JP2524593B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyphenylene sulfide resin composition.

[Conventional technology]

Polyphenylene sulfide [PPS] resin has excellent heat resistance, moldability, and chemical resistance, but PPS resin alone has little elongation and is fragile, and as an engineering plastic, it is an electronic and electrical equipment component, office equipment component, acoustic component. In order to be used in the field of equipment parts and other mechanical parts, it is necessary to improve many problems such as low mechanical strength such as bending strength, high thermal expansion coefficient and poor wear resistance. . Therefore, an attempt is made to improve strength, thermal expansion coefficient, and wear resistance by adding a fibrous reinforcing agent (filler) such as glass fiber or carbon fiber or a powdery filler such as silica powder or mica powder to PPS resin. Attempts are being made. However, when a large amount of these inorganic fillers are blended, melt moldability is deteriorated, and particularly when a large amount of fibrous filler is blended, a large anisotropy is generated in strength or dimension, and in parts requiring lubricity, etc. When it is used, it may significantly damage the mating material, but when the amount of the inorganic filler is too small or the amount of the organic filler is too large, the strengthening effect cannot be sufficiently obtained, or the molding shrinkage ratio is large, and It is not preferable because phenomena such as sink marks and warpage become noticeable on the molded product.

It is also well known to blend PPS resins with various thermoplastic resins (eg polyarylates, polysulfones, polyphenylene oxides, polyetherketones, polyamideimides, etc.), especially to improve moldability or brittleness. However, most of these blends do not have sufficient compatibility, and therefore mechanical properties such as bending strength have not been improved, and mold shrinkage, dimensional accuracy such as warpage and sink marks, sliding characteristics, etc. are said to be improved. It often decreases rather than.

In addition to the above method, a method of modifying with a thermosetting resin has been proposed. For example, JP-B-53-13391 proposes to improve mechanical strength and heat distortion temperature by blending an uncured or melt-moldable epoxy [EP] resin with a PPS resin containing an inorganic filler. Has been done. In this method, there is no mention of using a curing agent in combination with the EP resin main component, but when the curing agent is not used, the moldability is excellent, but due to the bleeding phenomenon of the EP resin, the molded product surface However, the molding shrinkage rate, dimensional accuracy such as warpage and sink marks, sliding characteristics, and the like tend to decrease with little improvement. In addition, when a curing agent is used, the melt fluidity of the EP resin itself may decrease significantly as the cross-linking of the EP resin progresses in some cases, making it impossible to stably supply the resin to the mold. Such a phenomenon is remarkable in the case of high filling of EP resin having a high temperature.

Further, in JP-A-59-33360, by compounding an EP resin cured product with a PPS resin containing an inorganic filler,
Although a method for improving the problems of the method disclosed in Japanese Patent Publication No. 53-13391 is proposed, this method improves the melt moldability and the mechanical strength, but the dimensions of the molded product. In order to improve the accuracy, it is necessary to further add a considerable amount of an inorganic filler, which causes the above-mentioned adverse effects. Further, in JP-A-59-51944 and JP-A-59-51945, a low-viscosity PPS resin that is not oxidatively crosslinked is treated with E
We have proposed compositions with excellent molding processability by stabilizing the melt viscosity by reacting P resin to increase the molecular weight, but the compositions obtained by these have the drawback of inferior sliding properties. are doing.

[Problems to be solved by the invention]

As described above, in the conventional technique, the PPS resin has excellent properties such as mechanical properties and heat resistance, and is excellent in melt moldability, dimensional accuracy, and sliding properties. There is a problem that a PPS resin composition for molding cannot be obtained.

[Means for solving problems]

In order to solve the above problems, the present invention uses a melt flow rate (inner diameter 2.09 mm, length 8.00 mm orifice, temperature 300 ° C., holding time 6 minutes, load 5000 g ASTM-D12
Heat-meltable epoxy resin containing 100 parts by weight of polyphenylene sulfide [PPS] resin having a value of 200 g / 10 min or less and a high molecular weight novolac type phenolic resin as a curing agent [EP A composition comprising 10 to 100 parts by weight of a resin (main agent and curing agent) and 0 to 250 parts by weight of a filler, preferably 30 to 250 parts by weight, which is a melt composition of a PPS resin and an EP resin. The PPS resin composition in which the difference in melt flow rate when the holding time was 6 minutes and 30 minutes (the same as the above conditions except the holding time) was 0.7 or less with respect to the value when the holding time was 6 minutes. It adopts the means of making things. The details are described below.

