forming a metal film have been proposed.

  Furthermore, a composition (for example, see Patent Document 2) in which mechanical properties, burr reduction, and fluidity are improved by adding a filler to linear polyphenylene sulfide resin and cross-linked polyphenylene sulfide resin has been proposed. .

  In addition, the present applicant is also composed of a specific linear polyphenylene sulfide, a specific cross-linked polyphenylene sulfide, a polyphenylene ether, a specific copolymer and an inorganic filler, and has an excellent balance between heat resistance, toughness and mechanical strength, and molding. The resin composition (for example, refer patent document 3) which improved whitening, surface appearance, and a flame retardance is proposed.

  The resin composition described in these documents is a resin composition obtained by alloying a specific polyphenylene sulfide resin, a specific inorganic filler, and a polyphenylene ether resin, and a balance between the heat resistance and toughness of the molded product and the mechanical strength. Excellent fluidity, burr and surface appearance.

JP 2010-007014 A JP 09-087518 A JP 2006-316245 A

  In recent years, precision molded products such as optical device mechanism parts, parts around light source lamps, printer parts, copier parts, automotive engine room parts, etc. have been made compact, lightweight and thin, so flame retardancy, molding processability, and toughness In addition to being excellent in balance between rigidity and rigidity, improvement in vibration fatigue resistance has been strongly demanded from the viewpoint of extending the life when used in a place where vibration occurs.

  Furthermore, there is also a demand for longer life in pipes and casings around water where polyphenylene sulfide resins having excellent chemical resistance and heat resistance have been used.

  However, the actual polyphenylene sulfide resin composition including the resin composition described in the above-mentioned literature does not sufficiently satisfy the requirements of such vibration fatigue characteristics.

  Therefore, an object of the present invention is to provide a resin composition that is a polymer alloy composed of a polyphenylene sulfide resin and a polyphenylene ether resin and has an excellent balance between toughness and rigidity and vibration fatigue characteristics.

  In order to solve the above-mentioned problems, the present inventors have intensively studied a resin composition containing a polyphenylene sulfide resin and a polyphenylene ether resin, and as a result, a specific polyphenylene sulfide resin and an inorganic filler subjected to a specific surface treatment, And using a specific manufacturing method, it was found that a resin composition excellent in the balance between toughness and rigidity and vibration fatigue characteristics was obtained, and the present invention was achieved.

  That is, the present invention relates to the following.

[1]
(A) Linear polyphenylene sulfide resin, (b) Cross-linked polyphenylene sulfide resin, (c) Polyphenylene ether resin, (d) Admixture and (e) Addition of raw material components containing inorganic filler to melt kneader And a resin composition obtained by melt-kneading,
The total addition amount of (a) and (b) component is 45-95 mass parts with respect to 100 mass parts of total addition amount of (a)-(c) component, and the addition amount of (c) component is 55-55 mass parts. 5 parts by mass, the addition amount of component (d) is 1-20 parts by mass, the addition amount of component (e) is 10-350 parts by mass,
The total addition amount of (a) and (b) component is 100% by mass, the addition amount of (a) component is 5-50% by mass, and the addition amount of (b) component is 95-50% by mass. ,
(A) The component has a melt viscosity of 40 to 120 Pa · s, (b) the component has a melt viscosity of 40 to 200 Pa · s,
(D) The component is a styrenic copolymer containing 0.3 to 20% by mass of a structural unit composed of an unsaturated monomer having a glycidyl group or an oxazolyl group,
(E) component is a surface-treated inorganic filler,
In the resin composition, the components (a) and (b) form a matrix phase, the component (c) forms a domain phase with an average dispersed particle size of 0.5 to 20 μm,
In the melt kneading, a polyphenylene sulfide resin composition in which the component (e) and at least a part of the component (a) and / or at least a part of the component (b) are added and kneaded at the same position of the melt kneader. object.
[2]
In a vibration fatigue test using a JIS K7139 type C test piece and applying a tensile load (100 MPa) with a sine wave with a frequency of 30 Hz in an atmosphere of 23 ° C. according to JIS K7118, the number of vibrations to break is 30,000 times or more. The polyphenylene sulfide resin composition according to [1].
[3]
(C) The polyphenylene sulfide resin composition according to [1] or [2], wherein the component forms a domain phase with an average dispersed particle size of 0.5 to 10 μm.
[4]
In the melt-kneading, the polyphenylene sulfide resin composition according to any one of [1] to [3], wherein the component (e) and the component (a) are supplied to the same position of the melt-kneader.
[5]
(E) The polyphenylene sulfide resin composition according to any one of [1] to [4], wherein the component is a glass fiber that has been surface-treated with aminosilane or epoxysilane, and further converged with epoxy resin or urethane resin.
[6]
The component (d) is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and a styrene-vinyl oxazoline-acrylonitrile copolymer. The polyphenylene sulfide resin composition according to any one of [1] to [5], which is at least one selected from the group consisting of polymers.
[7]
(B) a part of the component, a part of the component (a), a step of adding the component (c) and the component (d) to the melt-kneader and melt-kneading; and the remainder of the component (b) in the melt-kneader It is obtained by using a production method in which a step of adding and melt-kneading, and a step of adding the remainder of component (a) and component (e) to a melt-kneader and melt-kneading are sequentially performed in this order. The polyphenylene sulfide resin composition according to any one of 1] to [6].

  The resin composition of the present invention is excellent in the balance between toughness and rigidity and vibration fatigue characteristics.

The preferable example (manufacturing method 1-6) of the manufacturing method of the resin composition of this embodiment is shown typically. The example (manufacturing method 7-9) of the manufacturing method of the conventional resin composition is shown typically.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to the following embodiment. The present invention can be variously modified without departing from the gist thereof.

