JP2014141567A - Polyphenylenesulfide resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylenesulfide resin composition which exhibits high tensile elongation and have excellent creep characteristics and electrical characteristics and to provide a method for producing the same.SOLUTION: There is provided a resin composition which comprises: (a) 85 to 51 wt.% of a polyphenylenesulfide resin; and (b) 15 to 49 wt.% of a polyphenylene ether resin, where (a) component forms a continuous phase (sea phase) and (b) component forms a dispersed phase (island phase) and dispersed particles composed of (a) component are present in a dispersed phase composed of (b) component.

Description

  The present invention relates to a polyphenylene sulfide resin composition having excellent toughness and a low dielectric constant, and a method for producing the same.

  Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has properties suitable as an engineering plastic such as excellent heat resistance, chemical resistance, electrical insulation and wet heat resistance. For this reason, although widely used for electrical / electronic parts, communication equipment parts, automobile parts, etc., problems such as relatively low toughness and high dielectric constant have been pointed out. In particular, in the fields of electrical / electronics and communications, the present situation is that materials having a low dielectric constant are being demanded as the frequency increases for the purpose of high-speed information processing and high-speed transmission.

  On the other hand, polyphenylene ether (hereinafter sometimes abbreviated as PPE) resin is a material having high heat resistance and relatively low dielectric constant, similar to PPS resin, although it is somewhat difficult to mold.

  For this reason, some attempts have been reported so far to blend polyphenylene ether resin with polyphenylene sulfide resin. For example, Patent Document 1 discloses a polymer mixture composed of polyphenylene ether, polyarylene sulfide, and an epoxy compound. Patent Document 2 discloses a resin composition containing a polyphenylene sulfide resin, a polyphenylene oxide resin, and a coupling agent. Patent Document 3 discloses a resin composition containing a polyarylene sulfide resin having a melt viscosity of 30 Pa · s or less and a polyarylene ether resin. Patent Document 4 discloses a resin composition obtained by blending polyphenylene sulfide, polyphenylene ether, ethylene / ethylenically unsaturated carboxylic acid glycidyl ester / vinyl acetate copolymer.

  However, usually, the dielectric constant of the resin composition largely depends on the dielectric constant of each resin to be blended and the blending ratio thereof. Specifically, polyphenylene sulfide has a dielectric constant of about 3.5, polyphenylene ether of about 2.6, and polyethylene of about 2.2. From the viewpoint of heat resistance and chemical resistance, polyphenylene sulfide is a phase mainly composed of polyphenylene sulfide. In order to build the structure, the amount of low dielectric polymer such as polyphenylene ether and polyethylene is inevitably limited, so there is a substantial limit to the low dielectric constant of the polyphenylene sulfide resin composition, which is not necessarily on the market. The present condition is not able to satisfy the request of. In addition, olefin-based resins such as polyethylene also have new problems such as significantly increasing the amount of creep distortion of polyphenylene sulfide due to its flexibility.

JP-A-2-36262 JP-A-3-79661 JP 2002-121383 A JP 2011-57720 A

  The present invention provides a polyphenylene sulfide resin composition that has excellent toughness, low dielectric constant, and low creep strain without impairing the heat resistance, chemical resistance, and mechanical strength inherent to the polyphenylene sulfide resin. Is an issue.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that a polyphenylene sulfide resin is dispersed in a continuous phase (sea phase) and a polyphenylene ether resin is dispersed in a resin composition in which a polyphenylene ether resin is blended with a polyphenylene sulfide resin. In addition to forming a phase (island phase) and forming a specific phase structure in which dispersed particles made of polyphenylene sulfide resin are present in the dispersed phase made of polyphenylene ether resin, the dielectric constant has excellent toughness. As a result, the present inventors have found that the creep strain is drastically reduced and reached the present invention.

That is, the present invention is as follows.
1. A resin composition comprising (a) 85 to 51% by weight of a polyphenylene sulfide resin and (b) 15 to 49% by weight of a polyphenylene ether resin, wherein the total of the component (a) and the component (b) is 100% by weight. In the morphology observed with an electron microscope of a molded article comprising a resin composition, (a) component forms a continuous phase (sea phase), (b) component forms a dispersed phase (island phase), and (b) component A polyphenylene sulfide resin composition, wherein dispersed particles comprising the component (a) are present in a dispersed phase comprising:
2. 2. The polyphenylene sulfide resin according to 1, wherein the dispersed particles made of the (a) polyphenylene sulfide resin are present in the dispersed phase made of the (b) polyphenylene ether resin with a number average particle diameter of 1 to 200 nm. Composition,
3. In the dispersed phase composed of the (b) polyphenylene ether resin, the dispersed particles composed of the (a) polyphenylene sulfide resin are present in an area ratio of 2 to 50% based on the area of the dispersed phase. The polyphenylene sulfide resin composition according to any one of -2,
4). (B) The dispersed phase composed of the polyphenylene ether resin is composed of two groups of a dispersed phase (A) having a particle diameter exceeding 300 nm and a dispersed phase (B) having a particle diameter of 300 nm or less. Only for A), the polyphenylene sulfide resin composition according to any one of 1 to 3, which contains dispersed particles composed of the (a) polyphenylene sulfide resin,
5. (B) The ratio (n _A / n _B ) of the dispersed particle number n _A of the dispersed phase (A) comprising the polyphenylene ether resin to the dispersed particle number n _B of the dispersed phase ( _B ) is 0.05 to 1.00 4. The polyphenylene sulfide resin composition according to 4, wherein
6). A silane cup containing 100 parts by weight of the total of (a) polyphenylene sulfide resin and (b) polyphenylene ether resin, and further containing (c) at least one functional group selected from an epoxy group, an amino group, and an isocyanate group The polyphenylene sulfide resin composition according to any one of 1 to 5, which contains 0.1 to 5 parts by weight of a ring compound,
7). The total of (a) polyphenylene sulfide resin and (b) polyphenylene ether resin is 100 parts by weight, and (d) further contains 1 to 45 parts by weight of olefin-based resin. The polyphenylene sulfide resin composition according to the description,
8). The ratio (L / D) of the screw length L to the screw diameter D is 10 or more, and 3 to 20% of the L / D is composed of a stirring screw element having a notch in the screw flight. The method for producing a polyphenylene sulfide resin composition according to any one of 1 to 7, characterized by melt-kneading using a twin-screw extruder,
It is.

  According to the present invention, it is possible to obtain a polyphenylene sulfide resin composition in which the dielectric constant and creep strain are drastically reduced together with excellent toughness. The decrease in the dielectric constant is suitable for high-frequency applications such as electrical / electronic devices and communication devices because the radio wave delay time of signals can be shortened.