First, the PPS resin used in this invention has the general formula A polymer comprising a repeating unit represented by the formula (1), particularly a polymer containing 90% by mole or more of this repeating unit is preferable in view of characteristics, but if it is less than 90% by mole, a composition having expected properties becomes difficult to obtain. As a method for obtaining such a polymer, various known methods can be adopted, but sodium sulfide and p
It is preferable to react with dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. It is less than 10 mol% as a copolymerization component, within a range that does not affect the crystallinity of the polymer, for example, It may contain a copolymerization component such as. PPS like this
Resins are, for example, Japanese Patent Publication Nos.
Reaction of a halogen-substituted aromatic compound with an alkali sulfide as disclosed in Japanese Patent Publication No. 46-27255, condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst as disclosed in JP-B-46-27255 , Or U.S. Pat.
It is synthesized by a condensation reaction or the like in the presence of an alkali catalyst of thiophenols or a copper salt as disclosed in JP-A No. 2000-242, but a specific method can be arbitrarily selected according to the purpose.

The PPS resin is an uncrosslinked product that is close to white immediately after the reaction such as the condensation as described above, and as it is as it is, it has a low molecular weight and a low viscosity. It is heated to a temperature below its melting point, oxidatively crosslinked, or increased in molecular weight in the step of condensation reaction to change to a solvent viscosity suitable for extrusion molding, injection molding and the like. If the molecular weight is too small, the sliding characteristics, particularly the lubricity, are poor even if the resin is made to have a high molecular weight by reacting with the EP resin main agent.
300 ℃ specified in STM-D1238, holding time 6 minutes, load 50
The melt flow rate (orifice inner diameter 2.09 mm, length 8.00 mm) under the condition of 00 g is 200 g / 10 minutes or less.

Next, the EP resin used in the present invention is an uncured resin capable of being melt-molded, and the melt flow rate (conditions other than the holding time) when the holding time of the melt-blended with the PPS resin was set to 6 minutes and 30 minutes, respectively. Is the same as the above condition), and is preferably 0.7 or less with respect to the value when the holding time is 6 minutes. The reason for this is that if it exceeds 0.7, the melt fluidity of the melted mixture is significantly lowered, which is not preferable. And the type of the main agent of the EP resin itself may be any one having an epoxy group such as bisphenol type, alicyclic type, novolac type, but as the curing agent, amines, acid anhydrides, polysulfides, phenol resins Out of
Adopt high molecular weight novolac phenolic resin. In addition, imidazoles and other accelerators may be added to accelerate the curing reaction.

The high molecular weight novolac type phenolic resin to be blended as a curing agent in the resin composition of the present invention is a bifunctional phenol component as a constituent phenol component (the difunctional phenol is usually 70 to 100 mol%, preferably 80 to It is a high molecular weight novolac type phenolic resin having a number average molecular weight (n) of 1,500 or more and a substantially linear shape. Such a high molecular weight novolac type phenolic resin is composed of novolac repeating units which are all substantially linear, and each block of the novolac type repeating unit having a number average molecular weight of 250 to 1200 is composed of a divalent hydrocarbon group. It may be a high molecular weight novolac type phenolic resin containing chain-extending groups alternately in a ratio of 0.5 to less than 1 mol, particularly 0.6 to less than 1 mol per mol of this block. What is important is that the high molecular weight novolac type resin is substantially linear and has a number average molecular weight (n) in the range of 1500 or more, preferably 1700 to 15000. Here, the number average molecular weight (n) is a value measured by a vapor pressure osmotic pressure method in a N, N-dimethylacetamide solvent. Further, the above-mentioned "substantially linear" means that the polymer chain has a linear or branched linear structure and does not substantially contain a network structure, that is, a gelled product. When the number average molecular weight (n) is large, a composition excellent in heat resistance, mechanical properties and flame retardancy can be obtained when blended with a curable resin, which is preferable, and the molecular weight distribution n is 2000 or more. The content of resin component is usually 50% by weight
It is above, preferably 60% by weight or more, and particularly preferably 70% by weight or more. Further, the ratio of the weight average molecular weight (w) to the number average molecular weight (n) measured by gel permeation chromatography, that is, the molecular weight distribution represented by w / n is preferably 1.8 to 20.0, particularly 2-1.
A range of 0 is preferred. The melting point of the high molecular weight novolac resin is usually 120 ° C or higher, preferably 150 ° C or higher.