≪Polyphenylene sulfide resin composition≫
The polyphenylene sulfide resin composition of the present embodiment (hereinafter also abbreviated as “resin composition”) includes (a) a linear polyphenylene sulfide resin, (b) a crosslinked polyphenylene sulfide resin, (c) a polyphenylene ether resin, ( d) A resin composition obtained by adding a raw material component containing an admixture and (e) an inorganic filler to a melt kneader and melt kneading.
The total addition amount of (a) and (b) component is 45-95 mass parts with respect to 100 mass parts of total addition amount of (a)-(c) component, and the addition amount of (c) component is 55-55 mass parts. 5 parts by mass, the addition amount of component (d) is 1-20 parts by mass, the addition amount of component (e) is 10-350 parts by mass,
The total addition amount of (a) and (b) component is 100% by mass, the addition amount of (a) component is 5-50% by mass, and the addition amount of (b) component is 95-50% by mass. ,
(A) The component has a melt viscosity of 40 to 120 Pa · s, (b) the component has a melt viscosity of 40 to 200 Pa · s,
(D) The component is a styrenic copolymer containing 0.3 to 20% by mass of a structural unit composed of an unsaturated monomer having a glycidyl group or an oxazolyl group,
(E) component is a surface-treated inorganic filler,
In the resin composition, the components (a) and (b) form a matrix phase, the component (c) forms a domain phase with an average dispersed particle size of 0.5 to 20 μm,
In the melt kneading, the component (e) and at least a part of the component (a) and / or at least a part of the component (b) are added to the same position of the melt kneader and kneaded.

  The resin composition of the present embodiment includes (a) a linear polyphenylene sulfide resin and (b) a polyphenylene sulfide resin composed of a crosslinked polyphenylene sulfide resin, (c) a polyphenylene ether resin, (d) an admixture, ) Contains a surface-treated inorganic filler.

<Polyphenylene sulfide resin>
A polyphenylene sulfide resin (hereinafter also abbreviated as “PPS”) is produced by (a) a linear polyphenylene sulfide resin (hereinafter also abbreviated as “linear PPS”) and (b) a cross-linked polyphenylene sulfide resin (hereinafter referred to as “PPS”). It is also abbreviated as “crosslinked PPS”.

  Linear PPS is a polymer containing an arylene sulfide repeating unit represented by the following general formula (formula 1) usually at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%.

[—Ar—S—] (Formula 1)
(Here, Ar represents an arylene group, and the arylene group is not particularly limited. For example, p-phenylene group, m-phenylene group, substituted phenylene group (substituents are alkyl groups having 1 to 10 carbon atoms). And a phenyl group are preferred.), P, p'-diphenylenesulfone group, p, p'-biphenylene group, p, p'-diphenylenecarbonyl group, naphthylene group and the like.

  Linear PPS may be a homopolymer having one type of arylene group as a structural unit, and is a copolymer obtained by mixing two or more different arylene groups from the viewpoint of processability and heat resistance. Also good. Among these, a linear polyphenylene sulfide resin having a repeating unit of p-phenylene sulfide as a main constituent element is preferable because it is excellent in processability and heat resistance and is easily available industrially. (A) A component may be used individually by 1 type and may be used together 2 or more types.

  The method for producing this linear PPS is not particularly limited. For example, a method of polymerizing a halogen-substituted aromatic compound (for example, p-dichlorobenzene) in the presence of sulfur and sodium carbonate, a halogen-substituted aromatic compound (for example, p-type). -Dichlorobenzene) in a polar solvent, (i) in the presence of sodium sulfide, (ii) in the presence of sodium hydrogen sulfide and sodium hydroxide, (iii) in the presence of hydrogen sulfide and sodium hydroxide, Or (iv) a method of polymerizing in the presence of sodium aminoalkanoate, self-condensation of p-chlorothiophenol, etc., among which amide solvents such as N-methylpyrrolidone and dimethylacetamide, and sulfone solvents such as sulfolane Among them, a method of reacting sodium sulfide with p-dichlorobenzene is suitable.

  These production methods are known, for example, U.S. Pat. No. 2,513,188, JP-B 44-27671, JP-B 45-3368, JP-B 52-12240, JP-A 61-225217. And US Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 5-222196, etc., and prior art exemplified in these patents, etc. The linear PPS can be obtained by these methods.

  Preferred (a) linear PPS has an extraction amount by methylene chloride of 0.7% by mass or less, preferably 0.5% by mass or less, and a terminal-SX group (S is a sulfur atom, X is an alkali metal or hydrogen atom) Is a linear polyphenylene sulfide resin having a concentration of 20 μmol / g or more, preferably 20 to 60 μmol / g.

  Here, the amount of extraction with methylene chloride can be measured by the following method.

  That is, 5 g of linear PPS powder is added to 80 mL of methylene chloride, Soxhlet extraction is performed for 6 hours, and then cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Further, the container used for the above extraction is washed in three portions with a total of 60 mL of methylene chloride, and the washing liquid is collected in the weighing bottle. Next, the methylene chloride in the weighing bottle is removed by evaporation by heating to about 80 ° C., and the residue is weighed. From this amount of residue, the amount extracted with methylene chloride, that is, the ratio of the amount of oligomers present in the linear PPS can be determined.

  The terminal-SX group can be quantified by the following method. That is, the linear PPS powder is previously dried at 120 ° C. for 4 hours. 20 g of this dried linear PPS powder is added to 150 g of N-methyl-2-pyrrolidone, and vigorously stirred and mixed at room temperature for 30 minutes so as to eliminate powder agglomerates to obtain a slurry. After filtering the slurry, the obtained filter cake is repeatedly washed 7 times with 1 liter of warm water of about 80 ° C. each time. The filter cake obtained here is put into 200 g of pure water and slurried again, and then 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. The slurry is then stirred at 25 ° C. for 30 minutes, filtered, and then washed six times with 1 liter of warm water at about 80 ° C. each time. The obtained filter cake is re-slurried in 200 g of pure water, and then the slurry is titrated with 1N sodium hydroxide. The amount of terminal-SX groups present in the linear PPS can be known from the amount of sodium hydroxide consumed here.

  Specific examples of the method for producing linear PPS satisfying an extraction amount with methylene chloride of 0.7% by mass or less and a terminal-SX group satisfying 20 μmol / g or more are not particularly limited, but, for example, Japanese Patent Laid-Open No. 8-255357 Can be mentioned. Specifically, a reaction between an alkali metal sulfide and a dihaloaromatic compound in an organic amide solvent, and a part of the gas phase in the reaction vessel is cooled by cooling the gas phase portion of the reaction vessel during the reaction. Can be condensed, and the oligomer component can be reduced by refluxing it to the liquid layer above the reaction solution.

  (B) Crosslinked (including semi-crosslinked) polyphenylene sulfide resins are polymerized from the above-described linear polyphenylene sulfide resin, and then heat-treated at a temperature below the melting point of the polyphenylene sulfide resin in the presence of oxygen to undergo oxidative crosslinking. The polymer molecular weight and viscosity are moderately increased by promotion.