(A) PPS forms the continuous phase ( 1 ), (b) PPE forms the dispersed phase ( 2 ), and (b) dispersed particles composed of the PPS component ( 3 ) in the dispersed phase composed of the PPE component ( 3 ) It is a schematic diagram of the phase structure of the resin composition of this invention in which exists.

  Hereinafter, embodiments of the present invention will be described in detail.

(A) Polyphenylene sulfide resin (a) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula,

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula is preferred. In addition, (a) the PPS resin may be composed of a repeating unit having the following structure in an amount of less than 30 mol% of the repeating unit.

  Since the PPS copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

  Although there is no restriction | limiting in particular in the melt viscosity of (a) PPS resin used by this invention, The one where the melt viscosity is higher is preferable from the viewpoint of obtaining the more excellent tensile breaking elongation. For example, a range exceeding 30 Pa · s (310 ° C., shear rate 1000 / s) is preferable, 50 Pa · s or more is more preferable, and 100 Pa · s or more is more preferable. The upper limit is preferably 600 Pa · s or less from the viewpoint of maintaining melt fluidity.

  The melt viscosity in the present invention is a value measured using a Toyo Seiki Capillograph under conditions of 310 ° C. and a shear rate of 1000 / s.

  Although the manufacturing method of (a) PPS resin used for this invention is demonstrated below, if (a) PPS resin of the said structure is obtained, it will not be limited to the following method.

  First, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method will be described.

[Polyhalogenated aromatic compounds]
A polyhalogenated aromatic compound refers to a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexa Polyhalogenated aroma such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds, and preferably p-dichlorobenzene is used. Further, it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

  The polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 mol, preferably 0.95 to 1. mol per mol of sulfidizing agent, from the viewpoint of obtaining a (a) PPS resin having a viscosity suitable for processing. A range of 5 moles, more preferably 1.005 to 1.2 moles can be exemplified.

[Sulfiding agent]
Examples of the sulfiding agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

  Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  In addition, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide and transferred to a polymerization tank for use.

  Alternatively, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

  The amount of the sulfidizing agent charged means a residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the start of the polymerization reaction due to dehydration operation or the like.

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. A range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
An organic polar solvent is preferably used as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethyl sulfone, tetramethylene sulfoxide and the like, and mixtures thereof, and the like are all included. It is preferably used because of its high reaction stability. Of these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

  The amount of the organic polar solvent used is selected in the range of 2.0 to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol per mol of the sulfidizing agent.

[Molecular weight regulator]
(A) A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound for the purpose of forming a terminal of the PPS resin or adjusting the polymerization reaction or the molecular weight. Can be used together.

[Polymerization aid]
In order to obtain a relatively high degree of polymerization (a) PPS resin in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means (a) a substance having an action of increasing the viscosity of the PPS resin to be obtained. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferable. Further, alkali metal carboxylates are preferable as organic carboxylates, and lithium chloride is preferable as alkali metal chlorides.

  The alkali metal carboxylate is a general formula R (COOM) n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. Can be mentioned.

  The alkali metal carboxylate is an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates, and are allowed to react by adding approximately equal chemical equivalents. You may form by. Among the alkali metal carboxylates, lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in the polymerization system, is most preferably used.

  When using these alkali metal carboxylates as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles per mole of charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  Moreover, the addition amount in the case of using water as a polymerization aid is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, 0.6 to The range of 10 mol is preferable, and the range of 1 to 5 mol is more preferable.

  Of course, two or more kinds of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be obtained in a smaller amount.

  There is no particular designation as to the timing of addition of these polymerization aids, which may be added at any time during the previous step, polymerization start, polymerization in the middle to be described later, or may be added in multiple times. When using an alkali metal carboxylate as a polymerization aid, it is more preferable to add it at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound during the polymerization reaction after charging.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually in a proportion of 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Is preferably used. If this ratio is small, the stabilizing effect is insufficient. Conversely, if the ratio is too large, it is economically disadvantageous or the polymer yield tends to decrease.

  The addition timing of the polymerization stabilizer is not particularly specified, and may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. It is more preferable because it is easy to add at the start of the process or at the start of the polymerization.

  Next, a preferred method for producing the (a) PPS resin used in the present invention will be described in detail in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process. Of course, the process is limited to this process. It is not something.

[pre-process]
(A) In the production method of PPS resin, the sulfiding agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfiding agent is increased. It is preferable to warm and remove excess water out of the system.

  As described above, a sulfidizing agent prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used as the sulfidizing agent. Can do. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C. In addition, there is a method in which the temperature is raised to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, and water is distilled off. A polymerization aid may be added at this stage. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 moles per mole of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

[Polymerization reaction step]
(A) A PPS resin is produced by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.

  When starting the polymerization reaction step, the organic polar solvent, the sulfidizing agent, and the polyhalogenated aromatic compound are desirably mixed in an inert gas atmosphere at room temperature to 240 ° C., preferably 100 to 230 ° C. . A polymerization aid may be added at this stage. The order in which these raw materials are charged may be out of order or may be simultaneous.

  The mixture is usually heated to a temperature in the range of 200 ° C to 290 ° C. Although there is no restriction | limiting in particular in a temperature increase rate, Usually, the speed of 0.01-5 degreeC / min is selected, and the range of 0.1-3 degreeC / min is more preferable.

  In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is usually carried out at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

  In the stage before reaching the final temperature, for example, a method of reacting at 200 to 260 ° C. for a certain time and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 260 degreeC, the range of 0.25 to 20 hours is normally selected, Preferably the range of 0.25 to 10 hours is selected.

  In order to obtain a polymer having a higher degree of polymerization, it may be effective to perform polymerization in multiple stages. When the polymerization is performed in a plurality of stages, it is effective that the conversion of the polyhalogenated aromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol%.

The conversion rate of the polyhalogenated aromatic compound (herein abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When polyhalogenated aromatic compound is added excessively in a molar ratio with respect to the alkali metal sulfide, the conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol) -PHA excess (mole)]
(B) In cases other than (A) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
(A) In the method for producing a PPS resin, after the polymerization is completed, a solid is recovered from a polymerization reaction product containing a polymer, a solvent, and the like. Any known method may be adopted as the recovery method.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degree-C / min-about 3 degree-C / min. It is not necessary to perform slow cooling at the same rate in the entire process of the slow cooling step, such as a method of gradually cooling at a rate of 0.1 to 1 ° C / min until the polymer particles are crystallized and precipitated, and then at a rate of 1 ° C / min or more. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on quenching conditions, As a preferable method of this collection method, the flash method is mentioned. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery. This is a method, and the term “flash” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor at normal pressure, and the temperature is usually in the range of 150 ° C to 250 ° C.

