JP6497110B2 - Polyphenylene sulfide resin composition - Google Patents

Description

  The present invention relates to a polyphenylene sulfide resin composition that is flexible and high toughness, and has excellent heat aging resistance.

  Polyphenylene sulfide (hereinafter abbreviated as PPS) resin has properties suitable for engineering plastics, such as excellent heat resistance, chemical resistance, flame retardancy, electrical insulation, and moist heat resistance. -Widely used in electronic parts, communication equipment parts, automobile parts, etc. However, since there are relatively hard and brittle weak points, many improvements have been reported so far by blending an elastomer with a PPS resin to give flexibility, but in this case, the PPS resin inherently superior due to the elastomer. In addition to sacrificing heat resistance and chemical resistance, new problems such as significant deterioration in mechanical properties after high-temperature heat treatment occur.

  Thus, some attempts have been reported to blend a flexible component having high heat resistance into the PPS resin. For example, Patent Document 1 discloses a polymer blend in which a poly (imide-siloxane) block copolymer is blended with an engineering thermoplastic as an impact modifier. However, although blending with poly (imide-siloxane) block copolymer can give a certain degree of flexibility and impact resistance, it is still inadequate and is not suitable for fitting or free folding. The current situation is limited. Patent Document 2 discloses a polyarylene sulfide film in which siloxane-modified polyetherimide is blended with polyarylene sulfide. This makes it possible to provide a release film that is less likely to be embrittled, but its technical point is to suppress the crystallization of polyarylene sulfide by blending with a siloxane-modified polyetherimide, thereby increasing the thickness of the film. However, it was intended to enable uniform stretching, and it was still inadequate in terms of having dramatically superior heat aging resistance while being flexible and tough. Patent Document 3 discloses that an olefin copolymer may be blended as another additive to a resin composition comprising a polyphenylene sulfide resin and a poly (etherimide-siloxane) copolymer. In this case, however, the poly (ether imide-siloxane) copolymer forms a primary dispersed phase, and the olefin copolymer forms a specific phase structure in the primary dispersed phase. Therefore, even though it is possible to impart a high degree of flexibility and toughness, the heat aging resistance is extremely poor as in the case of a resin composition with a normal elastomer. Patent Document 4 discloses a thermoplastic resin composition in which core / shell polymer particles are dispersed in a continuous phase composed of polyphenylene sulfide. However, since the core is made of a crosslinked elastomer, it is insufficient in terms of imparting flexibility and toughness, and since the shell is a thermoplastic polymer having low heat resistance such as polymethyl methacrylate, the heat aging resistance is remarkably inferior. There were drawbacks.

JP-A 63-199737 JP2013-139532A JP 2012-46721 A Special table 2013-53115 gazette

  The present invention is to provide a polyphenylene sulfide resin composition that has drastically improved heat aging resistance as well as high flexibility and toughness without impairing the heat resistance, chemical resistance, and flame resistance inherent in the polyphenylene sulfide resin. It is to be an issue.

  Accordingly, as a result of intensive studies to solve the above problems, the present inventors have found that a resin composition comprising a polyphenylene sulfide resin, a poly (ether imide-siloxane) copolymer, and an olefin elastomer is poly (ether imide-siloxane). ) By constructing a specific phase structure in which the olefinic elastomer forms a secondary dispersed phase in the primary dispersed phase made of a copolymer, it has dramatically improved heat aging as well as high flexibility and toughness, which was difficult with conventional technologies. As a result, the present invention has been achieved.

That is, the present invention is as follows.
1. (A) Polyphenylene sulfide resin composition containing 1 to 150 parts by weight of (b) poly (ether imide-siloxane) copolymer and (c) 1 to 150 parts by weight of olefin elastomer with respect to 100 parts by weight of polyphenylene sulfide resin In the morphology observed by an electron microscope, (a) component forms a continuous phase, (b) component forms a primary dispersed phase, and (c) component is a secondary dispersed phase in the primary dispersed phase. A polyphenylene sulfide resin composition characterized by forming
2. 80% by volume or more of the (c) olefin-based elastomer is present as a secondary dispersed phase in the primary dispersed phase comprising the (b) poly (ether imide-siloxane) copolymer. The polyphenylene sulfide resin composition according to the description,
3. The polyphenylene sulfide resin composition according to any one of claims 1 to 2, wherein the number average dispersed particle size of the primary dispersed phase comprising the (b) poly (etherimide-siloxane) copolymer is 1500 nm or less. ,
4). The polyphenylene sulfide resin composition according to any one of 1 to 3, wherein the number average dispersed particle size of the secondary dispersed phase comprising the (c) olefin elastomer is 1000 nm or less,
5. The polyphenylene sulfide resin composition according to any one of 1 to 4, wherein the (a) polyphenylene sulfide resin contains 200 ppm or more of alkali metal and / or alkaline earth metal,
6). The dispersity represented by the weight average molecular weight / number average molecular weight of the (a) polyphenylene sulfide resin is 2.5 or less, and the heating rate is 20 ° C./50° C. to 340 ° C. in a normal pressure non-oxidizing atmosphere. The polyphenylene sulfide resin composition according to any one of 1 to 4, wherein the weight loss rate at 100 ° C. to 330 ° C. when thermogravimetric analysis is performed in minutes is 0.2% by weight or less,
7 . A method for producing a polyphenylene sulfide resin composition according to any one of 1 to 6, wherein a part of the (a) polyphenylene sulfide resin and the (b) poly (etherimide-siloxane) copolymer are previously melted After the kneading, (a) the remainder of the polyphenylene sulfide resin, and (c) the method for producing a polyphenylene sulfide resin composition, which is further melt-kneaded with the olefin elastomer,
8 . A molded article comprising the polyphenylene sulfide resin composition according to any one of 1 to 6,
It is.

  According to the present invention, it is possible to obtain a polyphenylene sulfide resin composition having dramatically improved heat aging resistance while exhibiting low elasticity and flexibility and high toughness. These characteristics are suitable for applications such as tubes and hoses used for fitting and bending, especially ducts and hoses around automobile engines used under high temperature and vibration.

It is a schematic diagram of the phase-separation structure which the PPS resin composition of this invention forms.

  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 toughness. For example, a range exceeding 30 Pa · 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 these, the easiest method is 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 and heat aging resistance, residual oligomers and residual salts are removed by repeating organic solvent cleaning and warm water of about 80 ° C. or hot water cleaning several times. After removal, an acid treatment or a method of treating with an alkali metal salt or alkaline earth metal salt is preferred, and a method of treating with an alkali metal salt or alkaline earth metal salt is particularly preferred.

  The polyphenylene sulfide resin composition of the present invention is extremely soft and excellent in high toughness, and retains high mechanical properties even after being exposed for a long time under high temperature conditions. In order to express such properties, the total of (a) alkali metal and / or alkaline earth metal content contained in the PPS resin is preferably 200 ppm or more, more preferably 500 ppm or more, and further 700 ppm. The above is preferable.

  For example, when (d) a compound having a functional group such as an amino group, an epoxy group, or an isocyanate group added as a compatibilizer is an epoxy compound, (a) an alkali metal contained in the PPS resin and / or When the total alkaline earth metal content is 200 ppm or more, the reaction between (a) the PPS resin and (d) the compound having an epoxy group is promoted, and (b) a poly (ether imide-siloxane) copolymer or (c This is because high toughness is easily developed as a result of finer dispersion of the olefin elastomer. In particular, when the compatibilizer is (c) a compound having an epoxy group, (a) the alkali metal and / or alkaline earth metal contained in the PPS resin is more preferably Na.

  Regardless of the type of functional group of the compound (d) amino group, epoxy group, or isocyanate group that is the compatibilizer, (a) the alkali metal and / or alkaline earth metal component contained in the PPS resin When the total is 200 ppm or more, as a result of improving the heat resistance stability, high mechanical properties are maintained even after being exposed for a long time under high temperature conditions.