The specific phenolic component of the novolac type repeating unit constituting the high molecular weight novolac type phenolic resin is represented by the general formula In the range of 70 to 100 mol%, preferably 80 to 100 mol%, and more preferably 90 to 100 mol%, and the trifunctional phenolic component is 0 to 30 mol%. %, Preferably 0-20 mol%,
More preferably, the phenol component is in the range of 0 to 10 mol% (however, the total amount of both phenol components is 100 mol%).

In the above general formula, two of three R ₁ are hydrogen atoms, and the other one is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom or a hydroxyl group, preferably Represents an alkyl group having 1 to 8 carbon atoms, more preferably methyl group, ethyl group, i-propyl group, sec-
It represents one kind of substituent selected from the group consisting of a butyl group, a tert-butyl group and an octyl group, and a methyl group is particularly preferable. Also, two Rs are hydrogen atoms and have 1 carbon atom.
~ 8 are the same or different groups selected from the group consisting of an alkyl group, a halogen atom and a hydroxyl group, preferably one of the two is a hydrogen atom and the other one is a hydrogen atom or a carbon number of 1 ~ 8 alkyl groups, more preferably two R's are both hydrogen atoms.

Therefore, among the phenolic components constituting the high molecular weight novolac type phenolic resin, one of the bifunctional phenolic components is one of two phenolic compounds having an activity for substitution reaction on the benzene nucleus of the above general formula. Having a hydrogen atom, such as an ortho of a phenol having an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen or a hydroxyl group at the ortho or para position to the hydroxyl group, that is, a phenol ortho group. Isomer or para isomer, and specific examples are cresol, ethylphenol, n-propylphenol, i-propylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, sec-amylphenol, tert-amylphenol, hexyl. Phenol, heptylphenol, octy Examples thereof include alkylphenols such as ruphenol, halogenated phenols such as chlorophenol and bromophenol, and ortho-type or para-type phenol isomers such as arylphenols such as phenylphenol and tolylphenol. Further, other than these bifunctional phenol components, 2,3-xylenol, 3,4-xylenol, 2,5-xylenol, 2,3-diethylphenol, 3,
4-diethylphenol, 2,5-diethylphenol, 2,
3-diisopropylphenol, 3,4-diisopropylphenol, 2,5-diisopropylphenol, 2,3-dichlorophenol, 3,4-dichlorophenol, 2,5-dichlorophenol, 2-methyl-3-phenylphenol, 3 Examples include -methyl-4-phenylphenol and 2-methyl-5-phenylphenol. In any case, the bifunctional phenol component is at least one kind of these components, and there is no problem even if it is a mixture of two or more kinds.

Further, among the phenol components constituting the high molecular weight novolac type phenolic resin, the trifunctional phenol component is a phenol compound having three hydrogen atoms active on the benzene nucleus for the substitution reaction. Yes, specifically, phenol, both meta-substituted products of phenol, and 3,5-substituted products of phenol. And these trifunctional phenols, as the substituents at both meta positions or at the 3,5 position, are usually alkyl groups, halogens or hydroxyl groups, and among these trifunctional phenols, preferred ones Is the general formula (Wherein R in the formula is the same as the above R), and specific examples include phenol, m-cresol, m-ethylphenol, m-
n-propylphenol, m-isopropylphenol, m-n-butylphenol, m-sec-butylphenol, m-tert-butylphenol, m-n-amylphenol, m-sec-amylphenol, m-tert-amylphenol, m -Meta-substituted phenols such as hexylphenol, m-heptylphenol, m-octylphenol, m-fluorophenol, m-chlorophenol, m-bromophenol, resorcin, 3,5-xylenol, 3,5-diethylphenol, 3 , 5-diisopropylphenol, 3,5-di-sec-butylphenol, 3,5-
Di-tert-butylphenol, 3,5-di-sec-amylphenol, 3,5-di-tert-amylphenol, 3,5-dihexylphenol, 3,5-diheptylphenol, 3,5
-Dioctylphenol, 3,5-difluorophenol,
3,5-dichlorophenol, 3,5-dibromophenol,
Mention may be made of 3,5-disubstituted phenols such as 3,5-diiodophenol.

