JP5742377B2 - Polyphenylene sulfide resin composition and molded article - Google Patents

Description

  The present invention relates to a polyphenylene sulfide resin composition that is flexible and extremely excellent in tensile elongation at break, and moreover, a polyphenylene sulfide resin composition that retains a relatively high tensile elongation even after being exposed for a long time under high temperature conditions. And a molded article.

  Polyphenylene sulfide (hereinafter may be abbreviated as PPS) resin has excellent properties as engineering plastics such as excellent heat resistance, chemical resistance, electrical insulation, moisture and heat resistance, and is mainly used for injection molding and extrusion molding. It is used for various electric / electronic parts, machine parts and automobile parts.

  However, since PPS resin has low flexibility and inferior tensile properties compared to other engineering plastics such as nylon and PBT, its application is limited and its improvement is strongly desired.

  Until now, several reports related to the composition of a PPS resin and a poly (etherimide-siloxane) copolymer (hereinafter sometimes abbreviated as PEI-siloxane copolymer) have been made. For example, Patent Document 1 discloses a polymer blend obtained by mixing a poly (imide-siloxane) block copolymer and a thermoplastic. However, there is no specific example of a PPS resin as a thermoplastic plastic, and a compound having an amino group, an epoxy group or an isocyanate group is added as a compatibilizing agent for well dispersing a poly (imide-siloxane) block copolymer in the PPS resin. There is no mention of what to do. Further, there is no description about the appearance of excellent tensile elongation by finely dispersing a poly (imide-siloxane) copolymer in a PPS resin to a particle size of 500 nm or less. Furthermore, there has been no description of a composition of PPS resin and poly (imide-siloxane) block copolymer that retains a relatively high tensile elongation even after treatment at a high temperature of 200 ° C.

  Patent Document 2 discloses that a polysulfide may be blended as another component to a resin composition containing a thermotropic liquid crystal polyester and a siloxane polyetherimide copolymer. However, there is no description about adding a compound having an amino group, an epoxy group, or an isocyanate group as a compatibilizing agent for favorably dispersing the siloxane polyetherimide copolymer in the polysulfide. The purpose of Patent Document 2 is to reduce the anisotropy of mechanical properties of liquid crystalline polyester, and to finely disperse a siloxane polyetherimide copolymer to a particle size of 500 nm or less in a PPS resin. Thus, there is no description regarding drastic improvement in the tensile elongation of the PPS resin. Furthermore, there has been no description of a composition of a polysulfide and a siloxane polyetherimide copolymer that retains a relatively high tensile elongation even after treatment at a high temperature of 200 ° C.

  Patent Document 3 discloses a resin composition in which a siloxane copolymer resin is added to a compatible blend composed of a poly (phenylene ether) resin and a poly (arylene sulfide) resin. However, there is no description about adding a compound having an amino group, an epoxy group, or an isocyanate group as a compatibilizing agent for well dispersing the siloxane copolymer resin in the poly (arylene sulfide) resin. In addition, the main purpose of Patent Document 3 is to impart flame retardancy to a compatible blend composed of a poly (phenylene ether) resin and a poly (arylene sulfide) resin without containing halogen and a phosphorus flame retardant, There is no description about the development of excellent tensile elongation by finely dispersing a siloxane copolymer in a particle size of 500 nm or less in a poly (arylene sulfide) resin. Furthermore, there has been no description of a composition of a poly (arylene sulfide) resin and a siloxane copolymer resin that retains a relatively high tensile elongation even after treatment at a high temperature of 200 ° C.

  Patent Document 4 discloses a flame-retardant thermoplastic resin composition containing polyphenylene sulfide as an additive in a resin composition containing a high-molecular-weight linear polyester and polyetherimide and an organopolysiloxane copolymer. However, there is no description about adding a compound having an amino group, an epoxy group, or an isocyanate group as a compatibilizing agent for well dispersing the polyetherimide and the organopolysiloxane copolymer in the polyphenylene sulfide. The purpose of Patent Document 4 is to obtain a non-halogen flame-retardant polyester, which is excellent by finely dispersing a polyetherimide and an organopolysiloxane copolymer to a particle size of 500 nm or less in polyphenylene sulfide. There is no description about the development of the tensile elongation. Furthermore, there has been no description of polyphenylene sulfide and polyetherimide / organopolysiloxane copolymer compositions that retain a relatively high tensile elongation after treatment at a high temperature of 200 ° C.

  As described above, in any patent document, as a compatibilizing agent for well dispersing a poly (etherimide-siloxane) copolymer in a PPS resin, a compound having an amino group, an epoxy group, or an isocyanate group is added. Is not described at all. Moreover, there is no description about the appearance of excellent tensile elongation by finely dispersing a poly (ether imide-siloxane) copolymer in a PPS resin to a particle size of 500 nm or less. Furthermore, there has been no description of a composition of a PPS resin and a poly (ether imide-siloxane) copolymer that maintains a relatively high tensile elongation even after treatment at a high temperature of 200 ° C.

JP 63-199737 A (Claims) JP-A-4-246458 (Claims) JP-A-8-269318 (Claims) JP-A-7-166040 (Claims)

  An object of the present invention is to obtain a polyphenylene sulfide resin composition that is flexible and has an extremely improved tensile elongation at break without significantly impairing the chemical resistance, flame retardancy, and mechanical strength inherent in the polyphenylene sulfide resin. Furthermore, it is an object of the present invention to obtain a polyphenylene sulfide resin composition and a molded product that retain a relatively high tensile elongation even after being exposed to high temperature conditions for a long time.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that at least one selected from the group consisting of a polyphenylene sulfide resin and a poly (etherimide-siloxane) copolymer, an amino group, an epoxy group, and an isocyanate group. As a result of the poly (ether imide-siloxane) copolymer being well-dispersed in the polyphenylene sulfide resin, the tensile rupture elongation is dramatically improved, and further, it is long in high temperature conditions. The inventors found that a relatively high tensile elongation was maintained even after being exposed to time, and reached the present invention.