  On the other hand, when (d) the compound having a functional group such as an amino group, an epoxy group, or an isocyanate group, which is a compatibilizer, is a compound having an amino group or an isocyanate group, (a) an alkali metal contained in the PPS resin When the total of alkaline earth metal content is less than 200 ppm, the reaction with (a) PPS resin may proceed more easily. However, from the viewpoint of improving the heat-resistant stability described above, it is preferable that the total amount of (a) alkali metal and / or alkaline earth metal contained in the PPS resin is 200 ppm or more. Therefore, after the reaction between the (a) PPS resin having a total alkali metal and / or alkaline earth metal content of less than 200 ppm and (d) the compound having an amino group or an isocyanate group is completed, the alkali metal and / or the above-described alkali metal and / or It is preferable to add (a) PPS resin treated with alkaline earth metal and adjust the total of alkali metal and / or alkaline earth metal content contained in final (a) PPS resin to be 200 ppm or more. It can be illustrated as a method. In addition, (a) a compound having an amino group, an epoxy group, or an isocyanate group by simultaneously using PPS with a total of less than 200 ppm and 200 ppm or more of alkali metals and / or alkaline earth metals contained in the PPS resin. Of course, it is also possible to use for reaction.

  When the total content of the alkali metal and / or alkaline earth metal is less than 200 ppm, the effect of improving the heat stability is insufficient, which is not preferable. Although there is no restriction | limiting in the upper limit of the total content of an alkali metal and / or alkaline-earth metal, 3000 ppm or less is preferable and 2000 ppm or less is more preferable from a viewpoint which does not impair wet heat resistance and electrical insulation. The total content of alkali metal and / or alkaline earth metal referred to here is a value measured by an atomic absorption method using an aqueous solution of an ash obtained by ashing a PPS resin as a sample.

  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 a substantially linear PPS resin that is not subjected to high molecular weight by thermal oxidation cross-linking treatment from the viewpoint of expressing excellent toughness, or is mildly oxidized cross-linking treatment The semi-crosslinked PPS resin is preferable. 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.

  Further, as the PPS resin used in the resin composition of the present invention, (a) the polyphenylene sulfide resin has a dispersity represented by a weight average molecular weight / number average molecular weight of 2.5 or less, under a normal pressure non-oxidizing atmosphere. It is also preferable to use a material having a weight loss rate of 100% to 330 ° C. at 0.2% by weight or less when thermogravimetric analysis is performed from 50 ° C. to 340 ° C. at a heating rate of 20 ° C./min. It is done.

  A more preferable range of the degree of dispersion represented by the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 2.3 or less, more preferably 2.1 or less, and 2.0 The following is even more preferred. When the degree of dispersion exceeds 2.5, (a) the amount of low molecular components contained in the PPS resin tends to increase, which is not preferable from the viewpoint of reducing the mechanical properties of the PPS resin composition of the present invention. . The weight average molecular weight and number average molecular weight can be determined using, for example, SEC (size exclusion chromatography) equipped with a differential refractive index detector.

  A more preferable range of the weight loss rate at 100 ° C. to 330 ° C. when the thermogravimetric analysis is performed from 50 ° C. to 340 ° C. at a rate of temperature increase of 20 ° C./min in a non-oxidizing atmosphere at normal pressure is as follows. It is 18 weight% or less, More preferably, it is 0.12 weight%, 0.1 weight% or less is much more preferable. When the weight reduction rate exceeds the range of 0.2% by weight, for example, the amount of generated gas increases when the PPS resin composition of the present invention is molded, and voids are easily formed in the molded product. This is not preferable because the mechanical properties are deteriorated.

  The weight reduction rate can be obtained by a general thermogravimetric analysis, and an atmospheric pressure non-oxidizing atmosphere is used as the atmosphere in this analysis. A non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the sample is 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas such as nitrogen, helium, or argon. A nitrogen atmosphere is particularly preferred from the standpoints of economy and ease of handling. The normal pressure is a pressure in the vicinity of the standard state of the atmosphere, and is an atmospheric pressure condition in which the temperature is about 25 ° C. and the absolute pressure is about 101.3 kPa. When the measurement atmosphere is other than the above, (a) the oxidation of the PPS resin occurs during the measurement, or it is actually different from the atmosphere used in the molding process of the PPS resin composition of the present invention. There is a possibility that it cannot be measured.

  In measuring the weight loss rate, thermogravimetric analysis is performed by raising the temperature from 50 ° C. to an arbitrary temperature of 340 ° C. or higher at a temperature rising rate of 20 ° C./min. Preferably, after holding at 50 ° C. for 1 minute, the temperature is increased at a rate of temperature increase of 20 ° C./min to perform thermogravimetric analysis. This temperature range is a temperature region frequently used when actually using the PPS resin composition of the present invention, and is frequently used when the solid (a) PPS resin is melted and then molded into an arbitrary shape. It is also a temperature range. The weight reduction rate in the actual use temperature region is related to (a) the amount of gas generated from the PPS resin during actual use, the amount of components attached to the die or mold during molding, and the like. Therefore, it can be said that the lower the weight loss rate in such a temperature range, the better the quality (a) PPS resin. The weight reduction rate is desirably measured with a sample amount of about 10 mg, and the shape of the sample is desirably a fine particle of about 2 mm or less.

  The (a) PPS resin having a dispersity of 2.5 or less and a weight reduction rate of 0.2% by weight or less can be obtained by heating cyclic polyarylene sulfide. The cyclic polyarylene sulfide is a simple compound of a cyclic compound such as the following general formula (Q) having a repeating unit of the formula: — (Ar—S) — as the main constituent unit, and preferably containing 80 mol% or more of the repeating unit. A mass or a mixture,

It contains at least 50% by weight or more of the cyclic compound of formula (Q), preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. The upper limit value of the cyclic polyarylene sulfide contained in the cyclic polyarylene sulfide is not particularly limited, but 98% by weight or less, preferably 95% by weight or less can be exemplified as a preferable range. Usually, the higher the weight ratio of the cyclic polyarylene sulfide in the cyclic polyarylene sulfide, the higher the molecular weight of the (a) PPS resin obtained after heating.

  In addition, as the cyclic compound of the formula (Q), particularly preferred as the cyclic polyarylene sulfide, a p-phenylene sulfide unit is used as a main structural unit.

Is a cyclic compound containing 80 mol% or more, particularly 90 mol% or more.

  Although there is no restriction | limiting in particular in the repeating number m in the said (Q) formula contained in cyclic polyarylene sulfide, 4-50 are preferable, 4-25 are more preferable, 4-15 can be illustrated as a further more preferable range, 8 The (Q) cyclic compound having the above as the main component is even more preferable. As will be described later, the conversion of the cyclic polyarylene sulfide to the polyarylene sulfide by heating is preferably performed at a temperature higher than the temperature at which the cyclic polyarylene sulfide is melted, but when m is increased, the melting temperature of the cyclic polyarylene sulfide is melted. Therefore, it is advantageous to set m in the above range from the viewpoint that the conversion of the cyclic polyarylene sulfide to the (a) PPS resin can be performed at a lower temperature. Since cyclic compounds having m of 7 or less tend to have low reactivity, it is advantageous to set m to 8 or more from the viewpoint that (a) a PPS resin can be obtained in a short time.

  The cyclic compound of the formula (Q) contained in the cyclic polyarylene sulfide may be either a single compound having a single repeating number or a mixture of cyclic compounds having different repeating numbers, but different repeating numbers. A mixture of cyclic compounds having a tendency to have a lower melt solution temperature than a single compound having a single number of repetitions, and the use of a mixture of cyclic compounds having different numbers of repetitions is (a) PPS resin This is preferable because the temperature during the conversion can be lowered.

  It is particularly preferable that the components other than the cyclic compound of the formula (Q) in the cyclic polyarylene sulfide are polyarylene sulfide oligomers. Here, the polyarylene sulfide oligomer is a linear homo-oligomer or co-oligomer having a repeating unit of the formula, — (Ar—S) —, as a main constituent unit, preferably containing 80 mol% or more of the repeating unit. . Typical examples of these include polyphenylene sulfide oligomers, polyphenylene sulfide sulfone oligomers, polyphenylene sulfide ketone oligomers, random copolymers, block copolymers, and mixtures thereof. Particularly preferred polyarylene sulfide oligomers include polyphenylene sulfide oligomers containing 80 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units as the main structural unit of the polymer.

  Examples of the molecular weight of the polyarylene sulfide oligomer include those having a molecular weight lower than that of the polyarylene sulfide, and specifically, the weight average molecular weight is preferably less than 10,000.