The amount of EP resin (base resin and curing agent) added above is
The amount is 10 to 100 parts by weight with respect to 100 parts by weight of the PPS resin, although it depends on the amount and the use of the filler. This is because if the amount added is less than 10 parts by weight, it is not possible to suppress factors closely related to dimensional accuracy, such as warpage, sink marks, and mold shrinkage, and conversely, if the amount exceeds 100 parts by weight, the mechanical strength is reduced. This is because, depending on the type of the EP resin or the type of EP resin, bleeding on the surface of the molded product may deteriorate the sliding property, and further, the melt flow stability may be adversely affected. Generally, the main component of the EP resin reacts with the end groups of the PPS resin, etc., but one of the important objects of the present invention is to improve the dimensional accuracy,
A high molecular weight novolac type phenolic resin as a curing agent is mixed to form a three-dimensional crosslinked structure of EP resin in the matrix of PPS resin, which suppresses warpage, sink marks, molding shrinkage, and the like. In addition, compared to a composition obtained from a low molecular weight PPS resin and an EP resin (only a small amount of the main resin or even if a curing agent is used in combination), such a structure makes it possible to obtain sliding properties, particularly lubricity. Is excellent. The reason is not clear, but in the structure of the resin composition of the present invention, it may be because the original property of the PPS resin, which has a small shear strength and is suitable for lubricity, is almost not impaired. Guessed.

Further, the filler used in the present invention is not particularly limited as long as it can withstand the temperature of heating when the PPS resin is melt-molded, and may be selected according to the purpose and application. . Examples of the filler include polyetherketone, polyimide, silicone, heat-resistant polymer materials such as fluororesin, glass fiber, carbon fiber,
Heat resistant inorganic single fiber such as graphite fiber, wollastonite, potassium titanate whiskers, steel wire, copper wire, stainless wire, etc., so-called boron fiber or tungsten fiber or carbon fiber with boron or silicon carbide deposited on it. Heat-resistant inorganic composite fibers such as silicon carbide fibers, heat-resistant organic fibers such as aromatic amide fibers, graphite or metals such as zinc, aluminum and magnesium, or inorganic powders for improving heat conduction such as oxides thereof,
Inorganic powder for improving heat insulation such as glass beads, silica balloon, diatomaceous earth, asbestos, magnesium carbonate, inorganic powder for improving lubricity such as molybdenum disulfide, graphite, carbon, mica, talc, and iron oxide, cadmium sulfide, A large number of inorganic powders such as cadmium selenide and carbon black for coloring can be exemplified.
And the addition amount of these fillers in the present invention is PPS.
0 to 250 parts by weight, preferably 30 to 100 parts by weight of resin
~ 250 parts by weight. This is because when the amount of filler is less than 30 parts by weight, the coefficient of thermal expansion is a little large, and the mechanical strength such as bending strength is a little low. On the contrary, when the amount of filler is more than 250 parts by weight, the mechanical strength such as bending strength is significantly reduced. Because.

The method for mixing the various raw materials such as the PPS resin, EP resin, and filler described above is not particularly limited, and for example,
PPS resin and EP resin and filler are dry-mixed individually or using a mixer such as a Henschel mixer, a ball mill, a tumbler mixer, and then melt-mixed with a hot roll, a kneader, a Banbury mixer, a melt extruder (for example, granulation). ) May be melt-molded into a predetermined shape.
At this time, the temperature at which the PPS resin is melted and mixed is equal to or higher than the temperature at which the PPS resin melts, specifically, 280 to 400 ° C, preferably 280 to 350 ° C. This is because the uniform dispersion of the two resins cannot be expected at a low temperature below 280 ° C at which the PPS resin does not melt or at a high temperature above 400 ° C at which the EP resin cures in a short time.

〔Example〕

Raw materials used in Examples and Comparative Examples are collectively shown as follows. The abbreviations are shown in []. The mixing ratios of these raw materials are all parts by weight.