That is, the present invention is as follows.
1. A resin composition comprising (a) 99 to 60% by weight of a polyphenylene sulfide resin and (b) 1 to 40% by weight of a poly (etherimide-siloxane) copolymer, where the total of (a) and (b) is 100% by weight. to 100 parts by weight of polyphenylene characterized by comprising at least one compounding 0.1 to 10 parts by weight of an alkoxysilane compound having a functional group selected from the group consisting of (c) d epoxy group, isocyanate group A sulfide resin composition,
2. In the morphology (phase structure) of the polyphenylene sulfide resin composition, (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), and the (b) poly (ether imide-siloxane) copolymer is a number average dispersed particle. 2. The polyphenylene sulfide resin composition according to 1, which has a sea-island structure in which a dispersed phase (island phase) dispersed with a diameter of 500 nm or less is formed,
3. The polyphenylene sulfide resin composition according to any one of 1 and 2 , wherein the (a) polyphenylene sulfide resin contains 200 ppm or more in total of alkali metal and alkaline earth metal components,
4). Any one of 1 to 3 characterized in that the tensile break elongation (measured at a distance between chucks of 64 mm and a tensile speed of 10 mm / min using a Tensilon UTA2.5T tensile tester) of the ASTM No. 4 dumbbell molded piece is 50% or more. A polyphenylene sulfide resin composition according to claim 1,
5. Tensile breaking elongation (measured at a distance between chucks of 64 mm and a tensile speed of 10 mm / min using a Tensilon UTA2.5T tensile tester) of 15% or more after processing for 300 hours at 200 ° C. The polyphenylene sulfide resin composition according to any one of 1 to 4 , wherein
6.1 A molded article comprising the polyphenylene sulfide resin composition according to any one of 1 to 5 ,
7). 6. The molded product according to 6 , wherein the molded product is an extrusion molded product,
It is.

  According to the present invention, it is possible to obtain a polyphenylene sulfide resin composition that is flexible and has dramatically improved tensile elongation at break. In addition, since a relatively high tensile elongation is maintained even after being exposed to a high temperature condition for a long time, a polyphenylene sulfide resin composition and a molded article suitable for applications that are continuously used at a high temperature can be obtained. Furthermore, since a relatively high tensile elongation is exhibited even under low temperature conditions, a polyphenylene sulfide resin composition and a molded product suitable for applications used under freezing conditions below freezing point can be obtained.

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

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

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

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

  Although there is no restriction | limiting in particular in the melt viscosity of (a) PPS resin used by this invention, The one where the melt viscosity is higher is preferable from the viewpoint of obtaining the more excellent tensile breaking elongation. For example, a range exceeding 80 Pa · s (310 ° C., shear rate 1000 / s) is preferable, 100 Pa · s or more is more preferable, and 150 Pa · s or more is more preferable. The upper limit is preferably 600 Pa · s or less from the viewpoint of maintaining melt fluidity.

  In addition, the melt viscosity in this invention is the value measured using the Toyo Seiki Co., Ltd. capilograph on the conditions of 310 degreeC and shear rate 1000 / s.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition having extremely excellent tensile elongation at break, residual oligomers and residual salts are removed by repeating organic solvent washing and hot water at about 80 ° C. or hot water washing several times. After removal, an acid treatment or a treatment with an alkali metal salt or alkaline earth metal salt is preferred.

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

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

  In addition, it is possible to carry out 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, (a) the PPS resin is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidation crosslinking treatment in order to achieve the object of the present invention. In the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

  The polyphenylene sulfide resin composition of the present invention is flexible and extremely excellent in tensile elongation at break, and retains a relatively high tensile elongation even after being exposed for a long time under high temperature conditions. In order to express such characteristics, (a) the total of alkali metal and alkaline earth metal contained in the PPS resin is preferably 200 ppm or more, more preferably 500 ppm or more, and further 700 ppm or more. Preferably there is.

  For example, when (c) the compound having a functional group such as an amino group, an epoxy group, or an isocyanate group, which is a compatibilizer, is an epoxy compound, (a) an alkali metal and an alkaline earth contained in the PPS resin When the total metal content is 200 ppm or more, the reaction between (a) the PPS resin and (c) the compound having an epoxy group is promoted, and (b) the poly (ether imide-siloxane) copolymer is further finely dispersed. As a result, high tensile elongation at break becomes easy to develop. In particular, when the compatibilizing agent is (c) a compound having an epoxy group, (a) the alkali metal and alkaline earth metal contained in the PPS resin is more preferably Na.

  Regardless of the type of functional group of the compound having (c) amino group, epoxy group, and isocyanate group, which is a compatibilizer, (a) the total amount of alkali metal and alkaline earth metal contained in the PPS resin is When it is 200 ppm or more, the heat resistance stability is improved. As a result, a relatively high tensile elongation is maintained even after being exposed for a long time under a high temperature condition.

  On the other hand, when (c) 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 the alkaline earth metal content is less than 200 ppm, the reaction with (a) the PPS resin may proceed more easily. However, from the viewpoint of improving the heat resistance stability described above, it is preferable that (a) the total content of alkali metal and alkaline earth metal contained in the PPS resin is 200 ppm or more. Accordingly, after the reaction between the (a) PPS resin having a total alkali metal and alkaline earth metal content of less than 200 ppm and (c) the compound having an amino group or an isocyanate group is completed, the alkali metal or alkaline earth metal described above is completed. A preferable method is to add the treated (a) PPS resin and adjust the total of the alkali metal and alkaline earth metal components contained in the final (a) PPS resin to 200 ppm or more. In addition, (a) a combination of (PS) a compound having an amino group, an epoxy group, and an isocyanate group is used together with PPS having a total of less than 200 ppm and 200 ppm or more of alkali metal and alkaline earth metal contained in the PPS resin. Of course, it is also possible to use for reaction.