  The upper limit of the molecular weight of the cyclic polyarylene sulfide is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 3,000 or less in terms of weight average molecular weight, while the lower limit is 300 or less in terms of weight average molecular weight. The above is preferable, 400 or more is preferable, and 500 or more is more preferable.

(B) Poly (ether imide-siloxane) copolymer The poly (ether imide-siloxane) copolymer used in the present invention is a generally known copolymer comprising a polyetherimide repeating unit and a polysiloxane repeating unit. A polymer is mentioned. Preferably, it consists of a repeating unit represented by the following structural formula (Formula 5) and a repeating unit represented by the following structural formula (Formula 6).

  Note that T in the structural formulas (Chemical Formulas 5 and 6) is —O— or —O—Z—O—, and the divalent bonds are 3, 3′-, 3, 4′-, 4 , 3'-, 4,4'-position, Z is composed of a divalent group represented by the following structural formula (Chemical Formula 7) and a divalent group represented by the following structural formula (Chemical Formula 8). Selected from the group.

X in the structural formula (Chemical Formula 8) is selected from the group consisting of a C _1-5 alkylene group or a halogenated derivative thereof, —CO—, —SO ₂ —, —O—, and —S—.

R in the structural formulas (Chemical Formula 5 and Chemical Formula 6) is an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, an alkylene group having 2 to 20 carbon atoms, 3 to 20 A divalent organic group selected from the group consisting of a cycloalkylene group having one carbon atom and a group represented by the following structural formula (Formula 9). Here, Q is selected from the group consisting of a C _1-5 alkylene group or a halogenated derivative thereof, —CO—, —SO ₂ —, —O—, —S—.

  M and n in the above structural formula (Formula 6) are each an integer of 1 to 10, and g is an integer of 1 to 40.

  Particularly preferably, the structure represented by the structural formula (Chemical Formulas 5 and 6) further contains a repeating unit represented by the following structural formula (Chemical Formula 10).

  M in the structural formula (Chemical Formula 10) is selected from the group represented by the following structural formula (Chemical Formula 11) (B in the formula is —S— or —CO—), and R ′ is defined above. It is the same as R or a divalent group represented by the following structural formula (Formula 12) (wherein m and n are each an integer of 1 to 10, and g is an integer of 1 to 40). .

  As a manufacturing method of the above-mentioned poly (ether imide-siloxane) copolymer, aromatic bis (ether anhydride) represented by the following structural formula (Formula 13) and organic diamine represented by the following structural formula (Formula 14) In a known method for producing a polyetherimide from the above, it is produced by replacing a part or all of the organic diamine of the above structural formula (Chemical Formula 14) with an amine-terminated organosiloxane represented by the following structural formula (Chemical Formula 15). .

  T in the structural formula (Chemical formula 13), R in the structural formula (Chemical formula 14), and n, m, and g in the structural formula (Chemical formula 15) are the same as those defined above.

  The poly (ether imide-siloxane) copolymer used in the present invention may be a random copolymer, an alternating copolymer, or a block copolymer, but the block copolymer is particularly flexible and exhibits excellent toughness. This is preferable. Examples of the poly (ether imide-siloxane) block copolymer include chemical structures represented by the following structural formula (Formula 16).

Here, a in the above structural formula (Formula 16) is an integer of 1 to 10,000, n is an integer of 1 to 50, m is an integer of 2 to 40, R ₁ is a tetravalent aromatic group, and has the following structure It is selected from the formula (Formula 17).

T in the above formula (Chemical Formula 17) is a C _1-5 alkylene group or a halogenated derivative thereof, —CO—, —SO ₂ —, —O—, —S—, and —O—Z—O—. Selected from divalent groups. Z is the same as described above.

R ₂ is the same as R described above.

R ₃ and R ₄ are each independently selected from a C _1-8 alkyl group, a halogen-substituted or nitrile-substituted derivative thereof, and a C _6-13 aryl group.

  As a method for producing the poly (ether imide-siloxane) block copolymer described above, a hydroxyl group-terminated polyimide oligomer having the following structural formula (Chemical Formula 18) is reacted with a siloxane oligomer having the following structural formula (Chemical Formula 19) under etherification conditions. A well-known method can be illustrated.

However, n, m, and R _{1 to} R ₄ are as defined above. Further, x in the structural formula (Chemical Formula 19) is a halogen or dialkylamino which can be substituted by a reaction with a hydroxyl group in the hydroxyl group-terminated polyetherimide oligomer of the structural formula (Chemical Formula 18) to form an ether bond. Group, acyl group, alkoxy group and hydrogen atom.

  In addition, as a method for producing a poly (etherimide-siloxane) block copolymer, in a known method for producing polyetherimide from aromatic bis (ether anhydride) and an organic diamine, the reactants are sequentially added. Of course, it can also be synthesized by addition.

  Although there is no restriction | limiting in particular about the glass transition temperature of the poly (ether imide- siloxane) copolymer used by this invention, From a heat resistant and a softness | flexibility viewpoint, it is preferable that it is 140 degreeC or more and 220 degrees C or less, 150 degreeC. The temperature is more preferably 210 ° C. or lower and even more preferably 160 ° C. or higher and 200 ° C. or lower.

(C) Olefin Elastomer The (c) olefin elastomer 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. Copolymers of α, β-unsaturated carboxylic acids and alkyl esters thereof, and the like. Among them, ethylene / α-olefin copolymer obtained by copolymerizing ethylene and α-olefin having 3 to 20 carbon atoms The coalescence is preferable in terms of imparting excellent flexibility and high toughness.
Specific examples of the α-olefin having 3 to 20 carbon atoms include 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-eicosene, 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, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof To be mentioned. Among these α-olefins, copolymers using α-olefins having 4 to 12 carbon atoms are even more preferable.

In addition, an olefin polymer or copolymer containing a reactive functional group is also included.
For example, as an olefin containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. are examples of olefins containing carboxyl groups and salts thereof, and acid anhydride groups. Include maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, and the like.

  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 having 1 to 30% by weight of an α, β-unsaturated carboxylic acid glycidyl ester as an essential copolymerization component is preferable, and an α, β-unsaturated carboxylic acid glycidyl ester of 5 to 25% by weight. Is more preferable, and the olefin copolymer having 15 to 20% by weight of glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymer component is flexible and suppresses gelation. From the viewpoint of

  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.

  More specifically, “Bond First” E (ethylene: glycidyl methacrylate = 88 wt%: 12 wt%), “Bond First” 2C (ethylene: glycidyl methacrylate = 94 wt%: 6 wt%) manufactured by Sumitomo Chemical, “ Bond First “7 L (ethylene: glycidyl methacrylate: methyl acrylate = 70 wt%: 3 wt%: 27 wt%),“ Bond First ”7M (ethylene: glycidyl methacrylate: methyl acrylate = 67 wt%: 6 wt%: 27 wt%) %), Bond First “CG5001 (ethylene: glycidyl methacrylate = 81 wt%: 19 wt%),“ LOTADE ”AX8900 (ethylene: glycidyl methacrylate: methyl acrylate = 68 wt%: 8 wt%: 24 wt%) manufactured by Arkema, etc. But It can be shown.

  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.

  From the viewpoint of developing excellent tensile elongation at break when using an olefin (co) polymer having no reactive functional group and an olefin (co) polymer having a reactive functional group, the reactive functional group is It is preferable to relatively increase the blending ratio of the olefin (co) polymer to be included. Specifically, when the total amount of the olefin (co) polymer having no reactive functional group and the olefin (co) polymer having a reactive functional group is 100% by weight, an olefin having a reactive functional group ( The proportion of the (co) polymer is preferably 20% or more, more preferably 40% or more, and still more preferably 50% or more. The upper limit of the amount of the olefin (co) polymer having a reactive functional group is not particularly limited, and even if it is 100% by weight, there is no particular problem, but there is a possibility of thickening, so the desired melting It is necessary to adjust appropriately according to the viscosity.

  The (c) 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 (c) 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 , handling properties are lowered, which is not preferable.

(D) Compound having at least one functional group selected from the group consisting of amino group, epoxy group and isocyanate group In the present invention, in order to obtain a polyphenylene sulfide resin composition having greatly improved toughness and heat aging resistance, (D) It is preferable to add a compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group as a compatibilizing agent. However, the compatibilizer mentioned here does not include the (c) olefin-based elastomer containing the reactive functional group described above.

