JP5206492B2 - Method for producing polyphenylene sulfide resin composition and polyphenylene sulfide resin composition - Google Patents

Description

  The present invention relates to a polyphenylene sulfide resin composition that is extremely excellent in toughness, particularly impact strength at low temperatures, without impairing the heat resistance and chemical resistance inherent in polyphenylene sulfide, and a method for producing the same.

  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, PPS resin has low toughness compared to other engineering plastics such as nylon and PBT, and its application is limited at present, and its improvement is strongly desired.

  Heretofore, several resin compositions comprising a PPS resin and an olefin resin having a carboxyl group and an acid anhydride group have been studied for the purpose of improving the toughness of the PPS resin.

  For example, Patent Document 1 discloses a resin composition comprising a polyarylene sulfide resin, a thermoplastic elastomer having a functional group, and an epoxy compound having three or more epoxy groups. However, only a general melt-kneading technique is described as a method for producing the resin composition. In this case, it is difficult to finely disperse the thermoplastic elastomer to a dispersed particle diameter of 500 nm or less. In the case of a general melt-kneading technique, the reaction between the polyarylene sulfide resin and the epoxy compound becomes insufficient and the phase structure becomes unstable. For example, an injection molded resin molded product is pulverized and injection molded again. The dispersed particle diameter of the thermoplastic elastomer in the molded piece was further coarsened, and the recyclability was extremely inferior. In addition, since the thermoplastic elastomer is not finely dispersed to a dispersion particle size of 500 nm or less, the toughness, particularly the low Izod impact strength under a low temperature condition such as −10 ° C. or −40 ° C. is low. There was a disadvantage that a thermoplastic elastomer had to be added.

  Patent Document 2 discloses a resin composition comprising a polyarylene sulfide resin, a thermoplastic elastomer, and an epoxy resin, wherein the thermoplastic elastomer is dispersed with a weight average particle diameter of 0.5 μm or less. However, only a general melt-kneading technique is described as a method for producing the resin composition. In this case, it is difficult to finely disperse the thermoplastic elastomer to a dispersed particle diameter of 500 nm or less. In the case of a general melt-kneading technique, the reaction between the polyarylene sulfide resin and the epoxy compound becomes insufficient, and the phase structure becomes unstable. For example, an injection molded resin molded product is pulverized and injection molded again. The dispersed particle diameter of the thermoplastic elastomer in the molded piece was further coarsened, and the recyclability was extremely inferior. In addition, since a general melt-kneading technique is adopted and the thermoplastic elastomer is not finely dispersed to a dispersion particle diameter of 500 nm or less, the toughness, particularly, the Izod impact strength under a low temperature condition such as −10 ° C. or −40 ° C. However, there was a drawback that a relatively large amount of thermoplastic elastomer had to be added for improvement.

  Patent Document 3 discloses a resin composition in which an olefin copolymer comprising an α-olefin and an α, β-unsaturated monocarboxylic acid is contained in a polyphenylene sulfide resin obtained by melt-kneading a non-blocking polyfunctional isocyanate compound. Has been. However, since the non-blocking polyfunctional isocyanate compound is used as a compatibilizing agent, the reaction with the polyphenylene sulfide resin and the olefin copolymer does not proceed sufficiently, and the olefin copolymer is finely dispersed to a dispersion particle size of 500 nm or less. It was difficult to do. For the same reason, since the phase structure becomes unstable, for example, the dispersion particle diameter of the thermoplastic elastomer in the molded piece obtained by pulverizing the injection molded resin product and performing the injection molding again becomes further coarse. The recyclability was extremely inferior. In addition, since the thermoplastic elastomer is not finely dispersed to a dispersion particle size of 500 nm or less, the toughness, particularly the low Izod impact strength under a low temperature condition such as −10 ° C. or −40 ° C. is low. There was a disadvantage that a thermoplastic elastomer had to be added.

JP 2004-3000272 A (Claims) JP 2004-143372 A (Claims) Japanese Patent No. 2747728 (Claims)

  The present invention provides a polyphenylene sulfide resin composition that is extremely excellent in toughness, particularly impact strength at low temperatures, and a method for producing the same, without significantly impairing the chemical resistance, heat resistance, and mechanical strength inherent in the polyphenylene sulfide resin. Is an issue.