  When the total content of alkali metal and alkaline earth metal is less than 200 ppm, the effect of improving the heat resistance stability becomes insufficient, which is not preferable. Although there is no restriction | limiting in the upper limit of the total content of an alkali metal and an alkaline-earth metal, 1000 ppm or less is preferable from a viewpoint which does not impair wet heat resistance and electrical insulation. Note that the total content of alkali metal and alkaline earth metal referred to here is a value measured by an atomic absorption method using an aqueous solution of ash obtained by ashing the PPS resin as a sample.

(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 3) and a repeating unit represented by the following structural formula (Formula 4).

  Note that T in the above structural formulas (Chemical Formulas 3 and 4) is —O— or —O—Z—O—, and the divalent bonds are 3, 3′-, 3, 4′-, 4 , 3′-, 4,4′-position, and Z is composed of a divalent group represented by the following structural formula (Formula 5) and a divalent group represented by the following structural formula (Formula 6). Selected from the group.

X in the structural formula (Formula 6) 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 formula (Chemical Formula 3, Chemical Formula 4) 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 7). 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 4) 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 3 and 4) further contains a repeating unit represented by the following structural formula (Chemical Formula 8).

  M in the structural formula (Chemical Formula 8) is selected from the group represented by the following structural formula (Chemical Formula 9) (B in the formula is —S— or —CO—), and R ′ is defined above. R is the same as R or a divalent group represented by the following structural formula (Formula 10) (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 11) and organic diamine represented by the following structural formula (Formula 12) In a known method for producing a polyetherimide from the above, it is produced by replacing part or all of the organic diamine of the structural formula (Chemical Formula 12) with an amine-terminated organosiloxane represented by the following structural formula (Chemical Formula 13). .

  T in the structural formula (Chemical Formula 11), R in the structural formula (Chemical Formula 12), and n, m, and g in the structural formula (Chemical Formula 13) 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. Among them, the block copolymer is flexible and has excellent tensile elongation at break. It is preferable in achieving the degree. Examples of the poly (ether imide-siloxane) block copolymer include chemical structures represented by the following structural formula (Formula 14).

Here, a in the structural formula (Formula 14) 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 15).

T in the above formula (Chemical Formula 15) 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 16) is reacted with a siloxane oligomer having the following structural formula (Chemical Formula 17) 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 17) 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 16) 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 190 ° C. or lower and even more preferably 160 ° C. or higher and 180 ° C. or lower.

(C) Compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group In the present invention, in order to obtain a polyphenylene sulfide resin composition that is flexible and dramatically improved in tensile rupture elongation, (C) It is necessary 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.

  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, epoxidized polyolefins, 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.

  Moreover, the olefin copolymer which has an epoxy group is also mentioned. Examples of the olefin copolymer having an epoxy group (epoxy group-containing olefin copolymer) include an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer. . Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.

  Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.

  The method for introducing these epoxy group-containing components is not particularly limited, and methods such as copolymerization with α-olefin and the like, or graft introduction to an olefin (co) polymer using a radical initiator can be used.

  The introduction amount of the monomer component containing an epoxy group is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to the whole monomer as a raw material of the epoxy group-containing olefin copolymer. It is appropriate to be within the range.

  As an epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer having an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as a copolymerization component is preferably exemplified. 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, styrene, acrylonitrile and the like.

  Such an olefin copolymer may be any random, alternating, block, or graft copolymerization mode.

  An olefin copolymer obtained by copolymerizing an glycidyl ester of an α-olefin and an α, β-unsaturated carboxylic acid is, among others, a glycidyl ester 1 of 60 to 99% by weight of an α-olefin and an α, β-unsaturated carboxylic acid. An olefin copolymer obtained by copolymerizing ˜40% by weight is particularly preferable.

  Specific examples of the glycidyl ester of α, β-unsaturated carboxylic acid 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" Representing graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidi methacrylate Copolymers thereof.

  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 tensile elongation at break, it is preferable that the compound contains one or more isocyanate groups or a compound containing two or more epoxy groups, and further contains an alkoxysilane or epoxy group containing an isocyanate group. More preferred is an alkoxysilane.

  The blending ratio of (a) PPS resin and (b) poly (ether imide-siloxane) copolymer in the polyphenylene sulfide resin composition of the present invention is (a) and (b) being 100% by weight as the sum of (a) and (b). ) / (B) = 99-60 wt% / 1-40 wt%. (B) When the poly (ether imide-siloxane) copolymer is less than 1% by weight, the effect of improving the tensile elongation at break is poor, and (b) the poly (ether imide-siloxane) copolymer exceeds 40% by weight. Then, not only is the phase structure unstable, but the melt fluidity is remarkably hindered. Furthermore, the preferable blending ratio of (a) PPS resin and (b) poly (ether imide-siloxane) copolymer is (a) / (b) = 97-80 wt% / 3-20 wt%, and the material cost In consideration of the balance between improvement of tensile elongation at break and (a) / (b) = 95 to 85% by weight / 5 to 15% by weight is more preferable.

  The compounding amount of the compound having at least one functional group selected from the group consisting of (c) amino group, epoxy group, and isocyanate group in the present invention is the same for (a) PPS resin and (b) poly (etherimide-siloxane). It is the range of 0.05-10 weight part with respect to a total of 100 weight part of a polymer, The range of 0.1-5 weight part is preferable, The range of 0.2-3 weight part is more preferable. (C) When the compounding amount of the compound having a functional group is less than 0.05 parts by weight, it is difficult to obtain a stable high tensile elongation at break, and in the range exceeding 10 parts by weight, the melt fluidity is significantly inhibited. Therefore, it is not preferable.

  The polyphenylene sulfide resin composition of the present invention has (a) an excellent tensile elongation at break without impairing the heat resistance, chemical resistance and flame retardancy inherent to the PPS resin, and is exposed to high temperatures for a long time. Even if this is done, a high tensile elongation at break can be maintained. In order to exhibit such characteristics, in the morphology (phase structure), (a) the PPS resin forms a sea phase (continuous phase or matrix), and (b) the poly (ether imide-siloxane) copolymer has an island phase. Forming (dispersed phase) can be exemplified as a preferred embodiment.