  Epoxy group-containing compounds include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1 , 5-dihydroxynaphthalene, cashew phenol, glycidyl ethers of bisphenols such as 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, those using halogenated bisphenol instead of bisphenol, butanediol di Glycidyl ether epoxy compounds such as glycidyl ether, glycidyl ester compounds such as glycidyl phthalate, glycidyl amine compounds such as N-glycidyl aniline, etc. Glycidyl epoxy resins, linear epoxy compounds such as epoxidized soybean oil, vinylcyclohexene dioxide, such as a non-glycidyl epoxy resins ring system such as dicyclopentadiene dioxide and the like.

  In addition, other novolac type epoxy resins are also included. The novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. Although there is no restriction | limiting in particular as phenols of a raw material, Phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and these condensates are mentioned.

  Furthermore, the alkoxysilane which has an epoxy group is mentioned. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. A compound etc. can be illustrated.

  Examples of the amino group-containing compound include alkoxysilanes having an amino group. Specific examples of such compounds include amino group-containing alkoxysilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. Compound etc. are mentioned.

  Isocyanate group-containing compounds include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, polymethylene polyphenyl polyisocyanate and the like, and γ-isocyanatopropyltriethoxysilane , Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, etc. The isocyanate group-containing alkoxysilane compound can be exemplified.

  Among them, in order to achieve excellent toughness and heat aging resistance, a compound containing one or more isocyanate groups or a compound containing one or more epoxy groups is preferable. Further, an alkoxysilane or epoxy group containing an isocyanate group is preferably used. More preferably, it is an alkoxysilane.

  In the polyphenylene sulfide resin composition of the present invention, the blending ratio of (a) polyphenylene sulfide resin, (b) poly (etherimide-siloxane) copolymer, and (c) olefin elastomer is (a) 100 weight of polyphenylene sulfide resin. It is necessary that (b) poly (ether imide-siloxane) copolymer is 1 to 150 parts by weight and (c) olefin elastomer is 1 to 150 parts by weight with respect to parts. (B) When the poly (ether imide-siloxane) copolymer is less than 1 part by weight, sufficient flexibility and toughness are not exhibited, and heat aging resistance is remarkably lowered. (C) When the olefin-based elastomer is less than 1 part by weight, flexibility and low toughness are hardly exhibited. On the other hand, when (b) the poly (ether imide-siloxane) copolymer and (c) the olefin elastomer exceeds 150 parts by weight, the heat resistance, chemical resistance, and flame retardancy inherent in the (a) polyphenylene sulfide resin Not only does this decrease, but the melt viscosity becomes high and the molding processability is extremely inferior. (B) A more preferable blending amount of the poly (ether imide-siloxane) copolymer is 5 to 100 parts by weight from the viewpoint of not only flexibility and toughness but also excellent heat aging resistance. 10 to 85 parts by weight is more preferable, and 20 to 70 parts by weight is most preferable. (C) As a more preferable compounding quantity of an olefin type elastomer, 5-100 weight part is mentioned from a viewpoint which expresses the outstanding softness | flexibility and high toughness, and 10 from a viewpoint of the high level balance with heat aging resistance. -80 weight parts are more preferable, 15-60 weight parts are still more preferable, and 20-30 weight parts can be illustrated as an increasingly preferable range. In particular, when an olefin-based elastomer having a low crystallinity and excellent flexibility, such as the α-olefin copolymer having a glycidyl methacrylate copolymer content of 15% or more, is selected, the blending amount is small. 20 to 25 parts by weight can be exemplified as the most preferable range because flexibility can be imparted and heat aging resistance can be improved.

  In the present invention, (d) the compounding amount of the compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group is (0.1) with respect to 100 parts by weight of the polyphenylene sulfide resin. -30 parts by weight is preferable, 0.3-10 parts by weight is more preferable, and 0.5-5 parts by weight can be exemplified as a more preferable range. When the blending amount is less than 0.1 parts by weight, the dispersibility of (a) poly (ether imide-siloxane) copolymer and (c) olefin elastomer in polyphenylene sulfide is inferior. When the amount exceeds 30 parts by weight, not only the melt viscosity is remarkably increased but also a gel-like product is formed during the molding process, which is not preferable.

Morphology of PPS Resin Composition The PPS resin composition of the present invention is excellent in flexibility and toughness without damaging the excellent heat resistance, chemical resistance, and flame resistance inherent in the PPS resin, and drastically heat aging. Is improved. In order to express such characteristics, as schematically shown in FIG. 1, in the morphology observed by an electron microscope, (a) the PPS resin is a continuous phase, and (b) a poly (etherimide-siloxane) copolymer. Forms a primary dispersed phase and (c) the olefin-based elastomer needs to form a secondary dispersed phase in the primary dispersed phase. Thus, (c) the olefin elastomer having relatively poor heat resistance is present as the secondary dispersed phase in the primary dispersed phase of the (b) poly (etherimide-siloxane) copolymer having relatively excellent heat resistance. By doing so, not only flexibility and high toughness, but also excellent heat aging resistance that has never been achieved will be exhibited.

  In this case, 80% by volume or more of the blended (c) olefin-based elastomer is not a primary dispersed phase but a secondary dispersed phase (b) a primary dispersed phase comprising a poly (ether imide-siloxane) copolymer. It is preferably present in the inside, and more preferably, 90% by volume or more of (c) the olefin elastomer is present as a secondary dispersed phase. When the amount of (c) olefinic elastomer present as the secondary dispersed phase is less than 80% by volume, the volume ratio of (c) olefinic elastomer present as the primary dispersed phase increases, resulting in relatively poor heat aging resistance. It is not preferable.

  Here, the volume% of the (c) olefin elastomer present as the secondary dispersed phase can be estimated by the following method. First, about the pellet or molded article of the PPS resin composition of the present invention, a thin piece of 0.1 μm or less from the center is cut in the cross-sectional area direction, dyed with ruthenium tetroxide, and 1000 to 5000 using a transmission electron microscope. Shoot the phase structure at a magnification of about double. Next, (c) an arbitrary 100 dispersed particles derived from the olefin-based elastomer in the photograph, a primary dispersed phase is formed (c) an area portion of the olefin-based elastomer, a secondary dispersed phase is formed (c) The weights obtained by cutting out and weighing the area of the olefin-based elastomer are set as V1 and V2, respectively, and the 100 fraction of V2 / (V1 + V2) is calculated.

  The distinction between (a) PPS resin, (b) poly (etherimide-siloxane) copolymer, and (c) olefin-based elastomer is the same for (a) PPS resin and (b) poly (etherimide-siloxane). It can be judged from the contrast when the phase structure is observed in the same manner as described above for the composition containing only the polymer and the composition containing only the (a) PPS resin and (c) olefin elastomer.

  In order to impart high toughness, the number average dispersed particle size of the primary dispersed phase comprising (b) a poly (ether imide-siloxane) copolymer is preferably 1500 nm or less, more preferably 1300 nm or less. Preferably, it is 1000 nm or less. (B) When the number average dispersed particle diameter of the primary dispersed phase composed of the poly (ether imide-siloxane) copolymer exceeds 1500 nm, (a) peeling easily occurs from the interface with the PPS resin, and before the heat treatment. This is not preferable because the toughness tends to decrease. For the primary dispersed phase, the lower limit of the number average dispersed particle diameter is not particularly limited, but is preferably 50 nm or more from the viewpoint of productivity.

  In order to exhibit excellent heat aging resistance as well as high flexibility and toughness, the number average particle diameter of the secondary dispersed phase comprising (c) the olefin elastomer is preferably 1000 nm or less, and 900 nm The following is more preferable, and it is still more preferable that it is 800 nm or less. (C) When the number average particle diameter of the secondary dispersed phase composed of the olefin-based elastomer exceeds 1000 nm, the elastic modulus becomes relatively high even with the same amount of addition, and tensile elongation and impact strength are the first. The toughness may be lowered, and the heat aging resistance is not so much improved, which is not preferable. For the secondary dispersed phase, the lower limit of the number average dispersed particle size is not particularly limited, but is preferably 10 nm or more from the viewpoint of productivity.