(1) Polyphenylene sulfide [PPS] resin, [PPS-1] (US Phillips Petroleum
International: Ryton P-4), [PPS-2] (Dojo: Ryton PR06), [PPS-3] (Dojo: Ryton V-1), [PPS-4] (Kureha Chemical Co., Ltd. : KPS- # 200), (2) Epoxy [EP] resin, [EP-1] (Nippon Kayaku Co., Ltd .: epoxidized phenol novolac EPPN-201), [EP-2] (Mitsui Petrochemical Epoxy Co., Ltd .: Bisphenol A type epoxy resin EPOMIK R-140), (3) Curing agent (the properties of each curing agent are collectively shown in Table 1), [Curing agent-1] (high molecular weight novolac type P-cresol-formaldehyde resin) ), [Curing agent-2] (high molecular weight novolac type P-cresol / m-cresol / formaldehyde resin), [Curing agent-3] (high molecular weight novolac type P-cresol / formaldehyde resin), [curing agent-4] (Novolak type phenol / formal Dehydrogenase resin) Curing agent -5] (novolac P- cresol-formaldehyde resin), Curing accelerator] (BF ₃ · 2-methylimidazole complex), (4) Filler Carbon fiber (Toho Rayon Co., Ltd .: chopped fiber, diameter 7 μm, length 6 mm, sizing agent epoxy), glass fiber (Asahi Fiber Glass Co., Ltd .: chopped strand, diameter 13 μm, length 3 mm, aminosilane cup) Ring-treated product), Mica (Canada Mica Co., Ltd .: Mica S-325), Examples 1 to 6: Raw materials were dry-mixed in advance in a mixing ratio shown in Table 2, and then a twin-screw extruder (made by Ikegai Tekko KK). : PCM-30), and extruded and granulated under the conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 50 rpm. Cylinder temperature 320
Injection molding under conditions of ℃, injection pressure 900kg / cm ² , mold temperature 130 ℃, cylinder (outer diameter 23mm, inner diameter 14mm, length 13mm), plate (width 12.7mm, length 126mm, thickness) 3.2mm), dimensional accuracy measurement disk 1 (outer diameter 20mm, thickness 3mm disk 2 8mm outer diameter, 3mm height protrusions 2 are coaxially formed on both sides, the diameter of the shaft core A 2 mm hole 3 was penetrated, see FIGS. 1 and 2), and a comb flow test piece (width 5 mm, thickness 0.4 mm and 0.6 mm) for flowability measurement was obtained. Furthermore, a prism for measuring the linear expansion coefficient from the plate material (section 3 mm x 3 mm, length 8 mm)
Also, a test piece was produced by cutting such that the two directions of the flow direction of the resin at the time of molding the plate material and the direction perpendicular thereto were the longitudinal directions. Comb flow test (melt molding stability), flexural strength, flexural modulus, coefficient of thermal expansion, dimensional accuracy (true circular conduction and sink of cylindrical inner diameter), sliding characteristics, etc. are measured on the various test pieces obtained. And evaluated. The evaluation method is as follows. That is, (1) Comb flow test: Injection molding was performed under certain conditions using a mold for comb flow test with thicknesses of 0.4 mm and 0.6 mm and width of 5 mm, and the flow length of each thickness was measured to obtain 100 pieces. The maximum value and the minimum value of the test piece of 1 were taken and used as a measure of the melt molding stability.

(2) Flexural strength and flexural modulus: According to ASTM-D790.

(3) Coefficient of thermal expansion: Using a TMA method (Shimadzu thermomechanical analyzer), use a prism (3 mm square, length 8 mm) such that the resin flow direction during molding or its right angle direction is in the longitudinal direction. , 0
Obtain the coefficient of thermal expansion in the range of ~ 90 ° C.

(4) Dimensional accuracy (roundness and sinkage): Roundness is measured in the axial center using Talylond 200 manufactured by Rank Taylor Hobson, UK, and the sink is the surf coder model SE-3E manufactured by Kosaka Laboratory. As shown in Figure 2 → mark, measure the inner diameter shape of the hole 3 with an inner diameter of 2 mm at 4 locations diagonally on each diagonal, and refer to the line connecting the two inlets of the hole 3 in the axial direction as the reference Find the highest value as a sink.