  Furthermore, the number average dispersed particle size of the (b) poly (ether imide-siloxane) copolymer is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) If the number average dispersed particle diameter of the poly (ether imide-siloxane) copolymer is in a range exceeding 500 nm, the tensile breaking elongation is not sufficiently improved, which is not preferable.

  Further, it is desirable that the polyphenylene sulfide resin composition of the present invention has stable and excellent toughness even when recycled. That is, after injection molding once, the molded piece is pulverized and injection molded again, and (a) PPS resin forms a sea phase (continuous phase or matrix), and (b) poly (ether) It is preferable that the (imido-siloxane) copolymer forms an island phase (dispersed phase). Furthermore, the number average dispersed particle size of the (b) poly (ether imide-siloxane) copolymer is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity.

  In order to form such a phase structure, it is possible to exemplify a method in which the shearing force is relatively strong in the process of melt kneading described later.

  Here, the number average dispersed particle size is as follows: (a) ASTM No. 4 dumbbell test piece is molded at a molding temperature of PPS resin melting peak temperature + 20 ° C., and a thin piece of 0.1 μm or less at −20 ° C. from the center. Is cut in the direction of the cross-sectional area of the dumbbell piece, and is magnified 10,000 to 20,000 times with a Hitachi H-7100 transmission electron microscope (resolution (particle image) 0.38 nm, magnification of 500 to 600,000 times) As for the dispersion part of 100 arbitrary (b) poly (ether imide-siloxane) copolymers when observed as follows, first, the respective maximum diameter and minimum diameter are measured, and the average value is taken as the dispersion particle diameter. Then, it is the number average dispersed particle size obtained after that.

  The polyphenylene sulfide resin composition of the present invention has excellent tensile elongation at break and also maintains high tensile elongation even when exposed to high temperatures for a long time. From the viewpoint of practicality, ASTM No. 4 dumbbell The tensile elongation at break (measured using a Tensilon UTA2.5T tensile tester at a chuck distance of 64 mm and a tensile speed of 10 mm / min) is preferably 50% or more, and more preferably 70% or more. preferable. When the tensile elongation at break is less than 50%, it is not preferable because breakage easily occurs when assembling various molded articles made of the polyphenylene sulfide resin composition of the present invention.

  Further, the tensile break elongation (measured at a distance between chucks of 64 mm and a tensile speed of 10 mm / min using a Tensilon UTA2.5T tensile tester) of 15% or more of ASTM No. 4 dumbbell molded pieces after being treated at 200 ° C. for 300 hours is 15% or more. Desirably, it is more preferably 20% or more. When the tensile elongation at break after treatment at 200 ° C. for 300 hours is less than 15%, various molded articles made of the polyphenylene sulfide resin composition of the present invention are destroyed when used continuously at high temperatures as automobile engine peripheral parts. This is not preferable because it tends to occur.

  In order to express such properties, the aforementioned (a) alkali metal and alkaline earth metal content in the PPS resin is 200 ppm or more, and the number of the aforementioned (b) poly (ether imide-siloxane) copolymer. Examples of preferable methods include an average dispersed particle size of 500 nm or less and a relatively strong shearing force in the melt-kneading process described later.

Method for Producing Resin Composition As a method for producing the polyphenylene sulfide resin composition of the present invention, raw materials are supplied to commonly known melt kneaders such as single-screw and twin-screw extruders, Banbury mixers, kneaders, and mixing rolls. (A) Melting and kneading at a processing temperature of 5 to 100 ° C. of the melting peak temperature of the PPS resin can be given as a representative example. At this time, it is preferable to use a twin-screw extruder and relatively increase the shearing force. Specifically, a twin screw extruder having L / D (L: screw length, D: screw diameter) of 20 or more, preferably 30 or more, and having two or more kneading portions, preferably three or more. A method of kneading so that the resin temperature at the time of mixing is (a) the melting peak temperature of the PPS resin +10 to 70 ° C. Etc. can be preferably used. The upper limit of L / D is not particularly limited, but 60 or less is preferable from the viewpoint of economy. The upper limit of the kneading portion is not particularly limited, but is preferably 10 or less from the viewpoint of productivity.

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

  The polyphenylene sulfide resin composition of the present invention is flexible and has a significantly improved tensile elongation at break. In order to exhibit such properties, it is preferable to finely disperse the (b) poly (ether imide-siloxane) copolymer to a number average dispersed particle diameter of 500 nm or less, and more detailed melt kneading method will be described in more detail. Then, all the raw materials are blended, melt-kneaded and pelletized by the above method, and further melt-kneaded once or more, (a) a group consisting of PPS resin and (c) amino group, epoxy group, isocyanate group Examples thereof include a method in which a compound having at least one functional group selected from the above is melt kneaded in advance to promote the reaction, and then (b) a poly (ether imide-siloxane) copolymer is further melt kneaded.

  For the latter, (a) a PPS resin and (c) a compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group are blended, melt-kneaded in advance, and pelletized. b) It may be blended with a poly (ether imide-siloxane) copolymer and further melt-kneaded, or (a) at least one selected from the group consisting of a PPS resin and (c) an amino group, an epoxy group, and an isocyanate group. (B) Poly (ether imide-siloxane) copolymer can be fed from the middle of the extruder and melt-kneaded using a side feeder during compounding with a compound having a functional group of It is.

  Further, a compound having at least one functional group selected from the group consisting of (a) a PPS resin, (b) a poly (etherimide-siloxane) copolymer, and (c) an amino group, an epoxy group, and an isocyanate group. (B) a poly (ether imide-siloxane) copolymer high-concentration master is prepared, and (a) a PPS resin is blended and further melt-kneaded one or more times. A kneading method in which the poly (ether imide-siloxane) copolymer is diluted to a desired ratio can also be exemplified as a preferred method.