  In addition, the number average dispersed particle diameter referred to here is, from the center of the PPS resin composition pellet or molded product of the present invention, after cutting a thin piece of 0.1 μm or less in the cross-sectional area direction, dyed with ruthenium tetroxide, 100 disperse parts of (b) poly (ether imide-siloxane) copolymer or (c) olefin-based elastomer when observed by magnifying at a magnification of about 1000 to 5000 times with a transmission electron microscope First, the maximum diameter and the minimum diameter of each are measured, the average value is set as the dispersed particle diameter, and then the average value is obtained.

  The PPS resin composition of the present invention has excellent flexibility and toughness without deteriorating the excellent heat resistance, chemical resistance, and flame resistance inherent in the PPS resin, and has dramatically improved heat aging resistance. Is. The term “flexibility” as used herein refers to the bending when a bending test piece of (length) 125 mm × (width) 12 mm × (thickness) 6 mm is measured under the conditions of a distance between tests of 100 mm and a crosshead speed of 3 mm / min. It can be quantified by the elastic modulus. The flexural modulus is preferably 3.4 GPa or less, more preferably 3.0 GPa or less, even more preferably 1.5 GPa or less, and even more preferably 1.0 GPa or less.

  The toughness as used herein can be quantified by the tensile elongation at break when an ASTM No. 1 dumbbell test piece is measured under the conditions of a distance between tests of 100 mm and a crosshead speed of 10 mm / min. The tensile elongation is preferably 30% or more, more preferably 50% or more, and still more preferably 100% or more.

  Moreover, heat aging resistance said here is defined by the 100-minute rate which remove | divided the tensile breaking elongation of the ASTM No. 1 dumbbell test piece after processing for 500 hours at 180 degreeC in the air by the tensile breaking elongation before a process. It can be quantified by the tensile elongation retention rate. The tensile break elongation of the ASTM No. 1 dumbbell test piece after treatment for 500 hours at 180 ° C. in air is preferably 5% or more, more preferably 20% or more, and further preferably 50% or more. The tensile rupture elongation retention is preferably 20% or more, more preferably 40% or more, and further preferably 50% or more. In addition, about the measuring method of tensile fracture elongation, it conforms to the quantitative determination method of toughness mentioned above.

Production method of polyphenylene sulfide resin composition As a method of producing the PPS resin composition of the present invention, production in a molten state or production in a solution state is possible, but from the viewpoint of simplicity, in a molten state 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 PPS resin composition of the present invention is not necessarily limited to this, but (a) a PPS resin, (b) a poly (etherimide-siloxane) copolymer, and (c) an olefin type. A typical example is a method in which an elastomer is supplied to a twin-screw extruder and melt-kneaded at a processing temperature of (a) PPS resin melting point + 5 to 100 ° C.
(B) In order to form a secondary dispersed phase composed of (c) an olefin elastomer in the primary dispersed phase of the poly (ether imide-siloxane) copolymer, it is necessary to make the shearing force relatively strong. From the above, in the screw arrangement configuration of the twin screw extruder, it is more preferable that the kneading portions are arranged at three or more locations, more preferably, the kneading portions are arranged at four or more locations.
The upper limit of the kneading portion may vary depending on the length of the kneading portion per location and the interval between the kneading portions, but is preferably 10 or less, and more preferably 8 or less. Moreover, the ratio of the total length of the kneading part with respect to the screw full length of an extruder has the preferable range of 10-60%, More preferably, it is 15-55%, Furthermore, the range of 20-50% is preferable.

  The L / D, which is the ratio of the screw length L to the screw diameter D of the twin screw extruder, is desirably 10 or more, more preferably 20 or more, and further preferably 30 or more. The upper limit of L / D of a twin screw extruder is usually 60. As the peripheral speed at this time, a range of 15 to 50 m / min is selected, and 20 to 40 m / min is more preferably selected. When the L / D of the twin-screw extruder is less than 10, the kneading part is insufficient, so that the dispersibility of the (b) poly (ether imide-siloxane) copolymer and (c) the olefin elastomer decreases. (B) It becomes difficult to construct a specific phase separation structure formed by a secondary dispersed phase comprising (c) an olefin elastomer in the primary dispersed phase of the poly (ether imide-siloxane) copolymer.

  Furthermore, a method of melt kneading by arranging a screw arrangement incorporating a stirring screw having a notch can also be exemplified as a preferred method. Here, the “notch” means that a part of the mountain portion of the screw flight is cut away. A stir screw with a notch can increase the resin filling rate and, unlike conventional kneading methods for grinding resin, it not only suppresses resin decomposition due to heat generation, but also stirs and stirs. (B) a specific phase formed by a secondary dispersed phase composed of (c) an olefin elastomer in the primary dispersed phase of (b) poly (ether imide-siloxane) copolymer. A separation structure is easily constructed.

  As a stirring screw having a notch, from the viewpoint of improving the cooling efficiency of the molten resin by filling the resin and improving the stirring and kneading properties, the screw pitch length is 0.1D to 0.3D, where D is the screw diameter, and It is preferable that it is a stirring screw which has a notch part whose notch number is 10-15 per pitch. Here, the length of the screw pitch refers to the screw length between the crest portions of the screw when the screw rotates 360 degrees.

  Moreover, it is preferable that the ratio of the total length of the stirring screw part which has a notch part with respect to the screw full length of an extruder is 3-20% of said L / D, and it is 5-15%. More preferred.

  About screw rotation speed, 150 rpm or more is preferable and 200 rpm or more is more preferable from a viewpoint of forming the specific phase structure of this invention. The upper limit of the screw rotation speed is not particularly limited, but is preferably 1500 rpm or less from the viewpoint of reducing the load on the extruder.

  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 blended and melt-kneaded by the above method, and this and the remaining raw materials are further blended and melt-kneaded. Any method may be used, such as a method of mixing a part of raw materials, or a method of mixing the remaining raw materials using a side feeder during melt kneading with a twin-screw extruder. Among these, (b) a poly (ether imide-siloxane) copolymer and (c) an olefin elastomer are mixed with (a) a PPS resin using a side feeder during melt-kneading. It is advantageous in constructing a specific phase separation structure in which a secondary dispersed phase comprising (c) an olefin elastomer is formed in the primary dispersed phase of the (imido-siloxane) copolymer. The method of mixing (a) the PPS resin and (b) the poly (etherimide-siloxane) copolymer with the (c) olefin elastomer using a side feeder during the melt-kneading is as follows: (c) the olefin elastomer This is advantageous in that it suppresses thermal degradation of the resin and imparts high flexibility and toughness.

  In order to improve the interfacial adhesion between (a) PPS resin and (b) poly (etherimide-siloxane) copolymer and further improve the tensile elongation, a part of (a) PPS resin And (b) a poly (ether imide-siloxane) copolymer previously melt-kneaded, and then the remaining (a) PPS resin and (c) an olefin elastomer are further melt-kneaded. In this pre-melt kneading, the blending weight ratio of a part of (a) PPS resin and (b) poly (etherimide-siloxane) copolymer is preferably 7: 3 to 1: 9, and 6: 4 to 2: 8 is more preferable, and 4: 6 to 3: 7 can be exemplified as a more preferable range.

  In this way, the amount of (b) poly (ether imide-siloxane) copolymer when melt-kneaded in advance is relatively larger than that of (a) PPS resin, so that (a) PPS resin and (b) poly In addition to improving the interfacial adhesion of the (etherimide-siloxane) copolymer, when the remaining (a) PPS resin and (c) olefin elastomer are further melt-kneaded, (c) the olefin elastomer is ( b) It becomes easy to form a secondary dispersed phase with a relatively small particle diameter in the primary dispersed phase comprising a poly (ether imide-siloxane) copolymer.

  Further, when a part of (a) PPS resin and (b) poly (etherimide-siloxane) copolymer are previously melt-kneaded, (d) selected from the group consisting of an amino group, an epoxy group, and an isocyanate group More preferably, the compound having at least one functional group is added as a compatibilizing agent. In order to obtain a final composition, it comprises a part of (a) a PPS resin, (b) a poly (etherimide-siloxane) copolymer, and (d) an amino group, an epoxy group, and an isocyanate group. A compound having at least one functional group selected from the group may be previously melt-kneaded and pelletized, and then the remaining (a) PPS resin and (c) olefin elastomer may be blended and further melt-kneaded. And (b) at least one functional group selected from the group consisting of (a) PPS resin, (b) poly (etherimide-siloxane) copolymer, (d) amino group, epoxy group, and isocyanate group. It is also possible to further melt-knead the remaining compound (a) with the PPS resin and (c) the olefin-based elastomer using a side feeder during melt-kneading in advance.