  Among these (b) cross-linked PPSs, the preferred cross-linked PPS is collected in a molten state at 320 ° C. from the viewpoints of gas / smear generation and releasability when the resin composition of the present embodiment is molded. It is a crosslinked polyphenylene sulfide resin having a volatile content of 1000 ppm or less. Here, the volatile matter collected in the 320 ° C. molten state can be determined by the following method. First, 0.5 g of crosslinked PPS powder is weighed in a test tube with a sealed stopper having an air flow inlet and outlet. While the crosslinked PPS powder weighed in the test tube is immersed in a solder bath heated to 320 ° C. for 30 minutes, nitrogen gas is injected at a flow rate of 100 cc / min from the air flow inlet of the test tube. A gas containing a volatile component derived from the cross-linked PPS generated in the test tube is purged from an air flow outlet of the test tube. The purged gas is injected from an air flow inlet of a sealed tube having an air flow inlet and outlet containing acetone, and bubbled in acetone in the test tube to dissolve volatile components in the crosslinked PPS in acetone. The volatile matter of the crosslinked PPS dissolved in acetone is subjected to temperature rise analysis in the range of 50 ° C. to 290 ° C. using a gas chromatograph mass spectrometer (GC-MS). All components detected by this temperature rise analysis are quantified assuming the same sensitivity as monochlorobenzene, and the volatile content in the crosslinked PPS can be obtained.

  The method for obtaining a crosslinked PPS having a volatile content of 1000 ppm or less collected in a molten state at 320 ° C. is not particularly limited. For example, a method of adjusting the polymer concentration and solvent composition in the step of polymerizing linear PPS, polymerized A method of performing specific washing when recovering the polymer in the stage, and a method of adjusting the temperature, time, etc. of the high temperature treatment in the subsequent crosslinking stage can be mentioned.

  (B) A component may be used individually by 1 type and may be used together 2 or more types.

  Further, these PPS (linear PPS, crosslinked PPS) may be acid-modified PPS. Here, the acid-modified PPS is obtained by modifying the PPS with an acid compound, and the acid compound is not particularly limited. For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, Examples thereof also include unsaturated carboxylic acids such as maleic anhydride or anhydrides thereof, saturated aliphatic carboxylic acids and aromatic substituted carboxylic acids. In addition, inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid and carbonic acid can also be mentioned as the acid compound.

  The melt viscosity of linear PPS is 40 to 120 Pa · s, preferably 50 to 100 Pa · s. The melt viscosity of the crosslinked PPS is 40 to 200 Pa · s, preferably 60 to 100 Pa · s. When the melt viscosity of the linear PPS and the crosslinked PPS is 40 Pa · s or more, the balance between toughness and rigidity of the resin composition and vibration fatigue characteristics can be improved. Further, the linear PPS has a melt viscosity of 120 Pa · s or less, and the cross-linked PPS has a melt viscosity of 200 Pa · s or less, thereby improving the reactivity between the components (a) and (b) and the component (d). The miscibility between the polyphenylene sulfide resin of the components (a) and (b) and the polyphenylene ether resin of the component (c) is improved. The resin composition obtained by this has the effect that it is excellent in the balance between toughness (impact strength) and rigidity, in addition to greatly suppressing the occurrence of burrs in the molded product.

  As a method of obtaining linear PPS having a melt viscosity within the above range, a method of appropriately changing the polymerization conditions, specifically, for example, a polymerization temperature, a polymerization time, a raw material concentration, a pressure in the reactor, a method at the time of washing, etc. The method of changing suitably is mentioned. Further, as a method of obtaining a crosslinked PPS having a melt viscosity within the above range, in addition to the method of obtaining the linear PPS during polymerization, a method of appropriately changing the conditions during the crosslinking reaction, specifically, for example, a crosslinking reaction temperature, Examples thereof include a method of appropriately changing the time and oxygen concentration.

  Here, in the specification, the melt viscosity is JIS K-7210 as a reference test method, and PPS was preheated at 300 ° C. for 6 minutes using a flow tester (CFT-500 manufactured by Shimadzu Corporation). Then, it is the value measured by load 196N, die length (L) / die diameter (D) = 10 mm / 1 mm.

  When the total of (a) linear PPS and (b) crosslinked PPS is 100% by mass, the blending ratio ((a) / (b)) of component (a) to component (b) is 5 to 50% by mass / It is 95-50 mass%, 10-50 mass% / 90-50 mass% is preferable, More preferably, it is 15-50 mass% / 85-50 mass%. When the blending ratio of the (a) linear PPS is 5% by mass or more and 50% by mass or less in the total polyphenylene sulfide resin composed of the components (a) and (b), toughness (impact strength), rigidity and A resin composition having an excellent balance of mold releasability during molding can be provided.

<(C) Polyphenylene ether resin>
The polyphenylene ether resin as component (c) is a homopolymer and / or copolymer polyphenylene ether resin (hereinafter also abbreviated as “PPE”) containing a repeating unit represented by the following bond unit (formula 2). is there. Further, the component (c) may be a mixture of the polyphenylene ether resin and the styrene resin in an arbitrary ratio.

(Where R1, R2, R3 and R4 are each a hydrogen atom, a halogen atom, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, And are selected from the group consisting of a hydrogenoxy group and a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different.

  PPE has a polystyrene-reduced number average molecular weight measured by GPC (gel permeation chromatography), preferably 1000 or more, more preferably 1500 to 50000, and still more preferably 1500 to 30000.

  Specific examples of the PPE are not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols ( Examples thereof include polyphenylene ether copolymers such as copolymers with 2,3,6-trimethylphenol and 2-methyl-6-butylphenol. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

  The method for producing such PPE is not particularly limited. For example, oxidative polymerization of 2,6-xylenol is performed using, for example, a complex of Hay cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. The method of manufacturing by is mentioned. In addition, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628. The method described in gazette gazette etc. is also mentioned.

  The component (c) can be used even at 100% by mass of the above-mentioned PPE component, but a component composed of PPE / styrene resin = 1 to 99% by mass / 99 to 1% by mass can be preferably used. . Among them, in the resin composition of the present embodiment, in improving the processability of the resin composition containing the inorganic filler of the component (e) described later, the ratio of PPE / styrene resin as the component (c) Is preferably a mixture of 80/20 to 20/80 (unit: mass%).