  In particular, in order to obtain a polyphenylene sulfide resin composition having excellent tensile elongation at break of the present invention and retaining high tensile elongation even when exposed for a long time under high temperature conditions, as described above, (a) PPS resin The total content of alkali metal and alkaline earth metal contained therein is preferably 200 ppm or more. Therefore, from the viewpoint of promoting the reaction between (a) the PPS resin and (c) a compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group, alkali metal and alkaline earth metal components are used. (B) after preparing a high concentration master of poly (ether imide-siloxane) copolymer using (a) PPS resin having a total of less than 200 ppm, the total of alkali metal and alkaline earth metal content is 200 ppm or more, Preferably, the alkali metal and alkaline earth contained in the (a) PPS resin in the polyphenylene sulfide resin composition finally obtained by blending 500 ppm or more of (a) PPS resin and further melt-kneading once or more. It is possible to adjust the total metal content to 200 ppm or more.

  In addition, (b) The melt viscosity of the PPS resin added to the high concentration master of the poly (ether imide-siloxane) copolymer can be freely selected, and the fluidity of the polyphenylene sulfide resin composition finally produced thereby Can be easily controlled.

  From the viewpoint of promoting the reaction between (a) the PPS resin and (c) a compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group, an alkali metal and an alkaline earth metal component are used. (B) after preparing a high concentration master of poly (ether imide-siloxane) copolymer using (a) PPS resin having a total of less than 200 ppm, the total of alkali metal and alkaline earth metal content is 200 ppm or more, Preferably, 500 ppm or more of (a) PPS resin is included in (a) PPS resin of the finally obtained polyphenylene sulfide resin composition molded product by blending and diluting during molding processing such as injection molding. Of course, the total of the alkali metal and alkaline earth metal components can be adjusted to 200 ppm or more.

  In addition, a method for producing a resin composition having a dispersion structure with a number average dispersed particle size of 500 nm or less by melt-kneading or dissolving in a common solvent or the like and uniformly dissolving at a molecular level, followed by spinodal decomposition However, from the viewpoint of simplicity and economy, a method of producing by melting and kneading in the category of a reactive incompatible polymer alloy that does not undergo molecular compatibility is preferable.

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 within a range of 30 parts by weight or less with respect to a total of 100 parts by weight of (a) polyphenylene sulfide resin and (b) poly (etherimide-siloxane) copolymer, and less than 10 parts by weight. Is preferable, the range of less than 1 part by weight is more preferable, and the range of 0.8 part by weight or less is still more preferable. 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, a resin other than (b) poly (ether imide-siloxane) copolymer may be added and blended in the polyphenylene sulfide resin composition of the present invention within a range not impairing the effects of the present invention. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone. Olefin-based polymers that do not contain epoxy groups such as resins, polyether ether ketone resins, polyimide resins, polyether imide resins, polyether sulfone resins, polyamide imide resins, tetrafluoropolyethylene resins, ethylene / 1-butene copolymers And a copolymer.

  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. Specific examples of injection molding applications include, for example, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, machine breakers, knife switches, and other pole rods. Electrical component parts such as electrical component 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 such as 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 .; VTRs Parts, TV , Iron, hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc / compact disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Household and office electrical parts: Office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters and other machine-related parts: microscopes, binoculars , Optical equipment and precision machinery-related parts represented by cameras, watches, etc .; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dials, various valves such as exhaust gas valves, fuel-related / exhaust systems / intake systems Various pipes 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, distributor, starter switch, starter relay, transmission Wire harness, window washer nozzle, air conditioner panel switch 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, ignition device case, etc. Examples of automobiles and vehicle-related parts. Among them, the polyphenylene sulfide resin composition of the present invention is useful as a member for fluid piping, a pipe for water heater, and a valve member because of excellent properties that express excellent toughness not only at room temperature and high temperature but also at low temperatures. is there.

  In addition, the polyphenylene sulfide resin composition of the present invention is flexible and extremely excellent in tensile elongation at break. In addition to maintaining high tensile elongation after being exposed for a long time under high temperature conditions, it has high heat resistance, Since it is difficult to deteriorate, it is particularly useful as an extrusion molding application having a relatively high molding temperature and a long melt residence time. 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.

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

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

[injection molding]
An ASTM No. 4 dumbbell test piece was molded at a resin temperature of 310 ° C. and a mold temperature of 150 ° C. using a Sumitomo-Nestal injection molding machine SG75.

[Extrusion molding]
A round bar having a diameter of 50 mm was extruded at a speed of 2500 mm / hr using a single screw extruder while air cooling the forming die at a resin temperature of 320 ° C. The center part of the obtained round bar was cut to obtain an ASTM No. 4 dumbbell test piece for tensile test.

[Evaluation of extrusion moldability]
The round bar obtained by the extrusion molding was cut into a length of 300 mm, and the protrusions and black foreign matters generated on the round bar surface were counted by visual observation. The total number of protrusions and black foreign bodies was evaluated as 1 or less, ◯, 2 to 5 as Δ, and 6 or more as ×.

[Dispersed particle size]
The center part of the injection-molded ASTM No. 4 dumbbell test piece was cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less at −20 ° C. was cut from the center part of the cross section. 100 pieces of (b) poly (b) when observed at a magnification of 10,000 times with an H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) Regarding the dispersed portion of the (etherimide-siloxane) copolymer, first, the maximum diameter and the minimum diameter were measured, the average value was defined as the dispersed particle diameter, and then the number average dispersed particle diameter, which was the average value, was obtained. .

[23 ° C tensile test of untreated molded product]
For the ASTM No. 4 dumbbell test piece obtained by injection molding or extrusion molding, using a Tensilon UTA2.5T tensile tester, the tensile breaking elongation was measured at 23 ° C. under the conditions of a distance between chucks of 64 mm and a tensile speed of 10 mm / min. It was measured.

[23 ° C tensile test of molded product treated at 200 ° C for 300 hours]
The ASTM No. 4 dumbbell test piece obtained by injection molding or extrusion molding was placed in a gear oven set at 200 ° C., treated for 300 hours and allowed to cool at room temperature, and then using a Tensilon UTA 2.5T tensile tester. The tensile elongation at break was measured at 23 ° C. under conditions of a distance between chucks of 64 mm and a tensile speed of 10 mm / min.