[Post-processing process]
(A) The PPS resin may be produced through the above polymerization and recovery steps, and then subjected to acid treatment, hot water treatment, washing with an organic solvent, and alkali metal or alkaline earth metal treatment.

  When acid treatment is performed, it is as follows. (A) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have the function of decomposing the (a) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but (a) those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of immersing (a) the PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous PH4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The PH after processing may be 4 or more, for example, about PH 4-8. The acid-treated (a) PPS resin is preferably washed several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effect of the preferred chemical modification of the (a) PPS resin by acid treatment.

  When performing hot water treatment, it is as follows. (A) In the hot water treatment of the PPS resin, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 degreeC, since the effect of the preferable chemical modification | denaturation of (a) PPS resin is small, it is unpreferable.

  The water used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of the (a) PPS resin by hot water washing. There is no particular restriction on the operation of the hot water treatment, and a predetermined amount of (a) PPS resin is put into a predetermined amount of water and heated and stirred in a pressure vessel, or a method of continuous hot water treatment is performed. Is called. (A) The ratio of the PPS resin and water is preferably larger, but usually a bath ratio of (a) 200 g or less of PPS resin is selected for 1 liter of water.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is desirably an inert atmosphere in order to avoid this. Furthermore, it is preferable that the (a) PPS resin that has finished this hot water treatment operation is washed several times with warm water in order to remove the remaining components.

  When washing with an organic solvent, it is as follows. (A) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have the action of decomposing (a) the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, Halogen solvents such as trachlorethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and the like Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like can be mentioned. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method such as (a) immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning (a) PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is no particular limitation on the cleaning time. Depending on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect can be obtained usually by cleaning for 5 minutes or more. It is also possible to wash in a continuous manner.

  As a method of treating alkali metal or alkaline earth metal, before the previous step, during the previous step, after the previous step, a method of adding an alkali metal salt or alkaline earth metal salt, before the polymerization step, during the polymerization step, during the polymerization step Examples include a method of adding an alkali metal salt or an alkaline earth metal salt into the polymerization vessel later, or a method of adding an alkali metal salt or an alkaline earth metal salt at the first, middle or last stage of the washing step. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers or residual salts by washing with an organic solvent or washing with warm water or hot water. Alkali metals and alkaline earth metals are preferably introduced into PPS in the form of alkali metal ions such as acetates, hydroxides and carbonates, and alkaline earth metal ions. It is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water. The concentration of alkali metal ions and alkaline earth metal ions when introducing the alkali metal and alkaline earth metal is preferably 0.001 mmol or more, more preferably 0.01 mmol or more, relative to 1 g of PPS. As temperature, 50 degreeC or more is preferable, 75 degreeC or more is more preferable, and 90 degreeC or more is especially preferable. Although there is no upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (the weight of the cleaning solution with respect to the dry PPS weight) is preferably 0.5 or more, more preferably 3 or more, and still more preferably 5 or more.

  In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition having excellent toughness, after removing residual oligomers and residual salts by repeating organic solvent washing and hot water of about 80 ° C. or hot water washing described above several times, A method of treating with an acid treatment or an alkali metal salt or an alkaline earth metal salt is preferred.

  In addition, (a) the PPS resin can be used after having been polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidation crosslinking treatment by heating with addition of a crosslinking agent such as peroxide.

  When the dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. The oxygen concentration is preferably 5% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  Moreover, it is also possible to perform dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing volatile matter. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 5% by volume, and more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  However, the (a) PPS resin of the present invention is preferably a substantially linear PPS resin that is not subjected to high molecular weight by thermal oxidation crosslinking treatment from the viewpoint of exhibiting excellent toughness. On the other hand, the PPS resin subjected to the thermal oxidative cross-linking treatment is suitable from the viewpoint of suppressing the creep distortion, and can be used by appropriately mixing with the linear PPS resin. In the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

  From the viewpoint of improving the affinity with (b) the PPE resin, the (a) PPS resin of the present invention includes a carboxyl group and a derivative group thereof as a preferred embodiment. (A) As a method of introducing a carboxyl group and a derivative group thereof into a PPS resin, a method of copolymerizing a polyhalogenated aromatic compound containing a carboxyl group and a derivative group thereof, a method including a carboxyl group and a derivative group thereof Examples thereof include a method of introducing a compound, for example, maleic anhydride, sorbic acid and the like by introducing (a) reaction with PPS resin while melt-kneading.

(B) Polyphenylene ether resin The polyphenylene ether resin used in the present invention is a polymer containing a structural unit represented by the following structural formula in the main chain, and either a homopolymer, a copolymer or a graft polymer may be used.

  Here, R1 to R4 are selected from hydrogen, halogen, an alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, and the like. R1 and R2 are preferably independent primary alkyl groups having 1 to 3 carbon atoms, and R3 and R4 are preferably hydrogen.

  Such polyphenylene ether resins can be obtained by oxidative polymerization in the presence of oxygen or an oxygen-containing gas using one or more phenolic compounds and an oxidative coupling catalyst.

  Examples of units other than those represented by the above structural formula include vinyl aromatic compounds. For example, a polymer obtained by graft polymerization of a vinyl aromatic compound to a polymer composed of the units represented by the above structural formula can be used.

  More specific structures of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2,6-phenylene). Dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2- Ethyl-6-propyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer Examples thereof include 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer.

  Further, a copolymer obtained by graft polymerization of styrene on poly (2,6-dimethyl-1,4-phenylene ether), and a styrene grafted on 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer. A copolymer etc. are mentioned.

  Of these, poly (2,6-dimethyl-1,4-phenylene) ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol and the like are preferable.

  In addition, polyphenylene ether modified with maleic anhydride or glycidyl methacrylate is also preferably used. In particular, for the PPS resin composition of the present invention, polyphenylene ether modified with maleic anhydride is more preferably used from the viewpoint of improving elongation. However, in the case of polyphenylene ether modified with excess maleic anhydride, since the melt viscosity of the resin composition becomes too high and the molding lower limit pressure increases, the amount of maleic anhydride added to 100 parts by weight of polyphenylene ether It is preferable to modify it to 5 parts or less. Further, when fluidity is important, unmodified polyphenylene ether is suitable, and it is of course possible to use it together with modified polyphenylene ether.