  The styrenic resin is not particularly limited. For example, a rubbery polymer is contained in a matrix composed of a homopolymer of a styrene compound, a copolymer of two or more styrene compounds, and a polymer of styrene compounds. Examples thereof include rubber-modified styrene resin (high impact polystyrene) dispersed in the form of particles. The styrenic compound that provides these polymers is not particularly limited, and examples thereof include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methyl. Examples include styrene, 2,4-dimethylstyrene, monochlorostyrene, p-tert-butylstyrene, and the like.

  These styrenic compounds may be a copolymer obtained by using two or more kinds in combination, but among them, polystyrene obtained by polymerization using styrene alone is preferable. As these polymers, polystyrene having a stereoregular structure such as atactic polystyrene and syndiotactic polystyrene can be used effectively.

  The styrene resin used in combination with PPE includes styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, and styrene-glycidyl methacrylate, which are admixtures of the following component (d). -Styrene copolymers such as acrylonitrile copolymer, styrene-vinyl oxazoline copolymer and styrene-vinyl oxazoline-acrylonitrile copolymer, and vinyl aromatic compounds corresponding to component (f) and conjugated diene compounds. A styrene-butadiene block copolymer represented by a block copolymer obtained by polymerization and a hydrogenated block copolymer obtained by further hydrogenation reaction of this block copolymer and a hydrogenated product thereof. Block copolymers are not included.

  (C) A component may be used individually by 1 type and may be used together 2 or more types.

  In the resin composition of the present embodiment, the total addition amount of the components (a) and (b) is 45 to 95 parts by mass with respect to 100 parts by mass of the total addition amount of the components (a) to (c). It is preferable that it is -90 mass parts, It is more preferable that it is 50-80 mass parts, The addition amount of (c) component is 55-5 mass parts, It is preferable that it is 60-10 mass parts, 50 More preferably, it is -20 mass parts.

  If the addition amount of the polyphenylene ether-based resin as the component (c) is 5 parts by mass or more and 55 parts by mass or less, generation of burrs during molding can be greatly suppressed, and mold releasability and heat resistance can be achieved. The resin composition excellent in the balance of property and toughness (impact strength) and rigidity can be provided.

<(D) Admixture>
The admixture used as the component (d) is a styrene copolymer containing 0.3 to 20% by mass of a structural unit composed of an unsaturated monomer having a glycidyl group or an oxazolyl group. The component (d) acts as an emulsifying dispersant when the polyphenylene sulfide resin of the components (a) and (b) and the polyphenylene ether resin of the component (c) are mixed, and the resulting resin composition is molded. In addition to remarkably reducing the occurrence of burrs in products, it has the effect of being excellent in the balance between toughness (impact strength) and rigidity.

  As the styrene copolymer of component (d), a copolymer of an unsaturated monomer having a glycidyl group and / or an oxazolyl group and a monomer having styrene as a main component can be more preferably used.

  The monomer having styrene as the main component herein may contain other monomer copolymerizable with styrene, but at least 65% by mass of the styrene component is contained, preferably 75-100 of the styrene component. The styrene component is contained in an amount of 100% by mass. When the content of the styrene component in the monomer containing styrene as the main component is within the above range, the miscibility of the polyphenylene sulfide resin of the components (a) and (b) and the polyphenylene ether resin of the component (c) is maintained. Can do.

  Specific examples of the styrene copolymer of component (d) are not particularly limited. For example, a copolymer of an unsaturated monomer having a glycidyl group and / or an oxazolyl group and a styrene monomer; glycidyl group and / or oxazolyl Examples thereof include a copolymer of an unsaturated monomer having a group and a monomer comprising styrene / acrylonitrile = 90 to 75% by mass / 10 to 25% by mass.

  The unsaturated monomer having a glycidyl group is not particularly limited. For example, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl Examples include itaconate, and glycidyl methacrylate is particularly preferable.

  As the unsaturated monomer having an oxazolyl group, for example, 2-isopropenyl-2-oxazoline is industrially available and can be preferably used.

  These other unsaturated monomers copolymerized with the unsaturated monomer having a glycidyl group and / or an oxazolyl group are not particularly limited, in addition to the styrene monomer. For example, a vinyl cyanide monomer such as acrylonitrile is used as a copolymerization component. , Vinyl acetate, (meth) acrylic acid ester and the like. The styrene copolymer of component (d) used in the present embodiment has at least 65 masses of structural units composed of styrene monomers in the structural units excluding the structural units composed of unsaturated monomers having a glycidyl group and / or an oxazolyl group. % Or more is preferable. Moreover, the structural unit which consists of an unsaturated monomer which has a glycidyl group and / or an oxazolyl group is 0.3-20 mass% in the styrene-type copolymer of (d) component, Preferably it is 1-15 mass%, More preferably Contains 3 to 10% by mass.

  If content of the structural unit which consists of an unsaturated monomer which has a glycidyl group and / or an oxazolyl group in this (d) component styrene-type copolymer is 0.3 mass% or more, and it is 20 mass% or less The miscibility between the polyphenylene sulfide resin of the components (a) and (b) and the polyphenylene ether resin of the component (c) is improved. The resin composition thus obtained can greatly suppress the occurrence of burrs in the molded product, and is excellent in the balance between toughness (impact strength) and rigidity.

  Examples of the styrene-based copolymer of the component (d) are not particularly limited. For example, styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene-glycidyl methacrylate-acrylonitrile copolymer, Examples thereof include a styrene-vinyl oxazoline copolymer and a styrene-vinyl oxazoline-acrylonitrile copolymer. These (d) components may be used individually by 1 type, and may be used together 2 or more types.

  In the resin composition of the present embodiment, the amount of the admixture of the component (d) is 1 to 20 parts by mass with respect to the total of 100 parts by mass of the components (a) to (c) described above, preferably It is 2-15 mass parts, More preferably, it is 3-10 mass parts. When the added amount of the component (d) is 1 part by mass or more, the miscibility between the polyphenylene sulfide resin of the components (a) and (b) and the polyphenylene ether resin of the component (c) is improved, and (d) If the added amount of the component is 20 parts by mass or less, the resulting resin composition can largely suppress the occurrence of burrs in the molded product, and also has a balance between vibration fatigue characteristics, toughness (impact strength) and rigidity. Excellent.

<(E) Inorganic filler>
The surface-treated inorganic filler used as the component (e) can improve the balance between vibration fatigue properties, heat resistance, toughness and rigidity of the resulting resin composition, and is further subjected to a specific surface treatment. Thus, the vibration fatigue characteristics of the resin composition obtained can be drastically improved.