[−20 ° C. tensile test of untreated molded product]
The ASTM No. 4 dumbbell test piece obtained by injection molding was subjected to an Instron Japan Company Limited 5581 type universal material testing machine equipped with a cooling thermostat at −20 ° C., a chuck distance of 64 mm, and a tensile speed. The tensile elongation at break was measured under the condition of 10 mm / min.

[Alkali metal and alkaline earth metal contents in PPS resin]
(A) After ashing 5 g of PPS resin 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, and an atomic absorption spectrophotometer AA manufactured by Shimadzu Corporation Measured by atomic absorption method using -6300.

[Reference Example 1] (a) Polymerization of PPS resin (a-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol 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] (a) Polymerization of PPS resin (a-2)
Dehydration, polymerization, washing, and drying were performed in the same manner as in Reference Example 1 except that 0.05 wt% acetic acid aqueous solution at the time of PPS washing was used as ion exchange water. The obtained a-2 had a melt viscosity of 250 Pa · s (310 ° C., shear rate of 1000 / s) and a total content of alkali metal and alkaline earth metal of 706 ppm.

[Reference Example 3] (a) Polymerization of PPS resin (a-3)
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-3 had a melt viscosity of 280 Pa · s (310 ° C., shear rate of 1000 / s) and a total content of alkali metal and alkaline earth metal of 276 ppm.

Reference Example 4 (b) Poly (ether imide-siloxane) copolymer b-1: Poly (ether imide-siloxane) block copolymer having a glass transition temperature of 170 ° C. (“SILTEM 1500” manufactured by SABIC Innovative Plastics) )
b-2: Poly (ether imide-siloxane) block copolymer having a glass transition temperature of 200 ° C. (“SILTEM 1700” manufactured by SABIC Innovative Plastics)

[Reference Example 5] Polyetherimide homopolymer b′-1: Polyetherimide homopolymer having a glass transition temperature of 217 ° C. (“ULTEM1010” manufactured by SABIC Innovative Plastics)

[Reference Example 6] Olefin-based resin b′-2: ethylene / glycidyl methacrylate copolymer (“Bond First” BF-E manufactured by Sumitomo Chemical Co., Ltd.)
b′-3: ethylene / 1-butene copolymer (“Tuffmer” TX610 manufactured by Mitsui Chemicals, Inc.)

[Reference Example 7] Compound having at least one functional group selected from the group consisting of amino group, epoxy group and isocyanate group c-1: Epoxy cresol novolac type epoxy resin (“EPICLON” N-695 manufactured by DIC Corporation)
c-2: 4,4′-diphenylmethane diisocyanate (reagent manufactured by Kanto Chemical Co., Inc.)
c-3: γ-aminopropyltriethoxysilane (KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.)
c-4: 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)
c-5: 2- (3,4 Epoxycyclohexyl) ethyltrimethoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Comparative Example 9-11, Example 4 ～8,10～13]
At least one functional group selected from the group consisting of (a) PPS resin, (b) poly (etherimide-siloxane) copolymer, and (c) amino group, epoxy group, and isocyanate group shown in Tables 1 and 2 After having dry-blended the compounds having the ratios shown in Table 1 and Table 2, using a TEX30α twin screw extruder (L / D = 45, 5 kneading sections) manufactured by Nippon Steel Works, equipped with a vacuum vent, At a screw rotation speed of 300 rpm, the cylinder temperature was set so that the die removal resin temperature would be 330 ° C. or less, and melt kneading was performed. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque. Next, the pellets dried overnight at 130 ° C. were subjected to injection molding, and (b) the number average dispersed particle diameter of the poly (ether imide-siloxane) copolymer in the molded piece, the 23 ° C. tensile elongation at break of the untreated molded product. The 23 ° C. tensile elongation at break of a molded product treated at 200 ° C. for 300 hours and the −20 ° C. tensile elongation at break of an untreated molded product were measured. The results were as shown in Tables 1 and 2.

[Example 9]
Except for the screw rotation speed of 200 rpm, after melt-kneading and injection molding in the same manner as in Example 8, (b) the number average dispersed particle size of the poly (etherimide-siloxane) copolymer in the molded piece, untreated molding The product was measured for 23 ° C. tensile break elongation, 200 ° C. × 300 hour treated molded product 23 ° C. tensile break elongation, and untreated molded product −20 ° C. tensile break elongation. The results were as shown in Table 2.

[Example 14]
(A) 70% by weight of a-1 as a PPS resin, (b) 30% by weight of b-1 as a poly (etherimide-siloxane) copolymer, (c) a group consisting of an amino group, an epoxy group, and an isocyanate group After dry blending a raw material consisting of 3 parts by weight of c-4 as a compound having at least one functional group selected from TEX30α type twin screw extruder (L / D = 45, 5 kneading portions), and at a screw rotation speed of 300 rpm, the cylinder temperature was set so that the resin temperature at which the die was removed was 330 ° C. or lower, and melt kneading was performed. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque.

  Next, after dry blending a raw material consisting of 34% by weight of the pellets dried at 130 ° C. overnight and (a) 66% by weight of a-3 as a PPS resin, TEX30α manufactured by Nippon Steel Works, which was equipped with a vacuum vent. Using a mold twin screw extruder (L / D = 45, 5 kneading portions), the cylinder temperature was set at a screw rotation speed of 300 rpm so that the resin temperature at which the die was discharged was 330 ° C. or less, and melt kneading was performed. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque.

  The pellets dried overnight at 130 ° C. were subjected to injection molding, and (b) the number average dispersed particle diameter of the poly (etherimide-siloxane) copolymer in the molded piece, the 23 ° C. tensile elongation at break of the untreated molded product, 200 The 23 ° C. tensile breaking elongation of the molded product treated at 300 ° C. for 300 hours and the −20 ° C. tensile breaking elongation of the untreated molded product were measured. Table 2 shows the composition ratio of the finally obtained polyphenylene sulfide resin composition, the contents of alkali metal and alkaline earth metal in PPS calculated from the composition ratio, and various physical property measurement results.