(C) Silane coupling compound containing at least one functional group selected from epoxy group, amino group, and isocyanate group (c) At least one type selected from epoxy group, amino group, and isocyanate group in the present invention Among the silane coupling compounds containing a functional group, the compound having an epoxy group (excluding the olefin resin) has one or more epoxy groups in one molecule and two or three alkoxy groups. The silane compound which has is mentioned. Examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  Of the silane coupling compounds containing at least one functional group selected from (c) an epoxy group, an amino group and an isocyanate group of the present invention, the compound having an amino group includes 1 amino group per molecule. Examples thereof include silane compounds having at least two and having two or three alkoxy groups. Examples thereof include γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane.

  Of the silane coupling compounds having at least one functional group selected from (c) an epoxy group, an amino group and an isocyanate group of the present invention, the compound having an isocyanate group includes 1 isocyanate group in one molecule. A silane compound having two or more alkoxy groups and two or three alkoxy groups can be given. For example, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane Examples include silane and γ-isocyanatopropyltrichlorosilane.

  By adding these silane coupling compounds, the tensile elongation of the PPS resin composition is likely to be improved. Among them, an alkoxysilane compound having an epoxycyclohexyl group or an isocyanate group is preferably used to stably exhibit excellent toughness. More preferably, it is more preferably an alkoxysilane compound containing an isocyanate group.

(D) Olefin Resin The (b) olefin resin used in the present invention may be either an olefin polymer or an olefin copolymer.

  Examples of olefin polymers or copolymers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 dimethyl-1-hexene, 4,4 dimethyl-1-pentene, 4-ethyl-1-hexene, Α-Oleph such as 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene Polymers obtained by polymerizing single or two or more kinds, such as α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Examples include α, β-unsaturated carboxylic acids and copolymers thereof with alkyl esters.

  In addition, examples of the olefin containing an epoxy group include monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid.

  Examples of the olefin containing a carboxyl group and a salt thereof and an acid anhydride group include maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5 And monomers such as heptene-2,3-dicarboxylic acid anhydride.

  As a method for introducing a monomer component containing these epoxy group, carboxyl group, acid anhydride group, etc., copolymerization is performed during polymerization, or a radical initiator is used for the olefin polymer or olefin copolymer. For example, a graft introduction method can be used.

  When a monomer component containing an epoxy group, a carboxyl group, or an acid anhydride group is introduced, the amount introduced is 0.001 to 40 mol%, preferably 0.01 to 35 mol, based on the entire olefin resin. % Is preferable.

  Examples of the olefin-based copolymer containing an epoxy group particularly useful in the present invention include an olefin copolymer having an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester as essential copolymerization components. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester and the like.

  In the present invention, an olefin copolymer containing 80 to 99% by weight of an α-olefin and 1 to 20% by weight of a glycidyl ester of an α, β-unsaturated carboxylic acid as an essential copolymerization component is preferable, and an α-olefin of 90 to 99 is preferable. Olefin copolymers containing 1% by weight to 10% by weight of glycidyl ester of α, β-unsaturated carboxylic acid as essential copolymer components are particularly preferred.

  The α, β-unsaturated carboxylic acid glycidyl ester is

(R represents a hydrogen atom or a lower alkyl group). Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used. As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer (“g” is a graft) Represents the same), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer And polymers and ethylene / methyl methacrylate / glycidyl methacrylate copolymers. Among these, a copolymer selected from ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer and ethylene / methyl methacrylate / glycidyl methacrylate copolymer is preferably used.

  Examples of the olefin copolymer containing a carboxyl group and an acid anhydride group that are particularly useful in the present invention include an ethylene / α-olefin copolymer using an α-olefin having 6 to 12 carbon atoms, a carboxyl group, and an acid. Those having an anhydride group introduced are preferred, and those having a carboxyl group and an acid anhydride group introduced to an ethylene / 1-butene copolymer and an ethylene / propylene copolymer are more preferred.

  The (d) olefin resin of the present invention preferably has a melt flow rate (hereinafter abbreviated as MFR) measured at 190 ° C. under a load of 2160 g in accordance with ASTM-D1238 of 0.01 to 70 g / 10 minutes, more preferably. Is 0.03 to 60 g / 10 min. When the MFR is less than 0.01 g / 10 minutes, the fluidity of the resin composition is lowered, which is not preferable. When the MFR exceeds 70 g / 10 min, the impact strength may be lowered depending on the shape of the molded product, which is not preferable.

The density of the (d) olefin resin of the present invention is preferably 850 to 990 kg / m ³ . When the density exceeds 990 kg / m ³ , the toughness tends to decrease, which is not preferable. If the density is less than 850 kg / m ³ , the handling property is lowered, which is not preferable.

  The blending ratio of (a) PPS resin and (b) PPE resin in the present invention is (a) 85 to 51% by weight of PPS resin, (b) with the total of component (a) and component (b) being 100% by weight. The PPE resin needs to be 15 to 49% by weight. (B) When the PPE resin is less than 15% by weight, not only a sufficiently low dielectric constant effect can be obtained, but also the effect of reducing creep strain becomes small. On the other hand, when (b) PPE resin exceeds 49 weight%, since the heat resistance of a resin composition and chemical resistance will fall remarkably, it is unpreferable. The more preferable blending ratio of (a) PPS resin and (b) PPE resin is (a) 80 to 51% by weight of PPS resin and (b) 20 to 49% by weight of PPE resin, which effectively reduces the dielectric constant. From the viewpoint, (a) 70 to 51% by weight of PPS resin and (b) 30 to 49% by weight of PPE resin are more preferable.

  The blending ratio of the silane coupling compound containing at least one functional group selected from (c) epoxy group, amino group and isocyanate group in the present invention is the sum of (a) PPS resin and (b) PPE resin. It is preferable that it is 0.1-5 weight part as 100 weight part. (C) When the silane coupling compound is less than 0.1 parts by weight, it is difficult to improve the elongation of the resin composition. On the other hand, when the amount of (c) the silane coupling compound exceeds 5 parts by weight, the melt viscosity of the resin composition is extremely increased and the molding lower limit pressure is increased. (C) The more preferable amount of the silane coupling compound is 0.2 to 3.0 parts by weight, and in addition to suppressing an increase in melt viscosity, it is also 0. More preferably, it is 4 to 2.0 parts by weight.