  (E) The surface-treated inorganic filler is not particularly limited. For example, glass fiber (long glass fiber, chopped strand glass fiber), glass flake, glass bead, glass microballoon, carbon fiber, potassium titanate. Fiber, stainless fiber, steel fiber, aramid fiber, boron whisker fiber, wollastonite, mica, talc, silica, clay, titanium oxide, magnesium oxide, calcium carbonate, fly ash, etc. fiber, powder, flake, spherical Inorganic fillers may be treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aliphatic metal salt, and treated with a urethane resin or an epoxy resin as a binder.

  Among these surface treatment agents, a silane coupling agent is preferable, and aminosilane or epoxysilane is more preferable.

  The component (e) is preferably a glass fiber that has been surface-treated with aminosilane or epoxysilane, and further converged with epoxy resin or urethane resin.

  In the resin composition of the present embodiment, the added amount of the inorganic filler of the component (e) is 10 to 350 parts by mass with respect to the total of 100 parts by mass of the components (a) to (c) described above. Preferably it is 10-150 mass parts, More preferably, it is 10-100 mass parts.

  When the added amount of the inorganic filler as the component (e) is 10 parts by mass or more, the heat resistance, the balance between toughness and rigidity, and vibration fatigue characteristics of the obtained resin composition can be improved. If the addition amount of the component inorganic filler is 350 parts by mass or less, a resin composition having excellent molding processability can be obtained.

<Other ingredients>
In the resin composition of the present embodiment, as long as the balance of toughness and rigidity and vibration fatigue characteristics are not impaired, a thermal stabilizer, an antioxidant, an ultraviolet absorber, etc., as necessary, in addition to the above components Known release agents such as stabilizers, crystal nucleating agents, conductivity imparting agents, antistatic agents, flame retardants, colorants such as pigments and dyes, polyethylene wax, polypropylene wax, montanate wax, stearate wax, etc. It can be added as appropriate.

<Characteristics of resin composition>
In the resin composition of the present embodiment, the polyphenylene sulfide resin of the components (a) and (b) forms a matrix phase, and the polyphenylene ether resin of the component (c) has an average dispersed particle size of 0.5 to 20 μm, preferably Forms a domain phase at 0.5 to 10 μm. Thereby, the resin composition of this embodiment is excellent in the balance of the more outstanding vibration fatigue characteristic, moldability, toughness, and mechanical strength.

  Such a morphology (the polyphenylene sulfide resin of the components (a) and (b) forms the matrix phase / the polyphenylene ether resin of the component (c) forms the domain phase) is obtained by cutting a test piece of the resin composition with a diamond knife, This can be confirmed by observing the cut surface in the reflection mode using a microscope. Furthermore, the average dispersed particle size of the polyphenylene ether resin of component (c) can be calculated by measuring the size of the domain phase particles using the photograph taken of the morphology observed above.

  As a method for controlling the average dispersed particle size of the component (c) within the above range, there may be mentioned a method in which the constituent components of the resin composition are adjusted as described above and a resin composition is obtained by the production method described later.

  The resin composition of the present embodiment is preferably subjected to a vibration fatigue test, and the number of vibrations when ruptured is preferably 30,000 or more. When the number of vibrations at the time of the fracture is 30,000 times or more, practically sufficient vibration fatigue resistance is obtained in a molded part using the resin composition (particularly a water-based part used at 120 ° C. or lower). be able to.

  This vibration fatigue test uses a JIS K7139 type C test piece, and applies a tensile load (100 MPa) with a sine wave with a frequency of 30 Hz in an atmosphere of 23 ° C. according to JIS K7118 using a vibration fatigue tester. Do. The number of vibrations broken by this vibration fatigue test can be determined.

<Method for producing resin composition>
The resin composition of the present embodiment contains (a) a linear polyphenylene sulfide resin, (b) a crosslinked polyphenylene sulfide resin, (c) a polyphenylene ether resin, (d) an admixture, and (e) an inorganic filler. It can obtain by adding the raw material component to melt-kneader and melt-kneading. In the melt kneading, the component (e), at least a part of the component (a) and / or at least a part of the component (b) are added to the same position of the melt kneader and kneaded. Further, in the melt kneading, it is preferable that the component (e) and the component (a) are supplied to the same position of the melt kneader.

  The resin composition containing the specific amount of components (a) to (e) is not necessarily excellent in the balance between toughness and rigidity and vibration fatigue properties. Satisfying this composition and "in the above melt kneading, the component (e) and at least a part of the component (a) and / or at least a part of the component (b) are supplied to the same position of the melt kneader. By satisfying the requirement of “kneaded”, the balance between toughness and rigidity of the obtained resin composition and vibration fatigue characteristics can be improved. As long as the resin can be melted and kneaded, the “melt kneader” is not particularly limited. For example, a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer Among them, a twin-screw extruder is preferable. Specific examples include the ZSK series manufactured by WERNER & PFLIDEERER, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

  In the present specification, “supply to the same position” does not mean that both are supplied to exactly the same point, but in the melt-kneading process, (a) and / or (b) component and ( As long as the work given to e) component becomes the same, both may be "supplied to the same position". In an extruder in which materials are supplied from a plurality of feeders, the components (a) and / or (b) and (e) are supplied from the same feeder. In an extruder having a plurality of barrels, a mode in which the same barrel is fed is a category of “feed to the same position”.

  The resin composition of this embodiment comprises a step of adding a part of component (b), a part of component (a), a component (c) and a component (d) to a melt-kneader and melt-kneading (b) The step of adding the remainder of the component to the melt kneader and melt kneading, and the step of adding the remainder of the component (a) and the component (e) to the melt kneader and melt kneading are performed in this order. It is preferably obtained using a manufacturing method.

  The preferable aspect of the manufacturing method of the resin composition of this embodiment using an extruder is described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is in the range of 20 to 60, preferably in the range of 30 to 50. The extruder is provided with a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second to third raw material supply port on the downstream side, and a second vacuum vent on the downstream side. Those provided are preferred. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and the second to third raw material supply ports and the second vacuum vent are provided. It is more preferable to provide a kneading section between them. Although the raw material supply method to the 2nd-3rd raw material supply port is not specifically limited, A forced side feeder is inserted from an extruder side opening port rather than mere addition supply from an extruder 2nd-3rd raw material supply port opening port. It is more stable and preferable to use and supply. In particular, when a large amount of powder, filler or the like is contained, the forced side feeder supplied from the extruder side is more preferable, and the forced side feeder is provided in the second to third raw material supply ports, and these powder, filler, etc. It is more preferable to divide and supply. And the upper open port of the extruder 2nd-3rd raw material supply port can also be made open in order to extract the air to carry. The melt kneading temperature and screw rotation speed at this time are not particularly limited, but can normally be arbitrarily selected from a melt kneading temperature of 300 to 350 ° C. and a screw rotation speed of 100 to 1200 rpm.