[Example 15]
(A) 70% by weight of a-1 as a PPS resin, (b) 30% by weight of b-1 as a poly (etherimide-siloxane) copolymer, (c) a group consisting of an amino group, an epoxy group, and an isocyanate group After dry blending a raw material consisting of 3 parts by weight of c-4 as a compound having at least one functional group selected from TEX30α type twin screw extruder (L / D = 45, 5 kneading portions), and at a screw rotation speed of 300 rpm, the cylinder temperature was set so that the resin temperature at which the die was removed was 330 ° C. or lower, and melt kneading was performed. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque.

  Next, after dry blending a raw material consisting of 34% by weight of the pellets dried at 130 ° C. overnight and (a) 66% by weight of a-1 as a PPS resin, TEX30α manufactured by Nippon Steel Works, equipped with a vacuum vent. Using a mold twin screw extruder (L / D = 45, 5 kneading portions), the cylinder temperature was set at a screw rotation speed of 300 rpm so that the resin temperature at which the die was discharged was 330 ° C. or less, and melt kneading was performed. The strand discharged from the die was rapidly cooled in a water bath and then pelletized by a strand cutter. The resulting pellet was opaque.

  The pellets dried overnight at 130 ° C. were subjected to injection molding, and (b) the number average dispersed particle diameter of the poly (etherimide-siloxane) copolymer in the molded piece, the 23 ° C. tensile elongation at break of the untreated molded product, 200 The 23 ° C. tensile breaking elongation of the molded product treated at 300 ° C. for 300 hours and the −20 ° C. tensile breaking elongation of the untreated molded product were measured. Table 2 shows the composition ratio of the finally obtained polyphenylene sulfide resin composition, the contents of alkali metal and alkaline earth metal in PPS calculated from the composition ratio, and various physical property measurement results.

[Comparative Example 1]
(A) Using only T-1 as a PPS resin, a TEX30α type twin screw extruder (L / D = 45.5, kneading part 5 locations) manufactured by Nippon Steel Works, equipped with a vacuum vent, screw rotation speed 300 rpm Then, the cylinder temperature was set so that the die ejection resin temperature would be 330 ° C. or lower, and the mixture was melt-kneaded and pelletized with a strand cutter.

  The pellets dried overnight at 130 ° C. are subjected to injection molding, 23 ° C. tensile breaking elongation of untreated molded product, 23 ° C. tensile breaking elongation of 200 ° C. × 300 hour treated molded product, −20 ° C. of untreated molded product. The tensile elongation at break was measured. The results are shown in Table 3.

[Comparative Example 2]
(C) Except for not adding a compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group, after melt-kneading and injection molding in the same manner as in Examples 1 to 5, (B) Number average dispersed particle size of poly (ether imide-siloxane) copolymer, 23 ° C. tensile elongation at break of untreated molded product, 23 ° C. tensile elongation at break of molded product treated at 200 ° C. for 300 hours, untreated The −20 ° C. tensile elongation at break of the molded product was measured. The results are shown in Table 3.

[Comparative Example 3]
A compound having at least one functional group selected from the group consisting of (a) PPS resin, (b) poly (etherimide-siloxane) copolymer and (c) amino group, epoxy group, and isocyanate group shown in Table 3. After dry blending at the ratio shown in Table 3, using a TEX30α twin screw extruder (L / D = 45, 5 kneading sections) manufactured by Nippon Steel Works, equipped with a vacuum vent, at a screw speed of 300 rpm. Then, the cylinder temperature was set so that the resin temperature for dicing out was 330 ° C. or lower, and the mixture was melt-kneaded and pelletized with a strand cutter.

  The pellets dried overnight at 130 ° C. were subjected to injection molding, and (b) the number average dispersed particle diameter of the poly (etherimide-siloxane) copolymer in the molded piece, the 23 ° C. tensile elongation at break of the untreated molded product, 200 The 23 ° C. tensile breaking elongation of the molded product treated at 300 ° C. for 300 hours and the −20 ° C. tensile breaking elongation of the untreated molded product were measured. The results are shown in Table 3.

[Comparative Example 4]
(B) Instead of the poly (ether imide-siloxane) copolymer, after melt-kneading and injection molding in the same manner as in Example 11 except that the polyetherimide homopolymer b′-1 was used, Number average dispersed particle size of polyetherimide homopolymer b′-1, 23 ° C. tensile elongation at break of untreated molded article, 23 ° C. tensile elongation at break of molded article treated at 200 ° C. for 300 hours, untreated molded article The −20 ° C. tensile elongation at break was measured. The results are shown in Table 3.

[Comparative Example 5]
(B) Instead of the poly (ether imide-siloxane) copolymer, after melt-kneading and injection molding in the same manner as in Example 14 except that the polyether imide homopolymer b′-1 was used, Number average dispersed particle size of polyetherimide homopolymer b′-1, 23 ° C. tensile elongation at break of untreated molded article, 23 ° C. tensile elongation at break of molded article treated at 200 ° C. for 300 hours, untreated molded article The −20 ° C. tensile elongation at break was measured. The results are shown in Table 3.

[Comparative Example 6]
(B) Instead of the poly (ether imide-siloxane) copolymer, melt-kneading was carried out in the same manner as in Example 11 except that the olefin resins b′-2 and b′-3 were used in the proportions shown in Table 3. After injection molding, the number average dispersed particle size of the olefinic resins b′-2 and b′-3 in the molded piece, 23 ° C. tensile elongation at break of untreated molded product, 23 of 200 ° C. × 300 hour treated molded product The tensile breaking elongation at 20 ° C. and the -20 ° C. tensile breaking elongation of the untreated molded product were measured. The results are shown in Table 3.

[Example 16]
The pellets obtained in Example 11 were dried overnight at 130 ° C., and then subjected to extrusion molding to form a round bar, and the extrusion moldability was evaluated. Next, after cutting the center part of the obtained round bar and collecting ASTM No. 4 dumbbell test piece for tensile test, 23 ° C. tensile test was performed on the untreated molded product and the molded product treated at 200 ° C. for 300 hours. . The results are shown in Table 4.