  In addition, about a small amount additive component, after kneading | mixing other components with said method etc. and pelletizing, it is also possible to add before shaping | molding and to use for shaping | molding.

Inorganic filler Although not an essential component, the polyphenylene sulfide resin composition of the present invention can be used by blending an inorganic filler as long as the effects of the present invention are not impaired. 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 Silicates such as silicates, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfuric acid Sulfates such as lucium and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite Non-fibrous fillers such as glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of the anticorrosive material and the lubricant. 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 blending amount of the inorganic filler is selected from the range of 30 parts by weight or less, preferably less than 10 parts by weight, more preferably less than 1 part by weight based on 100 parts by weight of the (a) polyphenylene sulfide resin. More preferably, the range is 8 parts by weight or less. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. While the blending of the inorganic filler is effective for improving the elastic modulus of the material, a large amount of blending exceeding 30 parts by weight is not preferable because it causes a large decrease in toughness. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

Other Additives Furthermore, the polyphenylene sulfide resin composition of the present invention contains (b) a poly (ether imide-siloxane) copolymer and (c) a resin other than an olefin-based elastomer, as long as the effects of the present invention are not impaired. You may add and mix. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, polyether imide resins, polyether sulfone resins, polyamide imide 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, (a) the original properties of the PPS resin are impaired, which is not preferable, and it is preferable to add 10% by weight or less, more preferably 1% by weight or less.

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 is flexible and extremely excellent in tensile elongation at break, and also has excellent heat aging resistance, so it is useful for extrusion applications with relatively high molding temperature and a long melt residence time. It is. Furthermore, the polyphenylene sulfide resin composition of the present invention is useful for blow molding applications because of its excellent characteristics such as melt tension and elongational viscosity. Specific examples include extrusion blow, injection blow, sheet blow, and multi-dimensional blow such as three-dimensional blow and suction blow. From the viewpoint of providing various properties in a composite manner, it is also preferable to design as a multi-layer blow of two types, two layers, three types, three layers, two types, five layers, or the like.

Applications of molded products obtained by injection molding include generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, machine breakers, knife switches, other poles Electrical equipment parts such as rods, electrical parts cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs Electronic components represented by printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc .; VTR parts, TE Bi-component, iron, hair dryer, rice cooker component, microwave oven component, acoustic component, audio equipment component such as audio / laser disc (registered trademark) / compact disc, lighting component, refrigerator component, air conditioner component, typewriter component, word processor Household / office electrical product parts typified by parts, etc .; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc. Related parts: Microscopes, binoculars, cameras, parts related to optical instruments such as cameras, watches, etc .; alternator terminals, alternator connectors, IC regulators, light potentiometer bases, various valves such as exhaust gas valves, fuel-related・ Exhaust system Intake system pipes and ducts, turbo ducts, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, Throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust Butter, starter switch, starter relay, transmission wire harness, win Dwasher nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter Examples include automobile / vehicle-related parts such as ignition device cases, primary batteries or secondary batteries such as mobile phones, notebook computers, video cameras, hybrid cars, and electric cars.

  Molded products obtained by extrusion include round bars, square bars, sheets, films, tubes, pipes, etc. More specific applications include electrical insulation for water heater motors, air conditioner motors, drive motors, etc. Materials, film capacitors, speaker diaphragms, magnetic tapes for recording, printed circuit board materials, printed circuit board peripheral components, semiconductor packages, semiconductor transport trays, process / release films, protective films, automotive film sensors, wire cable insulation tape , Insulation washers in lithium-ion batteries, hot water and cooling water, chemical tubes, automotive fuel tubes, hot water piping, chemical plant chemical piping, ultrapure water and ultrapure solvent piping, Automotive piping, piping pipes for chlorofluorocarbon and supercritical carbon dioxide refrigerant, workpieces for polishing equipment Such as lifting ring can be exemplified. In addition, wire harnesses and control wires for hybrid vehicles, electric vehicles, railways, motor coil windings for power generation facilities, heat-resistant electric wire cables for home appliances, flat cables used for wiring in automobiles, communications, For example, a covering molded body of a winding of a signal transformer for transmission, high frequency, audio, measurement, etc., or a transformer for vehicle mounting can be exemplified.

  Applications of molded products obtained by blow molding include automobile fuel tanks, oil tanks, resonators, intercoolers, intake manifolds, turbo ducts, intake / exhaust ducts, radiator pipes, radiator headers, expansion tanks, oil A circulation pipe etc. can be illustrated.

  Among them, it is useful as a coated body of windings for motor coils of hybrid vehicles, electric vehicles, railways, and power generation facilities, and various fuel and exhaust / intake system pipes and ducts of automobiles exposed to high-temperature environments, especially turbo ducts. It is.

  These various molded products can of course be subjected to secondary processing such as hot plate welding, laser welding, induction heating welding, high frequency welding, spin welding, vibration welding, ultrasonic welding, injection welding and the like.

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

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

[injection molding]
Using a Sumitomo Heavy Industries injection molding machine SE75-DUZ, 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 (length) 125 mm × (width) 12 mm × (thickness) A 6 mm bending test piece was formed.

[Phase structure 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. Stained with ruthenium oxide. This is magnified 1000 to 5000 times with a H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification 500 to 600,000 times) manufactured by Hitachi, Ltd., and the phase structure is formed. confirmed.

(A) PPS resin, (b) poly (etherimide-siloxane) copolymer, and (c) olefin-based elastomer are distinguished from each other by (a) PPS resin and (b) poly (etherimide-siloxane) copolymer. The composition of only (a) PPS resin and the composition of (c) olefin elastomer was judged from the contrast when the phase structure was observed in the same manner as described above.
(B) When a poly (ether imide-siloxane) copolymer forms a primary dispersed phase and (c) an olefin elastomer forms a secondary dispersed phase in the primary dispersed phase, it exists as a secondary dispersed phase. (C) The volume% of the olefin elastomer was estimated by the following method. That is, (c) the area part of the olefinic elastomer that forms the primary dispersed phase for any 100 dispersed particles derived from (c) the olefinic elastomer in the photograph taken by observing the phase structure as described above, secondary (C) The area part of the olefin-based elastomer forming the dispersed phase was cut out and weighed to be V1 and V2, respectively, and then the 100 fraction of V2 / (V1 + V2) was calculated.

  Regarding the number average dispersed particle size of (b) the primary dispersed phase composed of a poly (ether imide-siloxane) copolymer and (c) the secondary dispersed phase composed of an olefin-based elastomer, a photograph taken by observing the phase structure as described above. In (b) 100 dispersed particles of poly (ether imide-siloxane) copolymer or (c) olefin elastomer, the maximum diameter and the minimum diameter are first measured and the average value is defined as the dispersed particle diameter. Then, it was obtained by calculating their number average value.

[Alkali metal and / or alkaline earth metal content]
(A) After ashing 5 g of the PPS resin or the injection-molded PPS resin composition in an electric furnace at 500 ° C., an aqueous solution diluted with a 0.1 N hydrochloric acid aqueous solution and a 0.1% lanthanum chloride aqueous solution was used as a sample. It measured by the atomic absorption method using Shimadzu Corporation atomic absorption spectrophotometer AA-6300.

[Dry heat treatment]
The ASTM No. 1 dumbbell test piece obtained by injection molding was placed in a gear oven set at 180 ° C., treated for 500 hours, and allowed to cool at room temperature for 24 hours or more.

[Tensile test]
The tensile break elongation of the ASTM No. 1 dumbbell before and after the dry heat treatment, which was injection-molded, was measured using a Tensilon UTA2.5T tensile tester under conditions of a chuck distance of 114 mm, a test distance of 100 mm, and a tensile speed of 10 mm / min.

  Moreover, the 100-minute ratio which remove | divided the tensile fracture elongation after dry heat processing by the tensile fracture elongation before dry heat processing was computed as tensile fracture elongation retention.

[Bending test]
The injection-molded bending test piece was subjected to a bending test using an Instron 5561 type bending tester under the conditions of a distance between tests of 100 mm and a crosshead speed of 3 mm / min.