  The blending ratio of the (d) olefin resin in the present invention is preferably 1 to 45 parts by weight, with the total of (a) PPS resin and (b) PPE resin being 100 parts by weight. (D) When the amount of the olefin resin is less than 1 part by weight, not only is it difficult to improve the elongation of the resin composition, but also the effect of lowering the dielectric constant is reduced. On the other hand, when the amount of (d) the olefin resin exceeds 45 parts by weight, the melt viscosity of the resin composition is remarkably increased and the heat resistance is lowered, which is not preferable. (D) The more preferable blending amount of the olefin resin is 5 to 40 parts by weight, and 10 to 35 parts by weight can be exemplified as a more preferable range from the viewpoint of heat resistance, elongation improvement effect, and dielectric constant reduction effect. .

  In the polyphenylene sulfide resin composition of the present invention, in the morphology observed with an electron microscope, (a) the PPS resin forms a continuous phase (sea phase), (b) the PPE resin forms a dispersed phase (island phase), (B) Dispersed particles made of (a) PPS resin must be present in the dispersed phase made of PPE resin.

  Although a schematic diagram is shown in FIG. 1, by having such a phase structure, the dielectric constants of (a) PPS resin and (b) PPE resin, and the blending amount of (a) PPS resin and (b) PPE resin Thus, the effect of lowering the dielectric constant can be obtained more than the dielectric constant estimated from the above.

  Note that (b) dispersed particles made of PPS resin present in a dispersed phase made of PPE resin are basically (a) PPS resin as a main component, but (a) PPS resin. A resin other than the above and (a) a reaction product of a PPS resin and another resin may be partially included. However, from the viewpoint of effectively reducing the dielectric constant, it is preferable that (a) the PPS resin is contained in a proportion of 90% or more.

  At this time, it is more preferable that the dispersed particles made of (a) PPS resin exist in the dispersed phase made of (b) PPE resin in the range of the number average particle diameter of 1 to 200 nm. (A) The effect of lowering the dielectric constant of the PPS resin composition is further improved by making the dispersed particles made of PPS resin into fine particles in the range of the number average particle diameter of 1 to 200 nm. (A) When the number average particle diameter of the dispersed particles made of PPS resin is less than 1 nm, it approaches a partially compatible system, so that it is difficult to obtain an excellent low dielectric constant effect. On the other hand, when the thickness exceeds 200 nm, the contact interface between (a) PPS resin and (b) PPE resin is reduced, and it is difficult to obtain the same excellent low dielectric constant effect. (A) About the dispersed particle which consists of PPS resin, the range of a more preferable number average particle diameter is 5-180 nm, Furthermore, 10-150 nm is more preferable from a viewpoint of productivity.

  Furthermore, in this case, it can also be exemplified as a preferable phase structure that (a) dispersed particles made of PPS resin are present in an area ratio of 2 to 50% in the dispersed phase made of (b) PPE resin. (A) The area ratio of the dispersed particles made of PPS resin is 2 to 50% with respect to the dispersed phase made of (b) PPE resin, whereby the effect of reducing the dielectric constant of the PPS resin composition is further improved. . When the area ratio of the dispersed particles made of (a) PPS resin is less than 2%, the contact interface between (a) PPS resin and (b) PPE resin is reduced, so that it is difficult to obtain an excellent effect of reducing the dielectric constant. On the other hand, if it exceeds 50%, an excellent low dielectric constant effect can be obtained, but the tensile elongation is remarkably lowered, which is not preferable. (A) A more preferable area ratio of the dispersed particles made of the PPS resin is 3 to 30%, and further preferably 5 to 20% from the viewpoint of productivity.

In addition, (b) the dispersed phase composed of the PPE resin is composed of two groups of a dispersed phase (A) having a number average particle diameter of more than 300 nm and a dispersed phase (B) having a number of 300 nm or less. Only (a) a phase structure containing dispersed particles made of a PPS resin can be preferably exemplified. Thus, the presence of the dispersed phase (A) composed of (b) PPE resin having a particle diameter of more than 300 nm makes it easy to develop a relatively high tensile elongation. On the other hand, the presence of the dispersed phase (B) made of (b) PPE resin having a particle size of 300 nm or less tends to lower the dielectric constant, making it easy to achieve both elongation and low dielectric constant. The ratio (n _A / n _B ) between the number n _A of the dispersed phase (A) made of PPE resin and having a particle diameter exceeding 300 nm and the number n _B of the dispersed phase (B) having a particle diameter of 300 nm or less is 0. It is preferable that it is 05-1.00 from a viewpoint with which elongation and a low dielectric constant are compatible. In order to further reduce the dielectric constant, the range of 0.1 to 0.5 is more preferable, and in order to easily improve the elongation, the range of 0.5 to 0.9 is more preferable.

  The phase structure observed with an electron microscope referred to here is an ASTM No. 1 dumbbell test piece in which the resin composition of the present invention is injection-molded, and its central part is cut in a direction perpendicular to the resin flow direction. A thin piece of 0.1 μm or less is cut at −20 ° C. from the center of the cross section, and is applied to an H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) manufactured by Hitachi, Ltd. The photo was taken at a magnification of 10,000 times.

  Based on this observation photograph, the presence or absence of (a) PPS dispersed particles present in (b) the PPE dispersed phase was confirmed.

  In addition, regarding (b) the number average particle diameter of (a) PPS dispersed particles present in the PPE dispersed phase, first, for each (a) PPS dispersed particle portion, the respective maximum diameter and minimum diameter are measured and averaged. The value was defined as the dispersed particle size, and then the average value thereof was obtained.

  (B) Regarding the area ratio of the (a) PPS dispersed particles present in the PPE dispersed phase, the above-described morphology observation photograph was further magnified four times, and then for any (b) PPE dispersed phase, (b) From the weight (X) obtained by cutting out and weighing the area portion of PPE and (b) the weight portion (Y) obtained by cutting out and weighing the area portion of (a) PPS dispersed particles present in the PPE dispersed phase, (Y) / (( X) + (Y)). When (b) the PPE dispersed phase is divided into two groups of a dispersed phase (A) having a particle diameter of more than 300 nm and a dispersed phase (B) having a particle diameter of 300 nm or less, (a) The area ratio was estimated only for the dispersed phase (A) containing PPS dispersed particles.

(B) of the PPE dispersed phase, and the particle number _{n A} of the dispersed phase (A) consisting of particle size greater than 300 nm, number of particles _{n B} ratio _{(n A} of the dispersed phase consisting of the following particle size 300 nm (B) / N _B ) (a) For any (b) PPE dispersed particles present in the PPS continuous phase, after counting the number of particles n _A and n _B , respectively, according to the calculation formula of n _A / n _B Asked.