  Production methods 1 to 6 in FIG. 1 schematically show preferable examples of the production method of the resin composition. In the figure, a long arrow pointing to the right represents an extruder, and a short arrow pointing downward represents a position where a material is supplied from the feeder. Production methods 1 to 6 are as follows.

Manufacturing method 1. A part of the component (a) and the components (c) to (d) are supplied from the first supply port, the component (b) is then supplied to the second supply port, the remainder of the component (a) and the component (e) are third. A method in which melt kneading is continued from the supply port and melt kneading is continued.
Manufacturing method 2. A part of component (a) and components (b) to (d) are supplied from the first supply port, and then the remainder of component (a) and component (e) are supplied from the second supply port in a melt-kneaded state. Further, a method in which melt kneading is continued.
Manufacturing method 3. A part of (a) to (b) and the components (c) to (d) are supplied from the first supply port, then the rest of the components (a) to (b) and the component (e) are supplied from the second supply port. A method in which melt-kneading is performed and melt-kneading is continued.
Manufacturing method 4. A method in which the components (b) to (d) are supplied from the first supply port, the components (a) and (e) are then supplied from the second supply port in a melt-kneaded state, and the melt-kneading is continued.
Manufacturing method 5. (A) The method of supplying the whole quantity of a component-(e) component from a 1st raw material supply port, and melt-kneading.
Manufacturing method 6. Components (a), (c) to (d) are supplied from the first raw material supply port, components (b) and (e) are supplied from the second supply port in a melt-kneaded state, and further melt-kneaded. How to continue.

  On the other hand, the manufacturing methods 7-9 are shown in FIG. 2 as an example of the conventional resin composition. Conventionally, as shown in production methods 7 to 9, it is common to add the component (e) downstream of the components (a) and / or (b). This is to prevent the components (a) and / or the component (b) and the component (e) from being added at the same time to be defibrated by the indented side feeder and easily clogged. It has been found for the first time that a resin composition having good vibration fatigue resistance can be obtained by supplying the components a) and / or (b) and the component (e) to the melt-kneader. Production methods 7 to 9 are as follows.

Manufacturing method 7. A method in which the components (a) to (d) are supplied from the first raw material supply port, the component (e) is supplied from the second supply port in a melt-kneaded state, and the melt-kneading is continued.
Manufacturing method 8. Components (a), (c) to (d) are supplied from the first raw material supply port, then (b) component is supplied from the second supply port, and (e) component is supplied from the third supply port in a melt-kneaded state. A method of supplying and continuing melt kneading.
Manufacturing method 9. A part of (a) to (b) and the components (c) to (d) are supplied from the first supply port, the remainder of the components (a) to (b) is then supplied to the second supply port, and the component (e) is supplied. A method in which a melt kneaded state is supplied from a third supply port and the melt kneading is continued.

  As in production methods 1 to 6, the resin composition obtained by adopting a production method in which the components (a) and / or (b) and the component (e) are added at the same time is obtained from the components (a) to (e). Each component can take an excellent uniform dispersion form. Moreover, according to the manufacturing methods 1-6, the mixing | blending effect of (d) component which is an admixture is expressed most notably, and the crushing in the melt-kneading of the surface-treated inorganic type filler of (e) component is suppressed. In addition, since the interfacial wettability with the polyphenylene sulfide resin is improved, a resin composition having excellent vibration fatigue characteristics can be obtained.

  The resin composition thus obtained can be used as a molding material that can be a precision molded product. The molding method is not particularly limited. For example, molding methods such as injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, film molding, hot press molding, rotational molding, and lamination molding. Is applicable.

  Molded products obtained by these molding methods include parts in optical engine mechanisms such as optical device mechanism parts, light source lamp surrounding parts, optical fiber connector ferrules, printer parts, copying machine parts, automobile radiator tank parts, etc. It can be widely used as molded products such as water pipes and casings.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, it is not limited by these Examples.

  In addition, the used raw material is as follows.

(A) Component Linear Polyphenylene Sulfide Resin The following linear polyphenylene sulfide resin (hereinafter also referred to as “linear PPS”) obtained according to Example 1 of Japanese Patent Laid-Open No. 8-253587 was used.
(A-1): A linear PPS having a repeating unit of p-phenylene sulfide having a melt viscosity of 30 Pa · s, an extraction amount by methylene chloride of 0.7% by mass, and a terminal-SX group amount of 32 μmol / g (a -1).
(A-2): A linear PPS having a repeating unit of p-phenylene sulfide having a melt viscosity of 45 Pa · s, an extraction amount by methylene chloride of 0.4% by mass, and a terminal-SX group amount of 26 μmol / g (a -2).
(A-3): A linear PPS having a repeating unit of p-phenylene sulfide having a melt viscosity of 120 Pa · s, an extraction amount by methylene chloride of 0.5% by mass, and a terminal-SX group amount of 24 μmol / g (a -3).
(A-4): A linear PPS having a repeating unit of p-phenylene sulfide having a melt viscosity of 160 Pa · s, an extraction amount by methylene chloride of 0.6% by mass, and a terminal-SX group amount of 23 μmol / g (a -4).

  In this example, the melt viscosity is measured after preheating PPS at 300 ° C. for 6 minutes using a flow tester (CFT-500, manufactured by Shimadzu Corporation) using JIS K-7210 as a reference test method. , Load 196N, die length (L) / die diameter (D) = 10 mm / 1 mm.

  In this example, the amount of extraction with methylene chloride was measured by the following method.

  First, 5 g of linear PPS powder was added to 80 mL of methylene chloride, soxhlet extraction was performed for 6 hours, and then cooled to room temperature, and the extracted methylene chloride solution was transferred to a weighing bottle. Furthermore, the container used for the above extraction was washed in three portions with a total of 60 mL of methylene chloride, and the washing solution was collected in the weighing bottle. Next, the methylene chloride in the weighing bottle was removed by evaporation by heating to about 80 ° C., and the residue was weighed. The amount extracted with methylene chloride, that is, the ratio of the amount of oligomer present in the linear PPS was determined from the amount of the residue.