  Accordingly, as a result of intensive studies to solve the above problems, the present inventors have previously melt-kneaded a polyphenylene sulfide resin and a compound having two or more epoxy groups in one molecule (excluding an olefin resin) in advance. Thereafter, by further melt-kneading with an olefin resin having a carboxyl group and / or an acid anhydride group, the dispersed particle diameter of the olefin resin is finely dispersed to 500 nm or less, and the melt residence stability of the phase structure is also improved. As a result of the improvement, the inventors have found that the Izod impact strength at low temperatures such as −10 ° C. and −40 ° C. is drastically improved and reached the present invention.

That is, the present invention is as follows.
1. Olefin resin having at least one functional group selected from (a) 99 to 60% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight 0.1 to 10 parts by weight of (c) a compound having 2 or more epoxy groups in one molecule (excluding olefinic resins) is added to 100 parts by weight of a resin composition comprising 1 to 40% by weight. A method for producing a polyphenylene sulfide resin composition comprising: (a) a polyphenylene sulfide resin and (c) a compound having two or more epoxy groups in one molecule (excluding an olefin resin) previously melted After kneading, further (b) a method for producing a polyphenylene sulfide resin composition, which is melt-kneaded with an olefin resin having a functional group,
2. (B) The olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is an ethylene / butene copolymer having a carboxyl group and / or an acid anhydride group. A process for producing the polyphenylene sulfide resin composition according to claim 1,
3. (C) The compound having two or more epoxy groups in one molecule (excluding the olefin resin) is a compound having four or more epoxy groups in one molecule, A process for producing the polyphenylene sulfide resin composition according to claim 1,
4). (A) The method for producing a polyphenylene sulfide resin composition according to any one of 1 to 3, wherein the polyphenylene sulfide resin is an acid-treated polyphenylene sulfide resin,
5. Olefin resin having at least one functional group selected from (a) 99 to 85% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight The method for producing a polyphenylene sulfide resin composition according to any one of 1 to 4, which comprises 1 to 15% by weight,
6). Olefin resin having at least one functional group selected from (a) 99 to 60% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight 0.1 to 10 parts by weight of (c) a compound having 2 or more epoxy groups in one molecule (excluding olefinic resins) is added to 100 parts by weight of a resin composition comprising 1 to 40% by weight. A polyphenylene sulfide resin composition having a morphology (phase structure) in which (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), and (b) an olefin resin has a number average dispersed particle diameter of 500 nm. In a molded piece having a sea-island structure in which a dispersed phase (island phase) dispersed in the following is formed, pulverized after injection molding, and injection molded again, Serial (b) polyphenylene sulfide resin composition characterized in that the olefin resin is dispersed in the following number-average dispersed particle diameter 500nm having a functional group,
7). The polyphenylene sulfide resin composition according to 6, wherein the resin molded article has an Izod impact strength with a cut notch at −10 ° C. (measured according to ASTM D256) of 300 J / m or more,
8). Olefin resin having at least one functional group selected from (a) 99 to 60% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight 0.1 to 10 parts by weight of (c) a compound having 2 or more epoxy groups in one molecule (excluding olefinic resins) is added to 100 parts by weight of a resin composition comprising 1 to 40% by weight. A polyphenylene sulfide resin composition having a morphology (phase structure) in which (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), and (b) an olefin resin has a number average dispersed particle diameter of 500 nm. An Izod impact strength (AS) with a cut notch at −10 ° C. of a resin molded product having a sea-island structure in which a dispersed phase (island phase) is dispersed as follows Polyphenylene sulfide resin composition measured according to M D256) is characterized in that it is 300 J / m or more,
9. The polyphenylene sulfide resin composition according to any one of 7 to 8, wherein the resin molded article has an Izod impact strength with a cut notch at -40 ° C (measured according to ASTM D256) of 300 J / m or more,
10. (B) The polyphenylene according to any one of 6 to 9, wherein the number average dispersed particle size of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is 300 nm or less. A sulfide resin composition,
11. (B) The olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is an ethylene / butene copolymer having a carboxyl group and / or an acid anhydride group. 10 to 10, the polyphenylene sulfide resin composition according to any one of
12 (A) The polyphenylene sulfide resin composition according to any one of 6 to 11, wherein the polyphenylene sulfide resin is an acid-treated polyphenylene sulfide resin,
13. (C) Any one of 6 to 12, wherein the compound having two or more epoxy groups in one molecule (excluding olefin-based resins) is a compound having four or more epoxy groups in one molecule A polyphenylene sulfide resin composition according to claim 1,
14 Olefin resin having at least one functional group selected from (a) 99 to 85% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight The polyphenylene sulfide resin composition according to any one of 6 to 13, which comprises 1 to 15% by weight,
15. Olefinic resin having at least one functional group selected from (a) 93 to 85% by weight of (a) polyphenylene sulfide resin, (b) carboxyl group and acid anhydride group, with the total of (a) and (b) being 100% by weight The polyphenylene sulfide resin composition according to 14, characterized by comprising 7 to 15% by weight,
16. A polyphenylene sulfide resin composition obtained by the production method according to any one of 1 to 5, wherein in the morphology (phase structure), (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), b) A molded piece having a sea-island structure in which a dispersed phase (island phase) in which an olefin-based resin is dispersed with a number average dispersed particle size of 500 nm or less is formed, which is pulverized after injection molding and injection molded again. The polyphenylene sulfide resin composition, wherein the olefin resin having a functional group (b) is dispersed with a number average dispersed particle size of 500 nm or less,
17. 16. The polyphenylene sulfide resin composition according to 16, wherein the resin molded article has an Izod impact strength with a cut notch at −10 ° C. (measured according to ASTM D256) of 300 J / m or more,
18. A polyphenylene sulfide resin composition obtained by the production method according to any one of 1 to 5, wherein in the morphology (phase structure), (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), b) Izod impact strength with cut notch (ASTM D256) at −10 ° C. of a resin molded product having a sea-island structure in which a dispersed phase (island phase) in which an olefin resin is dispersed with a number average dispersed particle size of 500 nm or less is formed A polyphenylene sulfide resin composition characterized in that the measurement is 300 J / m or more,
19. The polyphenylene sulfide resin composition according to any one of 17 to 18, wherein the resin molded article has an Izod impact strength with a cut notch at -40 ° C (measured according to ASTM D256) of 300 J / m or more,
20. (B) The polyphenylene according to any one of 16 to 19, wherein the number average dispersed particle diameter of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is 300 nm or less. A sulfide resin composition,
It is.