[Comparative Example 7]
The pellets obtained in Comparative Example 4 were dried at 130 ° C. overnight, and then subjected to extrusion molding to form a round bar, and the extrusion moldability was evaluated. Next, after cutting the center part of the obtained round bar and collecting ASTM No. 4 dumbbell test piece for tensile test, 23 ° C. tensile test was performed on the untreated molded product and the molded product treated at 200 ° C. for 300 hours. . The results are shown in Table 4.

[Comparative Example 8]
The pellets obtained in Comparative Example 6 were dried overnight at 130 ° C., and then subjected to extrusion molding to form a round bar, and the extrusion moldability was evaluated. Next, after cutting the center part of the obtained round bar and collecting ASTM No. 4 dumbbell test piece for tensile test, 23 ° C. tensile test was performed on the untreated molded product and the molded product treated at 200 ° C. for 300 hours. . The results are shown in Table 4.

The results of Examples 4 to 16 and Comparative Examples 1 to 11 will be compared and described. In any of Examples 4 to 15, the tensile breaking elongation of the untreated product was dramatically improved as compared with the single PPS resin shown in Comparative Example 1. In Examples 10 to 12 and 14 using PPS having an alkali metal and alkaline earth metal content of 200 ppm or more, the tensile break elongation of the molded article treated at 200 ° C. for 300 hours was kept high.

In either embodiment 4-15 also, by adding an alkoxysilane compound having at least one functional group selected from the group consisting of (c) d epoxy group, isocyanate group, (b) poly (ether imide - siloxane ) The dispersed particle diameter of the copolymer was finely dispersed to 500 nm or less. On the other hand, (c) d epoxy group, in Comparative Example 2 was not added to the alkoxysilane compound having at least one functional group selected from the group consisting of isocyanate groups, (b) poly (ether imide - siloxane) copolymer As a result, the dispersion particle diameter exceeded 500 nm and the tensile elongation at break of the untreated product was low.

  (B) In Comparative Example 3 where the poly (ether imide-siloxane) copolymer was 45%, the phase structure became unstable, no clear sea-island structure was observed, and the tensile break elongation of the untreated product The result was also low.

  (B) In Comparative Examples 4 and 5 in which a polyetherimide homopolymer was used in place of the poly (etherimide-siloxane) copolymer, the polyetherimide homopolymer was finely dispersed with a particle size of 500 nm or less. Although the tensile fracture elongation of the treated product was also improved to some extent, the tensile fracture elongation of the molded product treated at 200 ° C. for 300 hours was extremely low compared to the corresponding Examples 11 and 14, respectively.

  (B) In Comparative Example 6 in which an olefin resin was used instead of the poly (ether imide-siloxane) copolymer, the olefin resin was finely dispersed with a particle size of 500 nm or less, and the tensile elongation at break of the untreated product was also Although it is a result which improves to some extent, the tensile fracture elongation of the molded article treated at 200 ° C. for 300 hours was lower than that of the corresponding Example 11.

  In Example 16 in which the pellets obtained in Example 11 were subjected to extrusion molding, the extrusion moldability was extremely good, and no protrusions or black foreign matters were observed. In addition, the tensile elongation of the extrusion molded product having a relatively high molding temperature and a long melt residence time is almost the same as that of the injection molded product, regardless of whether it is an untreated product or a 200 ° C. × 300 hr treated product. showed that.

  In Comparative Example 7 where the pellets obtained in Comparative Example 4 were subjected to extrusion molding, although the extrusion moldability was good, the tensile breaking elongation of the treated product obtained by extrusion molding at 200 ° C. × 300 hr was injection molding. It was low like the 200 degreeC x 300 hr processed product obtained by this. Further, the tensile elastic modulus was higher than that of Example 16, and the flexibility required for the fuel tube application was poor.

  In Comparative Example 8 in which the pellets obtained in Comparative Example 6 were subjected to extrusion molding, many projections and black foreign substances estimated to be caused by thermal deterioration and gelation of the olefin resin were observed in the round bar, and the extrusion moldability was The result was inferior. The tensile break elongation of the untreated product obtained by extrusion molding was considerably inferior to that of the untreated product obtained by injection molding with a relatively short melt residence time.

Claims (7)

A resin composition comprising (a) 99 to 60% by weight of a polyphenylene sulfide resin and (b) 1 to 40% by weight of a poly (etherimide-siloxane) copolymer, where the total of (a) and (b) is 100% by weight. to 100 parts by weight of polyphenylene characterized by comprising at least one compounding 0.1 to 10 parts by weight of an alkoxysilane compound having a functional group selected from the group consisting of (c) d epoxy group, isocyanate group A sulfide resin composition. In the morphology (phase structure) of the polyphenylene sulfide resin composition, (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), and the (b) poly (ether imide-siloxane) copolymer is a number average dispersed particle. 2. The polyphenylene sulfide resin composition according to claim 1, which has a sea-island structure in which a dispersed phase (island phase) dispersed with a diameter of 500 nm or less is formed. Wherein (a) polyphenylene sulfide resin, polyphenylene sulfide resin composition according to any one of claims 1-2, characterized in that it contains more than 200ppm in total of alkali metal and alkaline earth metal content. Tensile elongation at break ASTM4 dumbbell shaped pieces (Tensilon UTA2.5T tensile tester chuck distance 64mm using a measurement at a tensile speed of 10 mm / min) is, according to claim 1 to 3, characterized in that less than 50% The polyphenylene sulfide resin composition according to any one of the above. The tensile elongation at break (measured at a distance between chucks of 64 mm and a tensile speed of 10 mm / min using a Tensilon UTA2.5T tensile tester) of 15% or more of ASTM No. 4 dumbbell molded pieces after being treated at 200 ° C. for 300 hours. The polyphenylene sulfide resin composition according to any one of claims 1 to 4 . A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 5 . The molded product according to claim 6 , wherein the molded product is an extrusion molded product.