[Reference Example 1] 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 (a) -1 had a melt viscosity of 200 Pa · s (310 ° C., shear rate of 1000 / s) and a total content of alkali metal and alkaline earth metal of 65 ppm.

[Reference Example 2] PPS resin (a) -2
Dehydration, polymerization, washing, and drying were performed in the same manner as in Reference Example 1 except that the 0.05 wt% acetic acid aqueous solution at the time of PPS washing was changed to a 0.05 wt% calcium acetate monohydrate aqueous solution. The obtained (a) -2 had a melt viscosity of 280 Pa · s (310 ° C., shear rate of 1000 / s), and the total content of alkali metal and alkaline earth metal was 320 ppm.

[Reference Example 3] PPS resin (a) -3
A stainless steel autoclave equipped with a stirrer was charged with 14.03 g (0.120 mol) of a 48 wt% aqueous solution of sodium hydrosulfide and 12.50 g (0.144 mol) of a 48 wt% aqueous solution prepared using 96% sodium hydroxide. ), 615.0 g (6.20 mol) of N-methyl-2-pyrrolidone (NMP), and 18.08 g (0.123 mol) of p-dichlorobenzene (p-DCB). The reaction vessel was sufficiently purged with nitrogen, and then sealed under nitrogen gas.

  While stirring at 400 rpm, the temperature was raised from room temperature to 200 ° C. over about 1 hour. At this stage, the pressure in the reaction vessel was 0.35 MPa as a gauge pressure. Next, the temperature was raised from 200 ° C. to 270 ° C. over about 30 minutes. The pressure in the reaction vessel at this stage was 1.05 MPa as a gauge pressure. After maintaining at 270 ° C. for 1 hour, the contents were recovered after quenching to near room temperature.

  The content obtained was analyzed by gas chromatography and high performance liquid chromatography. As a result, the consumption rate of monomer p-DCB was 93%, and the sulfur content in the reaction mixture was assumed to be all converted to cyclic PPS. The formula PPS production rate was found to be 18.5%.

  500 g of the obtained contents were diluted with about 1500 g of ion-exchanged water, and then filtered through a glass filter having an average opening of 10 to 16 μm. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and filtered again in the same manner three times to obtain a white solid. This was vacuum dried at 80 ° C. overnight to obtain a dry solid.

The obtained solid was charged into a cylindrical filter paper, and Soxhlet extraction was performed for about 5 hours using chloroform as a solvent to separate low molecular weight components contained in the solid.
The solid component remaining in the cylindrical filter paper after the extraction operation was dried under reduced pressure at 70 ° C. overnight to obtain about 6.98 g of an off-white solid. As a result of analysis, this was a compound having a phenylene sulfide structure, and the weight average molecular weight was 6,300, from the absorption spectrum in infrared spectroscopic analysis.

  After removing the solvent from the extract obtained by the chloroform extraction operation, about 5 g of chloroform was added to prepare a slurry, which was added dropwise to about 300 g of methanol with stirring. The precipitate thus obtained was collected by filtration and vacuum dried at 70 ° C. for 5 hours to obtain 1.19 g of a white powder. This white powder was confirmed to be a compound composed of phenylene sulfide units from an absorption spectrum in infrared spectroscopic analysis. Moreover, this white powder has p-phenylene sulfide unit as the main constituent unit based on the mass spectrum analysis of the component divided by high performance liquid chromatography (apparatus; M-1200H manufactured by Hitachi) and molecular weight information by MALDI-TOF-MS. It was found to be a cyclic polyphenylene sulfide mixture containing about 98% by weight of a cyclic compound having 4 to 13 repeating units and suitably used for the production of the polyarylene sulfide of the present invention. As a result of GPC measurement, the cyclic polyphenylene sulfide mixture was completely dissolved in 1-chloronaphthalene at room temperature, and the weight average molecular weight was 900.

  2 g of the cyclic polyphenylene sulfide mixture obtained by the above method was charged into a glass ampule, and the inside of the ampule was replaced with nitrogen. The ampule was placed in an electric furnace adjusted to 340 ° C. and heated for 60 minutes, and then the ampule was taken out and cooled to room temperature to obtain a black solid. The product was completely dissolved in 1-chloronaphthalene at 250 ° C. As a result of HPLC measurement, it was found that the conversion of cyclic polyphenylene sulfide to PPS was 96.5%. The obtained PPS resin (a) -3 was found to have a weight average molecular weight of 76,000 and a dispersity of 2.11. The Na content of the obtained product was 3 ppm, and the weight loss rate during heating at 100 ° C. to 330 ° C. was 0.089%.

[Reference Example 4] Poly (ether imide-siloxane) copolymer (b) -1
A commercially available poly (ether imide-siloxane) block copolymer (“SILTEM 1500” manufactured by SABIC Innovative Plastics) was used. The glass transition temperature was 170 ° C.

[Reference Example 5] Poly (ether imide-siloxane) copolymer (b) -2
A commercially available poly (ether imide-siloxane) block copolymer (“SILTEM 1700” manufactured by SABIC Innovative Plastics) was used. The glass transition temperature was 200 ° C.

[Reference Example 6] Olefin Elastomer (c) -1
When the total amount of olefin-based elastomer is 100% by weight, 60% by weight of ethylene / 1-butene copolymer (Mitsui Chemicals “Toughmer” TX610) and ethylene / glycidyl methacrylate copolymer (Sumitomo Chemical “Bond First”) E, ethylene: glycidyl methacrylate = 88 wt%: 12 wt%) blended at a ratio of 40 wt% was used.

[Reference Example 7] Olefin elastomer (c) -2
When the total amount of olefin elastomer is 100% by weight, 40% by weight of ethylene / 1-butene copolymer (Mitsui Chemicals'"Toughmer" TX610) and ethylene / glycidyl methacrylate copolymer (Sumitomo Chemical "Bond First") E, ethylene: glycidyl methacrylate = 88 wt%: 12 wt%) blended at a ratio of 60 wt% was used.

[Reference Example 8] Olefin Elastomer (c) -3
When the total amount of olefin-based elastomer is 100% by weight, 40% by weight of ethylene / 1-butene copolymer (“Tafmer” TX610 made by Mitsui Chemicals) and ethylene / glycidyl methacrylate / methyl acrylate copolymer (“LOTADER” made by Arkema) “AX8900, ethylene: glycidyl methacrylate: methyl acrylate = 68 wt%: 8 wt%: 24 wt%) blended at a ratio of 60 wt% was used.

[Reference Example 9] Olefin Elastomer (c) -4
An ethylene / glycidyl methacrylate copolymer (“Bond First” E, manufactured by Sumitomo Chemical Co., Ltd., ethylene: glycidyl methacrylate = 88 wt%: 12 wt%) was used.

[Reference Example 10] Olefin Elastomer (c) -5
An ethylene / glycidyl methacrylate copolymer (“Bond First” CG5001, manufactured by Sumitomo Chemical Co., Ltd., ethylene: glycidyl methacrylate = 81 wt%: 19 wt%) was used.

[Reference Example 11] Compatibilizer (d)
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent having an epoxy group.

[Examples 1-7, 11-12, Comparative Examples 1-4]
(A) PPS resin, (b) poly (ether imide-siloxane) copolymer, (c) polyolefin elastomer, and (d) compatibilizer shown in Tables 1 and 3 are shown in Tables 1 and 3. After dry blending, a TEX30α type twin screw extruder (L / D = 45, 3 kneading parts, 10% ratio of screw with notch to L / D) equipped with a vacuum vent. The cylinder temperature was set and melt kneaded so that the die removal resin temperature was 330 ° C. or lower at a screw rotation speed of 300 rpm, and pelletized by a strand cutter.
Pellets dried overnight at 130 ° C. are subjected to injection molding, phase separation structure of molded pieces, alkali metal and / or alkaline earth metal content, tensile elongation at break before and after heat treatment, tensile elongation at break, bending The elastic modulus was evaluated. The results were as shown in Tables 1 and 3.

[Example 8]
(D) Except for not adding a compatibilizer, melt kneading, pelletizing, and property evaluation of the molded product were performed in the same manner as in Example 1. The results were as shown in Table 1.