  According to the present invention, a polyphenylene sulfide resin composition having extremely excellent toughness, particularly impact strength at low temperatures, can be obtained. In addition, because it is extremely excellent in toughness, high toughness is easily developed even if the composition of the olefin resin is relatively small, so that the toughness is maintained without significantly impairing the chemical resistance, heat resistance, and mechanical strength inherent in the polyphenylene sulfide resin. A polyphenylene sulfide resin composition is 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 (I),

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 with the higher melt viscosity is preferable from the meaning which obtains the more excellent toughness. 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 the shear rate of 1000 / s.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Such a mixture is usually heated to a 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. 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 or washing with an organic solvent.

  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 / sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone and 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.

  In the present invention, PPS obtained by introducing antari earth metal salt such as Ca into PPS may be used. As a method for introducing the alkaline earth metal salt, a method of adding an alkaline earth metal salt before, during, or after the previous step, before the polymerization step, during the polymerization step, after the polymerization step, in the polymerization vessel Or a method of adding an alkaline earth metal salt at the beginning, middle, or last stage of the washing step. Among them, the easiest method is a method of adding an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with warm water or hot water. The alkaline earth metal salt is preferably introduced into the PPS in the form of an alkaline earth metal ion such as acetate, hydroxide or carbonate. It is preferable to remove excess alkaline earth metal salt by washing with warm water. The alkaline earth metal ion concentration at the time of introducing the alkaline earth metal ion is preferably 0.001 mmol or more, more preferably 0.01 mmol or more with respect 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 toughness, after removing residual oligomers and residual salts by repeating organic solvent washing and hot water at about 80 ° C. or hot water washing described above several times Particularly preferred is an acid treatment method.

  (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 oxidative crosslinking treatment in order to achieve the toughness target. In addition, preferable (a) PPS resins used in the present invention include Toray Industries, Ltd. M2588, M2888, M2088, T1881, L2120, L2480, M2100, M2900, E2080, E2180, E2280, and the like.

(B) Olefin resin having at least one functional group selected from carboxyl group and acid anhydride group (b) Olefin resin having at least one functional group selected from carboxyl group and acid anhydride group used in the present invention Examples of the resin include an olefin resin obtained by introducing a monomer component having a functional group such as a carboxyl group, a salt thereof, and an acid anhydride group into a polymer obtained by polymerizing or copolymerizing an olefin.