  Furthermore, in this example, the terminal-SX group was quantified by the following method.

  First, the linear PPS powder was previously dried at 120 ° C. for 4 hours. 20 g of this dried linear PPS powder was added to 150 g of N-methyl-2-pyrrolidone, and the mixture was vigorously stirred and mixed at room temperature for 30 minutes so as to eliminate powder agglomerates to obtain a slurry. After filtering the slurry, washing of the obtained filter cake was repeated 7 times using 1 liter of warm water of about 80 ° C. each time. The filter cake obtained here was put into 200 g of pure water to make a slurry again, and then 1N hydrochloric acid was added to adjust the pH of the slurry to 4.5. Next, the slurry was stirred at 25 ° C. for 30 minutes and filtered, and then the obtained filter cake was repeatedly washed 6 times with 1 liter of hot water of about 80 ° C. each time. The obtained filter cake was put into 200 g of pure water and slurried again, and then the slurry was titrated with 1N sodium hydroxide. The amount of terminal-SX group present in the linear PPS was calculated from the amount of sodium hydroxide consumed here.

(B) Component Crosslinked Polyphenylene Sulfide Resin The following crosslinked polyphenylene sulfide resin (hereinafter also referred to as “crosslinked PPS”) was used.
(B-1): Cross-linked PPS (K-1G, manufactured by DIC EP) having a melt viscosity of 35 Pa · s and a volatile content of 200 ppm was defined as (b-1).
(B-2): A cross-linked PPS (MB600-80G manufactured by DIC EP Co., Ltd.) having a melt viscosity of 45 Pa · s and a volatile content of 170 ppm was defined as (b-2).
(B-3): Cross-linked PPS (K-2G, manufactured by DIC EP) having a melt viscosity of 60 Pa · s and a volatile content of 160 ppm was defined as (b-3).
(B-4): A cross-linked PPS having a melt viscosity of 200 Pa · s and a volatile content of 120 ppm was defined as (b-4).
(B-5): A cross-linked PPS having a melt viscosity of 250 Pa · s and a volatile content of 180 ppm was defined as (b-5).

  In this example, the volatile matter was determined by the following method.

  First, 0.5 g of cross-linked PPS powder was weighed into a test tube with a sealed plug having an air flow inlet and outlet. While the crosslinked PPS powder weighed in this test tube was immersed in a solder bath heated to 320 ° C. for 30 minutes, nitrogen gas was injected from the air flow inlet of the test tube at a flow rate of 100 cc / min. A gas containing volatile components derived from the cross-linked PPS generated in the test tube was purged from the air flow outlet of the test tube. The purged gas was injected from the airflow inlet of a sealed tube having an airflow inlet and outlet containing acetone, and bubbled in acetone in the test tube to dissolve the volatile matter of the crosslinked PPS in acetone. The volatile content of the cross-linked PPS dissolved in acetone was subjected to a temperature rise analysis in the range of 50 ° C. to 290 ° C. using a gas chromatograph mass spectrometer (GC-MS). All components detected by this temperature rise analysis were quantified assuming the same sensitivity as monochlorobenzene, and the volatile content in the crosslinked PPS was calculated.

(C) Component polyphenylene ether-based resin (c-1): 2,6-xylenol was oxidatively polymerized, and polyphenylene ether having a number average molecular weight of 24,000 was defined as (c-1).

  In addition, in a present Example, the number average molecular weight was measured using GPC (gel permeation chromatography), and was set as the value converted into polystyrene.

Component (d) Admixture (d-1): A styrene-glycidyl methacrylate copolymer (mass average molecular weight 110,000) containing 5% by mass of a structural unit composed of glycidyl methacrylate was defined as (d-1).

(E) Component surface-treated inorganic filler (e-1): An average diameter of 10 μm, a length of 3 mm, surface-treated with an aminosilane coupling agent, and further treated with a urethane resin as a sizing agent. (E-1).
(E-2): Glass fiber treated with an epoxy resin as a sizing agent was treated with (e-2) as an average diameter 10 μm, length 3 mm, surface treatment with an aminosilane coupling agent.
(E-3) Glass fiber which was surface-treated with an average diameter of 10 μm, length of 3 mm, an epoxysilane coupling agent, and further treated with an epoxy resin as a sizing agent was designated as (e-3).
(E-4): An average diameter of 10 μm, a length of 3 mm, a glass fiber treated with an epoxy resin as a sizing agent without surface treatment was designated as (e-4).
(E-5): An average diameter of 10 μm, a length of 3 mm, a glass fiber not subjected to the surface treatment and the sizing agent treatment was defined as (e-5).

[Examples 1 to 17 and Comparative Examples 1 to 21]
As shown in Tables 1 to 4, the polyphenylene sulfide resins of the components (a) and (b), the polyphenylene ether resin of the component (c), the admixture of the component (d) and the inorganic filler of the component (e) Were supplied to a twin-screw extruder with a vent port (ZSK-40; manufactured by COPERION WERNER & PFLIDEERER, Germany) and melt-kneaded to obtain pellets of a resin composition. The twin-screw extruder was provided with a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a second and third raw material supply ports on the downstream side, and a vacuum vent on the downstream side. Moreover, the raw material supply method to the 2nd and 3rd raw material supply port was set as the method of supplying using a forced side feeder from an extruder side open port.

  The melt-kneading conditions in the extruder set as described above were such that the extrusion temperature was 290 to 310 ° C., the screw rotation speed was 300 rpm, and the discharge rate was 80 kg / hour.

  Each characteristic was evaluated as follows using the pellet of the obtained resin composition. The evaluation results are shown in Tables 1 to 4.

(Releasability)
The obtained pellets of the resin composition were supplied to a screw in-line injection molding machine set at 290 to 310 ° C. to mold a test piece. Next, the protrusion pin pressure at the time of mold release was measured using a cup mold release evaluation mold under the condition of a mold temperature of 130 ° C. The measured value was used as an evaluation of releasability. That is, it was evaluated that the smaller the protruding pin pressure at the time of releasing the test piece, the better the releasing property.

(Create various test specimens)
JIS K7139 type C test piece (vibration fatigue test piece) was prepared under the same molding conditions by using the obtained resin composition pellets and the same injection molding machine as in the above-mentioned mold release evaluation. Based on K7152-1 and K7313-2, a JIS K7139 type A1 test piece was molded and cut to prepare a test piece for measuring a flexural modulus and a test piece for measuring a Charpy impact strength.