[Example 9]
Melt-kneading, pelletizing, and evaluating the characteristics of the molded product were carried out in the same manner as in Example 1 except that the kneading part of the twin-screw extruder was 5 places and the ratio of the screw having a notch to L / D was 0%. went. The results were as shown in Table 1.

[Example 10]
Except that the screw rotation speed of the twin screw extruder was 150 rpm, melt kneading, pelletization, and evaluation of the properties of the molded product were performed in the same manner as in Example 1. The results were as shown in Table 1.

[Examples 13 to 14]
(A) 55 parts by weight of 100 parts by weight of the PPS resin shown in Table 2, (b) 35 parts by weight of a poly (etherimide-siloxane) copolymer, and (d) 2 parts by weight of a compatibilizer were dry blended. After that, using a TEX30α type twin screw extruder (L / D = 45, kneading part at 3 locations, 10% ratio of notched part to L / D) equipped with a vacuum vent, screw rotation The cylinder temperature was set at several 300 rpm so that the die removal resin temperature would be 330 ° C. or lower, melt-kneaded in advance, and pelletized with a strand cutter.

Next, after dry blending the obtained pellets, the remaining 45 parts by weight of (a) 100 parts by weight of the PPS resin shown in Table 2, and (c) 45 parts by weight of the olefin elastomer, Japan equipped with a vacuum vent. Using a TEX30α type twin screw extruder (L / D = 45, kneading part, 3% ratio of screw having notch part to L / D 10%) at a steel rotation speed of 300 rpm, dicing resin The cylinder temperature was set so that the temperature would be 330 ° C. or less, and the mixture was melt-kneaded and pelletized with a strand cutter.
Pellets dried overnight at 130 ° C. are subjected to injection molding, phase separation structure of molded pieces, alkali metal and / or alkaline earth metal content, tensile elongation at break before and after heat treatment, tensile elongation at break, bending The elastic modulus was evaluated. The results were as shown in Table 2.

[Example 15]
(A) 15 parts by weight of 100 parts by weight of PPS resin shown in Table 2, (b) 35 parts by weight of a poly (etherimide-siloxane) copolymer, and (d) 2 parts by weight of a compatibilizer were dry blended. After that, using a TEX30α type twin screw extruder (L / D = 45, kneading part at 3 locations, 10% ratio of notched part to L / D) equipped with a vacuum vent, screw rotation The cylinder temperature was set at several 300 rpm so that the die removal resin temperature would be 330 ° C. or lower, melt-kneaded in advance, and pelletized with a strand cutter.

Next, the obtained pellets, (a) the remaining 85 parts by weight of 100 parts by weight of the PPS resin shown in Table 2, and (c) 45 parts by weight of the olefin elastomer were dry blended, and then Japan equipped with a vacuum vent. Using a TEX30α type twin screw extruder (L / D = 45, kneading part, 3% ratio of screw having notch part to L / D 10%) at a steel rotation speed of 300 rpm, dicing resin The cylinder temperature was set so that the temperature would be 330 ° C. or less, and the mixture was melt-kneaded and pelletized with a strand cutter.
Pellets dried overnight at 130 ° C. are subjected to injection molding, phase separation structure of molded pieces, alkali metal and / or alkaline earth metal content, tensile breaking elongation before and after heat treatment, tensile breaking elongation retention rate, bending The elastic modulus was evaluated. The results were as shown in Table 2.

[Example 16]
(C) Melt kneading, pelletization, and evaluation of the properties of the molded product were performed in the same manner as in Example 14 except that the olefin elastomer was (c) -5 and the blending amount was 25 parts by weight. The results were as shown in Table 2.

[Comparative Example 5]
Except for the two kneading parts of the twin screw extruder, the ratio of the screw having a notch with respect to L / D was 0%, and the screw rotation speed was 100 rpm, melt kneading, pelletizing, as in Example 1, The characteristics of the molded product were evaluated. The results were as shown in Table 3.

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

  In Examples 1 to 16, (b) a poly (ether imide-siloxane) copolymer forms a primary dispersed phase, and (c) an olefin-based elastomer forms a secondary dispersed phase in the primary dispersed phase. By constructing this phase structure, high flexibility and toughness were developed, and the tensile rupture elongation retention ratio before and after the dry heat treatment was high, and the heat aging resistance was dramatically improved.

  In particular, in Examples 11 to 12, by increasing the blending ratio of the (c) olefin elastomer having a reactive functional group, the tensile fracture elongation before the heat treatment is dramatically improved and the tensile fracture after the heat treatment is increased. The elongation was also improved.

  In Examples 13 to 15, (a) a part of the PPS resin, (b) a poly (etherimide-siloxane) copolymer, and (d) a compatibilizing agent were previously melt-kneaded, and then the remaining ( By further melt-kneading the a) PPS resin and (c) the olefin elastomer, the tensile elongation at break before and after the heat treatment was further improved.

  Furthermore, in Example 16 in which (c) -4 having a large copolymerization amount of glycidyl methacrylate was selected, the blending amount of (c) olefin elastomer was relatively at least, and the same flexibility could be imparted. Later tensile elongation at break increased.

  On the other hand, as in Comparative Examples 1 to 3, when (b) a poly (ether imide-siloxane) copolymer is not blended, (c) depending on the blending amount of the olefin elastomer, relatively excellent flexibility and toughness are obtained. Although it appears before the dry heat treatment, the tensile rupture elongation after the dry heat treatment was extremely low, and the tensile rupture elongation retention rate was also low.

  On the contrary, as in Comparative Example 4, when (c) an olefin-based elastomer is not blended, high toughness is exhibited before dry heat treatment, but flexibility is insufficient and tensile elongation at break before and after dry heat treatment is maintained. The rate was low compared to Examples 1-10.

  Further, as in Comparative Example 5, (c) the olefin-based elastomer does not form a secondary dispersed phase, and (b) the poly (etherimide-siloxane) copolymer and (c) the olefin-based elastomer are both primary. When forming the dispersed phase, relatively excellent flexibility and toughness are exhibited before the dry heat treatment, but the tensile elongation at break before and after the dry heat treatment was extremely low as in Comparative Examples 1 to 3. .

1 (a) PPS resin continuous phase 2 (b) Primary dispersed phase made of poly (ether imide-siloxane) copolymer 3 (c) Secondary dispersed phase made of olefin elastomer

Claims (8)

(A) Polyphenylene sulfide resin composition containing 1 to 150 parts by weight of (b) poly (ether imide-siloxane) copolymer and (c) 1 to 150 parts by weight of olefin elastomer with respect to 100 parts by weight of polyphenylene sulfide resin In the morphology observed by an electron microscope, (a) component forms a continuous phase, (b) component forms a primary dispersed phase, and (c) component is a secondary dispersed phase in the primary dispersed phase. A polyphenylene sulfide resin composition characterized by forming 80% by volume or more of the (c) olefin-based elastomer is present as a secondary dispersed phase in the primary dispersed phase composed of the (b) poly (ether imide-siloxane) copolymer. 2. The polyphenylene sulfide resin composition according to 1. 3. The polyphenylene sulfide resin according to claim 1, wherein the number average dispersed particle size of the primary dispersed phase comprising the (b) poly (ether imide-siloxane) copolymer is 1500 nm or less. Composition. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the number average dispersed particle size of the secondary dispersed phase comprising (c) the olefin-based elastomer is 1000 nm or less. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the (a) polyphenylene sulfide resin contains 200 ppm or more of alkali metal and / or alkaline earth metal. The dispersity represented by the weight average molecular weight / number average molecular weight of the (a) polyphenylene sulfide resin is 2.5 or less, and the heating rate is 20 ° C./50° C. to 340 ° C. in a normal pressure non-oxidizing atmosphere. 5. The polyphenylene sulfide resin composition according to claim 1, wherein a weight reduction rate at 100 ° C. to 330 ° C. when thermogravimetric analysis is performed in minutes is 0.2% by weight or less. It is a manufacturing method of the polyphenylene sulfide resin composition in any one of Claims 1-6, Comprising: A part of said (a) polyphenylene sulfide resin and said (b) poly (ether imide-siloxane) copolymer are included. A method for producing a polyphenylene sulfide resin composition, which is obtained by further melt-kneading the remaining (a) polyphenylene sulfide resin and the (c) olefin elastomer after melt-kneading in advance. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 6.