  Although the polyphenylene sulfide resin composition of the present invention has a low dielectric constant, it is desirable that the dielectric constant is 3.2 or less from the viewpoint of practicality. The dielectric constant referred to here is a relative dielectric constant which is a ratio to a so-called vacuum dielectric constant, and a frequency of a (vertical) 100 mm × (horizontal) 70 mm × (thickness) 3 mm square plate test piece. It is measured by a transformer bridge method based on ASTM D 150 under the conditions of 1 MHz, measurement temperature 23 ° C., and 50% RH.

  The polyphenylene sulfide resin composition of the present invention has excellent tensile elongation as well as low dielectric constant, but from the viewpoint of practicality, the tensile break elongation of ASTM No. 1 dumbbell molded piece (manufactured by Instron) (Measured using a 5581 type tensile tester at a distance between tests of 100 mm and a tensile speed of 10 mm / min) is preferably 5% or more, and more preferably 8% or more. When the tensile elongation at break is less than 5%, it is not preferable because sufficient durability is not obtained due to insufficient toughness of various molded articles made of the polyphenylene sulfide resin composition of the present invention.

Production method of polyphenylene sulfide resin composition As a method of producing the thermoplastic resin composition of the present invention, production in a molten state, production in a solution state, etc. can be used. Manufacturing can be preferably used. For production in a molten state, melt kneading with an extruder, melt kneading with a kneader, or the like can be used. From the viewpoint of productivity, melt kneading with an extruder that can be continuously produced can be preferably used. For melt kneading by an extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improvement in productivity, reactivity, and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt kneading with a twin-screw extruder is most preferable.

  A more specific method for producing the resin composition of the present invention is not necessarily limited to this, but L / D (L: screw length, D: screw diameter) is 10 or more, preferably 20 or more, A twin screw extruder having a kneading screw element having 2 or more, preferably 3 or more kneading parts and having a notch in the screw flight in a length of 3 to 20% of the total L / D Is preferably used. By using the stirring screw element having a notch in the screw flight with the above-described specific length, dispersed particles made of (a) PPS resin are present in the (b) PPE resin dispersed phase of the present invention. A specific phase structure can be easily formed. As a stirring screw which has a notch part, it is preferable that the number of notches in a screw flight part is 10-15 per pitch. As a more preferable length of the stirring screw element having a notch, 5 to 15% can be exemplified, and 7 to 13% can be further exemplified as a preferable range.

  In addition, the screw rotation speed of the twin screw extruder is 150 to 1000 rotations / minute, preferably 300 to 1000 rotations / minute, and the resin temperature during mixing is (a) the melting peak temperature of the PPS resin +10 to 70 ° C. Thus, the method of kneading is preferred.

  In addition, although there is no restriction | limiting in particular about the upper limit of L / D of a twin-screw extruder, 60 or less is preferable from a viewpoint of economical efficiency. The upper limit of the kneading portion is not particularly limited, but is preferably 10 or less from the viewpoint of productivity.

  The mixing order of the raw materials is not particularly limited, and a method in which all the raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are melted and kneaded by the above-described method, and this and the remaining raw materials are blended Any method may be used, such as a method of melt-kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw extruder. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.

  In the resin composition of the present invention, when the modified (b) PPE resin is used together with the (c) silane coupling agent, (a) the PPS resin and (c) the silane coupling agent are previously melt-kneaded. Thereafter, (b) a technique of melt-kneading with the PPE resin is mentioned as a preferable technique from the viewpoint of further reducing the dielectric constant. In this case, (a) PPS resin and (c) silane coupling agent may be previously melt-kneaded and pelletized, then (b) mixed with PPE resin and further melt-kneaded, or (a) PPS resin (C) A silane coupling agent may be mixed with (b) PPE resin using a side feeder during melt kneading in advance.

  Furthermore, when (d) the olefin resin is used in combination, the method of mixing the (d) olefin resin using a side feeder during melt kneading of other raw materials is the (d) thermal oxidation degradation of the olefin resin. It is preferable at the point which suppresses.

Inorganic filler The polyphenylene sulfide resin composition of the present invention is not an essential component, but there is no problem even if an inorganic filler is blended within a range not impairing the effects of the present invention. Specific examples of such inorganic fillers include glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber. , Ceramic filler, asbestos fiber, stone fiber, metal fiber, etc., or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina Silicate such as silicate, metal compound such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, iron oxide, metal powder such as copper, nickel, zinc, cobalt, iron, manganese or Gold, calcium carbonate, magnesium carbonate, carbonates such as dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, Non-fibrous fillers such as ceramic beads, boron nitride, silicon carbide, carbon black and silica, and graphite are used. Of these, glass fibers, silica, and calcium carbonate are preferable, and calcium carbonate and silica are anticorrosives and lubricants. It is particularly preferable from the viewpoint of the effect. These inorganic fillers may be hollow, and two or more kinds may be used in combination. Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the anticorrosive material, the lubricant, and the effect of imparting conductivity.

  The compounding quantity of this inorganic filler can illustrate the range of 1-300 weight part with respect to a total of 100 weight part of (a) PPS resin and (b) PPE resin.

Other Additives Further, other resins may be added to the polyphenylene sulfide resin composition of the present invention within a range not impairing the effects of the present invention. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone resin, polyether ether. Examples thereof include ketone resins, polyimide resins, polyamideimide resins, and tetrafluoropolyethylene resins.

  Moreover, the following compounds can be added for the purpose of modification. Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, crystal nucleating agents such as organophosphorus compounds, polyetheretherketone, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensates, release agents such as silicone compounds, anti-coloring agents such as hypophosphite, (3,9-bis [2- (3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) Antioxidants, phosphorus such as (bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite) Ordinary additives such as water-based antioxidants, water, lubricants, ultraviolet light inhibitors, colorants, foaming agents and the like can be blended. If any of the above compounds exceeds 20% by weight of the total composition, the properties of the present invention are impaired, so that it is not preferred, and 10% by weight or less, more preferably 1% by weight or less is added.

The polyphenylene sulfide resin composition of the present invention can be molded by various molding techniques such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding and the like, but is particularly useful for injection molding applications.
In addition, the polyphenylene sulfide resin composition of the present invention has excellent tensile elongation at break, low dielectric constant, and low creep deformation, so that it is an electric / electronic component, communication device component, automobile component, home appliance component, OA device component. For example, it can be widely used for cables, tubes, fibers, blow molded articles, films, sheets and the like.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

  In the following examples, material characteristics were evaluated by the following methods.

[injection molding]
Using an injection molding machine SE75-DUZ manufactured by Sumitomo Heavy Industries, under the conditions of a resin temperature of 320 ° C. and a mold temperature of 150 ° C., an ASTM No. 1 dumbbell test piece and (vertical) 100 mm × (horizontal) 70 mm × (thickness) 3 mm ( A square plate specimen having a gate shape (film gate) was formed.