(5) Sliding characteristics (dynamic friction coefficient and wear coefficient): Using a test piece with an inner diameter of 14 mm, an outer diameter of 23 mm, and a length of 13 mm, using a thrust type friction wear tester, a load of 1 kg / cm ² , a speed of 100
The value after sliding for 1 hour with the bearing rope (SUJ2) under the condition of m / min is the dynamic friction coefficient, and the wear coefficient is 100.
Calculate the weight change before and after sliding over time.

The results obtained by each of the above measuring methods are summarized in Table 3.

Comparative Examples 1 to 7: Example 1 except that the raw materials were mixed in the proportions shown in Table 4.
Various test pieces were prepared by performing the same operation as above, the same various characteristics were evaluated, and the obtained results are summarized in Table 5.

Comparing Table 3 and Table 5, Examples 1 to 7 show small variations in the comb flow test, good melt molding stability, and good bending strength and bending elastic modulus. Further, although the anisotropy of the coefficient of thermal expansion is small, the dimensional accuracy and the sliding characteristics are good, Comparative Example 1 using the PPS resin having a large melt flow rate even if the heat-resistant EP-1 resin is used In comparison with Example 3 or 4 in which the same filler was mixed in the same amount, both dimensional accuracy and sliding characteristics were poor, and Comparative Example 2 in which the EP resin main agent was used and no curing agent was used was also compared to Comparative Example 1. Similarly, not only was the dimensional accuracy and sliding characteristics poor, but the anisotropy of the coefficient of thermal expansion also showed a large value, and the effect of adding the EP resin was not observed at all. In addition, in Comparative Examples 3 and 4 in which the heat resistance of the added EP resin is inferior to that used in the Examples, there are large variations in the comb flow test, lack of melt molding stability, and dimensional accuracy and sliding characteristics. It was unsatisfactory. Comparative Example 5 with a small amount of heat-resistant EP resin compounded
Has no effect of the addition of EP resin and is inferior in dimensional accuracy, wear resistance, anisotropy of thermal expansion coefficient and the like. On the contrary, in Comparative Example 6 in which the heat-resistant EP resin was excessively mixed and Comparative Example 7 in which the filler was excessively large, the flexural strength was remarkably lowered, and the sliding characteristics were also unsatisfactory. In addition, in Example 8 in which no filler is added, the flexural strength and the coefficient of thermal expansion are slightly inferior as compared with Examples 1 to 7 in which the filler is added in an amount of 30 parts by weight or more. Compared with Comparative Example 8 in which no filler is added, all physical properties are superior,
In particular, it was found that the dimensional accuracy and sliding characteristics were excellent.

〔effect〕

The PPS resin composition of the present invention is not only excellent in melt moldability, but a molded product obtained by melt molding the same is PP
It possesses excellent heat resistance, chemical resistance, and low frictional properties peculiar to S resin, and also has excellent mechanical strength, abrasion resistance, and dimensional accuracy.
It can be widely used as parts for space equipment, general industrial machinery, office equipment, optical, electrical, electronic and other fields, but it also includes various bearings, thrust washers, gears, cams, piston rings, compressor vanes. Excellent dimensional accuracy and sliding characteristics when used for various parts such as valves, housings, connectors, sockets, holders, trays, cases, mounts, fuses, and parts around engines in the automobile and space / aircraft fields. It can be said that the significance of the present invention is extremely great since the above can be sufficiently exerted.

[Brief description of drawings]

FIG. 1 is a sectional view of a disk for measuring dimensional accuracy, and FIG. 2 is a plan view thereof. 1 ... Disc, 2 ... Projection, 3 ... Hole.

Claims (1)

(57) [Claims] 1. Melt flow rate (inside diameter 2.09 mm, length 8.
(Value measured by ASTM-D1238 with a temperature of 300 ° C, holding time of 6 minutes, load of 5000 g, using an orifice of 00 mm)
Is less than 200g / 10 minutes, polyphenylene sulfide [P
PS] 100 parts by weight of a resin and a heat-resistant melt-moldable epoxy [EP] resin (main agent and curing agent) containing a high molecular weight novolak type phenolic resin as a curing agent 10 to 100
And a melt flow rate when the holding time of the melt-blended PPS resin and EP resin is 6 minutes and 30 minutes (the conditions other than the holding time are the same as the above conditions). Is 0.7 or less with respect to the value when the holding time is 6 minutes, the polyphenylene sulfide resin composition.