(Average dispersion particle size)
In order to observe the flow direction of the central part of the JIS K7139 type A1 test piece created above, 1/4 was cut with a diamond knife with respect to the thickness, and using an optical microscope (Olympus metal microscope EM3) in a reflection mode. The morphology (matrix phase and domain phase) of the cut surface was observed. Using the photograph of the observed morphology, the size of each domain phase particle was measured, and the average dispersed particle size of the domain phase particle (component (c)) was calculated.

(Vibration fatigue characteristics)
About the created JIS K7139 type C test piece (test piece for vibration fatigue test) using a hydraulic servo fatigue tester (EHF-50-10-3 manufactured by Enomiya Seisakusho Co., Ltd.) according to JIS K7118 at 23 ° C. Under the atmosphere, a tensile load (100 MPa) was applied with a sine wave with a frequency of 30 Hz, and the number of vibrations that were broken was obtained. The more the number of vibrations until the break, the better the vibration fatigue resistance.

(Flexural modulus: rigidity)
About the created test piece for bending elastic modulus measurement, it measured based on JIS K7171 (measurement temperature 23 degreeC).

(Charpy impact strength: toughness)
The Charpy impact strength measurement test piece prepared above was measured in accordance with JIS K7111-1 / 1eA (measurement temperature 23 ° C.).

  From these results, vibration fatigue characteristics and toughness (impact) are obtained when the melt viscosity of the linear and cross-linked polyphenylene sulfide blended in the resin composition comprising the polyphenylene sulfide resin and the polyphenylene ether resin is within the range of this embodiment. It has been clarified that a resin composition having an excellent balance between strength and rigidity is provided. Furthermore, since the mass ratio of the linear polyphenylene sulfide resin and the cross-linked polyphenylene sulfide resin is within the range of the present embodiment, the resin composition has excellent releasability and excellent balance between toughness (impact strength) and rigidity. It became clear to give.

  Moreover, the resin composition excellent in vibration fatigue characteristic and the balance of toughness (impact strength) and rigidity was obtained by using the surface-treated inorganic filler.

  Furthermore, it is clear that the obtained resin composition is excellent in toughness (impact strength) and vibration fatigue characteristics when the average dispersed particle size of the domain phase made of polyphenylene ether resin is within the range of this embodiment. Became.

  Furthermore, it has been clarified that a resin composition having a further excellent balance between vibration fatigue characteristics and toughness (impact strength) and rigidity can be obtained by taking a specific manufacturing method.

  In particular, the linear polyphenylene sulfide of component (a) is divided and supplied to the first raw material supply port and the second or third raw material supply port, and the linear polyphenylene sulfide and the surface-treated inorganic filler are simultaneously supplied. It has been clarified that the resin composition obtained by the production method is a resin composition having a remarkably excellent balance between vibration fatigue characteristics and toughness (impact strength) and rigidity.

  The resin composition of the present invention provides a resin composition having excellent balance between heat resistance, toughness (impact strength) and rigidity, and vibration fatigue characteristics. Therefore, compact disk read only memory (CDROM), digital versatile tile Disc Read Only Memory (DVDROM), Compact Disc Recordable (CDR), Digital Versatile Disc Recordable -R Standard (DVD-R), Digital Versatile Disc Recordable + R Standard (DVD + R) ), Compact disc rewritable (CDRW), digital versatile disc rewritable -R standard (DVD-RW), digital versatile disc rewritable + R standard (DVD + RW), digital versatile disc run Chassis and cabinets such as optical memory (DVDRAM), optical equipment mechanism parts such as optical pickup slide base, parts around the light source lamp, optical fiber connector ferrules, laser beam printer internal parts, inkjet printer internal parts, copier internal parts, It can be used for automobile engine compartment parts such as automobile radiator tank parts, automobile lamp parts, water pipes and casings.

Claims (7)

(A) Linear polyphenylene sulfide resin, (b) Cross-linked polyphenylene sulfide resin, (c) Polyphenylene ether resin, (d) Admixture and (e) Addition of raw material components containing inorganic filler to melt kneader And a resin composition obtained by melt-kneading,
The total addition amount of (a) and (b) component is 45-95 mass parts with respect to 100 mass parts of total addition amount of (a)-(c) component, and the addition amount of (c) component is 55-55 mass parts. 5 parts by mass, the addition amount of component (d) is 1-20 parts by mass, the addition amount of component (e) is 10-350 parts by mass,
The total addition amount of (a) and (b) component is 100% by mass, the addition amount of (a) component is 5-50% by mass, and the addition amount of (b) component is 95-50% by mass. ,
(A) The component has a melt viscosity of 40 to 120 Pa · s, (b) the component has a melt viscosity of 40 to 200 Pa · s,
(D) The component is a styrenic copolymer containing 0.3 to 20% by mass of a structural unit composed of an unsaturated monomer having a glycidyl group or an oxazolyl group,
(E) component is a surface-treated inorganic filler,
In the resin composition, the components (a) and (b) form a matrix phase, the component (c) forms a domain phase with an average dispersed particle size of 0.5 to 20 μm,
In the melt kneading, a polyphenylene sulfide resin composition in which the component (e) and at least a part of the component (a) and / or at least a part of the component (b) are added and kneaded at the same position of the melt kneader. object.   In a vibration fatigue test using a JIS K7139 type C test piece and applying a tensile load (100 MPa) with a sine wave with a frequency of 30 Hz in an atmosphere of 23 ° C. according to JIS K7118, the number of vibrations to break is 30,000 times or more. The polyphenylene sulfide resin composition according to claim 1.   The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the component (c) forms a domain phase with an average dispersed particle size of 0.5 to 10 µm.   The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein in the melt kneading, the component (e) and the component (a) are supplied to the same position of the melt kneader.   The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the component (e) is a glass fiber that has been surface-treated with aminosilane or epoxysilane and further converged with an epoxy resin or a urethane resin.   The component (d) is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and a styrene-vinyl oxazoline-acrylonitrile copolymer. The polyphenylene sulfide resin composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of polymers.   (B) a part of the component, a part of the component (a), a step of adding the component (c) and the component (d) to the melt-kneader and melt-kneading; and the remainder of the component (b) in the melt-kneader It is obtained by using a production method in which the step of adding and melt-kneading, and the step of adding the remainder of component (a) and the component (e) to the melt-kneader and melt-kneading are sequentially performed in this order. Item 7. The polyphenylene sulfide resin composition according to any one of Items 1 to 6.