[Morphological observation]
The center part of the injection-molded ASTM No. 1 dumbbell test piece was cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less was cut at −20 ° C. from the center part of the cross section. After being photographed at a magnification of 10,000 times with a H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times), (b) present in the PPE dispersed phase (A) The presence or absence of PPS dispersed particles was confirmed.

  (B) Regarding the number average particle diameter of (a) PPS dispersed particles existing in the PPE dispersed phase, first, for each (a) PPS dispersed particle portion, the respective maximum diameter and minimum diameter are measured to obtain the average value. It was set as the dispersed particle diameter, and it calculated | required as those average values after that.

  (B) Regarding the area ratio of the (a) PPS dispersed particles present in the PPE dispersed phase, the above-described morphology observation photograph was further magnified four times, and then for any (b) PPE dispersed phase, (b) From the weight (X) obtained by cutting out and weighing the area portion of PPE and (b) the weight portion (Y) obtained by cutting out and weighing the area portion of (a) PPS dispersed particles present in the PPE dispersed phase, (Y) / (( X) + (Y)). When (b) the PPE dispersed phase is divided into two groups of a dispersed phase (A) having a particle diameter of more than 300 nm and a dispersed phase (B) having a particle diameter of 300 nm or less, (a) The area ratio was estimated only for the dispersed phase (A) containing PPS dispersed particles.

(B) of the PPE dispersed phase, and the particle number _{n A} of the dispersed phase (A) consisting of particle size greater than 300 nm, number of particles _{n B} ratio _{(n A} of the dispersed phase consisting of the following particle size 300 nm (B) / N _B ) (a) For any (b) PPE dispersed particles present in the PPS continuous phase, after counting the number of particles n _A and n _B , respectively, according to the calculation formula of n _A / n _B Asked.

[Tensile elongation]
The injection molded ASTM No. 1 dumbbell test piece was subjected to a tensile test using an Instron 5581 type tensile tester under the conditions of an atmospheric temperature of 23 ° C., a tensile speed of 10 mm / min, and an inter-test distance of 100 mm.

[Creep distortion]
The above-mentioned injection molded ASTM No. 1 dumbbell test piece was subjected to tensile creep under the conditions of an ambient temperature of 80 ° C., a load of 20 MPa, and a distance between tests of 100 mm, using a 6-clamp creep tester CP6-L-10KN manufactured by Orientec Co., Ltd. A test was conducted. About the displacement amount at the time of 100-hour progress, the creep distortion (%) was computed with the following formula.
(Displacement amount (mm) −initial strain amount (mm)) / 100 (mm) × 100 (%)

[Dielectric constant]
Transformer bridge method according to ASTM D 150 under the conditions of frequency 1 MHz, measurement temperature 23 ° C., and 50% RH for the injection molded (longitudinal) 100 mm × (horizontal) 70 mm × (thickness) 3 mm square plate test piece Was used to measure the dielectric constant.

[Reference Example 1] (a) Polymerization of PPS resin (a-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm while stirring at 0.6 ° C./min. The temperature was increased to 238 ° C. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS (a-1) had a melt viscosity of 200 Pa · s (310 ° C., shear rate of 1000 / s).

[Reference Example 2] (a) Polymerization of PPS resin (a-2)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2962.50 g (71.10 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 516.60 g (6.30 mol), and ion-exchanged water 10500 g, gradually heated to 230 ° C. over about 3 hours while flowing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.017 mol per mol of the charged alkali metal sulfide.

  Next, 10363.50 g (70.50 mol) of p-dichlorobenzene and 9078.30 g (91.70 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm while stirring at 0.6 ° C./min. The temperature was raised to 270 ° C. at a speed of 270 ° C. and held at 270 ° C. for 140 minutes. Thereafter, 2520 g (140 mol) of ion-exchanged water was injected into the autoclave while cooling to 250 ° C. at a rate of 1.3 ° C./min. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS (a-2) had a melt viscosity of 50 Pa · s (310 ° C., shear rate 1000 / s).

[Reference Example 3] (b) PPE resin b-1: poly (2,6-dimethylphenylene oxide) ("Iupiace" PX-100F manufactured by Mitsubishi Engineering Plastics)
b-2: Poly (2,6-dimethylphenylene oxide) obtained by melt mixing 100 parts by weight of “Iupiace” PX-100F with 1 part of maleic anhydride.

[Reference Example 4] (c) Silane coupling compound c-1: 3-isocyanatopropyltriethoxysilane containing at least one functional group selected from epoxy group, amino group and isocyanate group (KBE manufactured by Shin-Etsu Chemical Co., Ltd.) -9007).

[Reference Example 5] (d) Olefinic resin d-1: ethylene / 1-butene copolymer modified with maleic anhydride (“Tuffmer” MH5020 manufactured by Mitsui Chemicals).

[Reference Example 6] Screw configuration of twin-screw extruder I: Configuration with kneading screw and notch screw II: Configuration with kneading screw (no notch screw)

[Examples 1-4, 9, 10]
After dry blending (a) PPS resin, (b) PPE resin, (c) silane coupling agent, and (d) olefin resin shown in Table 1 and Table 2 at the ratio shown in Table 1, a vacuum vent was provided. Using a TEX30α type twin screw extruder manufactured by Nippon Steel Works (screw configuration I, L / D = 45, ratio of notched screw in L / D 10%), at a screw rotation speed of 300 rpm, a die out resin temperature is 330 ° C. The cylinder temperature was set so as to be as follows, and the mixture was melt-kneaded and pelletized with a strand cutter. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding.

  The obtained molded product was evaluated for morphology observation, tensile elongation, creep strain, and dielectric constant.

[Example 5]
(A) PPS resin and (c) silane coupling agent shown in Example 5 of Table 1 were dry blended so as to have the ratio shown in Example 5 of Table 1, and then manufactured by Nippon Steel Works with a vacuum vent. Using a TEX30α type twin screw extruder (screw configuration I, L / D = 45, notch screw ratio in L / D 10%), at a screw speed of 300 rpm, the die extrusion resin temperature should be 330 ° C. or lower. The cylinder temperature was set to melt kneading and pelletized with a strand cutter. Next, the obtained pellets and (b) PPE resin were dry-blended so as to have the ratio shown in Example 5 of Table 1, and then a TEX30α twin screw extruder (screw) manufactured by Nippon Steel Works equipped with a vacuum vent. Using composition I, L / D = 45, ratio of notched screw in L / D 10%), melting at a screw rotation speed of 300 rpm and setting the cylinder temperature so that the resin temperature at which the die is released is 330 ° C. or less. It knead | mixed and pelletized with the strand cutter. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding.