  Examples of olefin polymers or copolymers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 dimethyl-1-hexene, 4,4 dimethyl-1-pentene, 4-ethyl-1-hexene, Α-Oleph such as 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene Polymers obtained by polymerizing single or two or more kinds, such as α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Examples include α, β-unsaturated carboxylic acids and copolymers thereof with alkyl esters. Preferable specific examples of the olefin polymer or copolymer include an ethylene / α-olefin copolymer using an α-olefin having 6 to 12 carbon atoms. Among these, an ethylene / 1-butene copolymer is more preferable.

The ethylene / α-olefin copolymer suitably used in the present invention preferably has a density of 0.880 g / cm ³ or less, more preferably in the range of 0.830 to 0.880 g / cm ^3. A range of 0.850 to 0.875 g / cm ³ is more preferable. The glass transition temperature (measured according to JISK7121) is preferably −40 ° C. or lower.

  Examples of functional group-containing components for introducing a monomer component having a functional group such as a carboxyl group and a salt thereof or an acid anhydride group into the olefin polymer or copolymer include maleic anhydride, fumaric anhydride, and the like. Examples thereof include monomers containing acid anhydride groups such as acid, itaconic anhydride, citraconic anhydride, and endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride. The method for introducing these functional group-containing components is not particularly limited, and a method such as copolymerization or graft introduction using an olefin polymer or copolymer using a radical initiator can be used. The amount of the monomer component containing a functional group is suitably 0.001 to 40 mol%, preferably 0.01 to 35 mol%, relative to the olefin polymer or copolymer. is there.

(C) Compounds having two or more epoxy groups in one molecule (excluding olefin-based resins)
Compounds having two or more epoxy groups in one molecule (excluding olefin resins) include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol Bisphenol glycidyl such as S, trihydroxy-diphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane Those using halogenated bisphenol instead of ether or bisphenol, glycidyl ether type epoxy compounds such as diglycidyl ether of butanediol, glycidyl ester type compounds such as glycidyl phthalate, N -Glycidyl epoxy resins such as glycidyl amine compounds such as glycidyl aniline, linear epoxy compounds such as epoxidized soybean oil, and cyclic non-glycidyl epoxy resins such as dicyclopentadiene dioxide.

  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.

  More preferred examples of the compound having two or more epoxy groups in one molecule (excluding olefin-based resins) include compounds having four or more epoxy groups in one molecule. Include epoxy cresol novolac resins having 8 or more epoxy groups in one molecule (for example, EOCN-104S manufactured by Nippon Kayaku Co., Ltd.) and special polyfunctionals having 4 epoxy groups in one molecule. An epoxy resin (for example, “Epicoat” 1031S manufactured by Japan Epoxy Resin Co., Ltd.) has (b) an olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group in (a) PPS resin. It is preferable from the viewpoint of fine dispersion and heat resistance.

The blending ratio of (a) PPS resin and (b) olefin resin having at least one functional group selected from carboxyl group and acid anhydride group in the present invention is 100% by weight of the total of (a) and (b). as, (a) / (b) = 99~60 in the range of weight% / 1 to 40% by weight, preferably (a) / (b) = 99 range of to 85% by weight / 1-15% by weight, The range of (a) / (b) = 93 to 85% by weight / 7 to 15% by weight is more preferable. It should be noted that (a) the effect of improving toughness is poor when the PPS resin exceeds 99% by weight, and if the amount of (a) PPS resin is less than 60% by weight, the heat resistance, chemical resistance, extrudability, and melt fluidity are significantly inhibited. Therefore, it is not preferable.

  In the present invention, the compounding amount of (c) a compound having two or more epoxy groups in one molecule (excluding the olefin resin) is determined from (a) polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group. It is the range of 0.1-10 weight part with respect to a total of 100 weight part of the olefin resin which has at least 1 type of functional group chosen, The range of 0.2-5 weight part is preferable, 0.3-3 weight A range of parts is more preferred. When the blending amount of the component (c) is less than 0.1 parts by weight, it is difficult to obtain a stable high toughness. When the blending amount of the component (c) exceeds 10 parts by weight, the melt fluidity is inhibited. Therefore, it is not preferable.

  The PPS resin composition of the present invention has (a) excellent toughness as well as excellent heat resistance and chemical resistance inherently possessed by the PPS resin. In order to develop such properties, in morphology, (a) the PPS resin forms a sea phase (continuous phase or matrix), and (b) has at least one functional group selected from a carboxyl group and an acid anhydride group. It is necessary for the olefinic resin to form an island phase (dispersed phase). Further, (b) the number average dispersed particle size of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is essential to be 500 nm or less, preferably 400 nm or less, more preferably 300 nm. The following are particularly preferred: The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) If the number average dispersed particle size of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is in a range exceeding 500 nm, the effect of improving toughness and chemical resistance are significantly impaired. It is not preferable.