  The obtained molded product was evaluated for morphology observation, tensile elongation, creep strain, and dielectric constant.

[Example 6]
Melt kneading, injection molding, and evaluation were performed in the same manner as in Example 3 except that the screw rotation speed was 150 rpm.

[Example 7]
Melt kneading, injection molding, and evaluation were performed in the same manner as in Example 3 except that the ratio of the notched screw in L / D was set to 5%.

[Example 8]
(A) PPS resin, (b) PPE resin, and (c) silane coupling agent shown in Example 8 in Table 1 were dry blended in the proportions shown in Example 8 in Table 1, and then Nippon Steel Corporation equipped with a vacuum vent. Using a TEX30α type twin screw extruder (screw configuration I, L / D = 45, ratio of notched screw in L / D 10%) at a screw rotation speed of 500 rpm, the die extrusion resin temperature is 330 ° C. or lower. The cylinder temperature was set so as to be melt-kneaded and pelletized with a strand cutter.

  Subsequently, the obtained pellet was further melt-kneaded under the same conditions and pelletized with a strand cutter. The pellets were dried at 130 ° C. overnight and then subjected to injection molding.

  The obtained molded product was evaluated for morphology observation, tensile elongation, creep strain, and dielectric constant.

[Comparative Example 1]
A TEX30α type twin screw extruder manufactured by Nippon Steel Works, which was dry-blended with (a) PPS resin, (b) PPE resin, and (c) silane coupling agent shown in Table 2 in the proportions shown in Table 1, and equipped with a vacuum vent. (Screw configuration II, L / D = 45, notch screw ratio in L / D 0%), and at a screw speed of 100 rpm, the cylinder temperature is set so that the die-out resin temperature is 330 ° C. or less. And kneaded and pelletized with a strand cutter. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding.

  The obtained molded product was evaluated for morphology observation, tensile elongation, creep strain, and dielectric constant.

[Comparative Examples 2-3]
Nippon Steel Works equipped with a vacuum vent after dry blending (a) PPS resin, (b) PPE resin, (c) silane coupling agent, and (d) olefin resin shown in Table 2 in the ratio shown in Table 1. Using a TEX30α type twin screw extruder (screw configuration II, L / D = 45, notch screw ratio in L / D 0%), the resin temperature of the die is 330 ° C. or less at a screw speed of 300 rpm. Thus, the cylinder temperature was set and melt-kneaded, and pelletized with a strand cutter. The obtained pellets were dried at 130 ° C. overnight and then subjected to injection molding.

  The obtained molded product was evaluated for morphology observation, tensile elongation, creep strain, and dielectric constant.

  The results of the above examples and comparative examples will be compared and described.

  In Example 3, the relative dielectric constant decreased to 2.85 due to the presence of dispersed particles composed of (a) PPS in the (b) PPE dispersed phase.

  On the other hand, the dielectric constant was relatively high in Comparative Examples 1 and 2 in which (b) the dispersed particles of (a) PPS were not included in the (b) PPE dispersed phase.

  In Example 4, by using PPE kneaded with maleic anhydride, a high tensile elongation was obtained together with a low dielectric constant.

In Example 5, as a result of changing the kneading method based on the composition of Example 4, the value of n _A / n _B was reduced, the relative permittivity was further lowered, and the creep strain was also reduced.

  In Example 9, in which (d) an olefin was blended based on the composition of Example 3, high tensile elongation was exhibited and the relative dielectric constant decreased to 2.66.

  On the other hand, in Comparative Example 3 in which (b) the PPE resin did not contain dispersed particles made of (a) PPS resin, the dielectric constant was increased and the creep strain was remarkably increased although the composition was the same.

1: PPS resin continuous phase 2: PPE dispersed phase 3: Dispersed particles composed of PPS component present in dispersed phase composed of PPE

Claims (8)

A resin composition comprising (a) 85 to 51% by weight of a polyphenylene sulfide resin and (b) 15 to 49% by weight of a polyphenylene ether resin, wherein the total of the component (a) and the component (b) is 100% by weight. In the morphology observed with an electron microscope of a molded article comprising a resin composition, (a) component forms a continuous phase (sea phase), (b) component forms a dispersed phase (island phase), and (b) component A polyphenylene sulfide resin composition, wherein dispersed particles comprising the component (a) are present in a dispersed phase comprising: 2. The polyphenylene according to claim 1, wherein the dispersed particles composed of the (a) polyphenylene sulfide resin are present in a dispersed phase composed of the (b) polyphenylene ether resin with a number average particle diameter of 1 to 200 nm. A sulfide resin composition. The dispersed phase consisting of (a) polyphenylene sulfide resin is present in the dispersed phase consisting of (b) polyphenylene ether resin in an area ratio of 2 to 50% based on the area of the dispersed phase. Item 3. The polyphenylene sulfide resin composition according to any one of Items 1 and 2. (B) The dispersed phase composed of the polyphenylene ether resin is composed of two groups of a dispersed phase (A) having a particle diameter exceeding 300 nm and a dispersed phase (B) having a particle diameter of 300 nm or less. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein only (A) contains dispersed particles composed of the (a) polyphenylene sulfide resin. (B) The ratio (n _A / n _B ) of the dispersed particle number n _A of the dispersed phase (A) comprising the polyphenylene ether resin to the dispersed particle number n _B of the dispersed phase ( _B ) is 0.05 to 1.00 The polyphenylene sulfide resin composition according to claim 4, wherein the polyphenylene sulfide resin composition is present. A silane cup containing 100 parts by weight of the total of (a) polyphenylene sulfide resin and (b) polyphenylene ether resin, and further containing (c) at least one functional group selected from an epoxy group, an amino group, and an isocyanate group The polyphenylene sulfide resin composition according to claim 1, comprising 0.1 to 5 parts by weight of a ring compound. The total amount of the (a) polyphenylene sulfide resin and the (b) polyphenylene ether resin is 100 parts by weight, and further comprises (d) 1 to 45 parts by weight of an olefin-based resin. A polyphenylene sulfide resin composition according to claim 1. The ratio (L / D) of the screw length L to the screw diameter D is 10 or more, and 3 to 20% of the L / D is composed of a stirring screw element having a notch in the screw flight. The method for producing a polyphenylene sulfide resin composition according to any one of claims 1 to 7, wherein melt kneading is performed using a twin screw extruder.