  In addition, the PPS resin composition of the present invention stably exhibits excellent toughness even when the number of melt residences and time increase. In order to express such characteristics, even after the injection molding is performed once, the molded piece is pulverized and the injection molded again, (a) the PPS resin forms a sea phase (continuous phase or matrix). (B) It is necessary that the olefin resin having a kind of functional group selected from a carboxyl group and an acid anhydride group forms an island phase (dispersed phase). Further, (b) the number average dispersed particle size of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is essential to be 500 nm or less, preferably 400 nm or less, more preferably 300 nm. It is particularly preferred that The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) If the number average dispersed particle diameter of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is in a range exceeding 500 nm, the effect of improving toughness is remarkably impaired.

  In addition, the number average dispersed particle diameter referred to here is: (a) A ASTM No. 4 test piece is molded at a molding temperature of PPS resin melting peak temperature + 20 ° C. Cut in the direction of the cross-sectional area of the dumbbell piece and observed with a magnification of 10,000 times with an H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification of 600 to 600,000 times) manufactured by Hitachi, Ltd. For the dispersed portion of the olefin resin having at least one functional group selected from 100 (b) carboxyl groups and acid anhydride groups, first, the maximum and minimum diameters were first measured and averaged. Is the number average dispersed particle size obtained by determining the average particle size of the dispersed particles.

  The PPS resin composition of the present invention has (a) excellent toughness as well as excellent heat resistance and chemical resistance inherently possessed by the PPS resin. Accordingly, the Izod impact strength with cut notch at −10 ° C. (measured according to ASTM D256) of the resin molded product is desirably 300 J / m or more. In particular, when the total of (a) and (b) is 100% by weight, and (b) the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is 15% by weight or less. In addition, the Izod impact strength with a cut notch (measured according to ASTM D256) at −10 ° C. of the resin molded product is preferably 300 J / m or more.

  Furthermore, the PPS resin composition of the present invention desirably has a cut notched Izod impact strength (measured according to ASTM D256) at −40 ° C. of the resin molded product of 300 J / m or more, preferably 350 J / m or more. More preferably, it is 400 J / m or more.

  Another PPS resin composition of the present invention has excellent toughness as well as excellent heat resistance and chemical resistance inherent in (a) PPS resin. In order to develop such properties, in morphology, (a) the PPS resin forms a sea phase (continuous phase or matrix), and (b) has at least one functional group selected from a carboxyl group and an acid anhydride group. It is necessary for the olefinic resin to form an island phase (dispersed phase). Further, (b) the number average dispersed particle size of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is essential to be 500 nm or less, preferably 400 nm or less, more preferably 300 nm. The following are particularly preferred: The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) If the number average dispersed particle size of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is in a range exceeding 500 nm, the effect of improving toughness and chemical resistance are significantly impaired. It is not preferable.

  In addition, the number average dispersed particle size referred to here is: (a) A ASTM No. 4 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 is formed at −20 ° C. from the center. Cut in the direction of the cross-sectional area of the dumbbell piece and observed with a magnification of 10,000 times with an H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification of 600 to 600,000 times) manufactured by Hitachi, Ltd. For the dispersed portion of the olefin resin having at least one functional group selected from 100 (b) carboxyl groups and acid anhydride groups, first, the maximum and minimum diameters were first measured and averaged. Is the number average dispersed particle size obtained by determining the average particle size of the dispersed particles.

  Further, another PPS resin composition of the present invention has (a) excellent toughness as well as excellent heat resistance and chemical resistance inherent in the PPS resin. Therefore, it is necessary that the Izod impact strength with cut notch at -10 ° C. (measured according to ASTM D256) of the resin molded product is 300 J / m or more. In particular, when the total of (a) and (b) is 100% by weight, and (b) the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is 15% by weight or less. However, it is preferable that the Izod impact strength with cut notch at -10 ° C. (measured according to ASTM D256) of the resin molded product is 300 J / m or more.

  The PPS resin composition of the present invention desirably has a cut notched Izod impact strength (measured according to ASTM D256) at −40 ° C. of the resin molded product of 300 J / m or more, preferably 350 J / m or more. More preferably, it is 400 J / m or more.

Kneading process method Melt kneading is performed by supplying to a commonly known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll (a) Processing at a melting peak temperature of PPS resin + 5 to 100 ° C. A typical example is a method of kneading at a temperature, but (b) in order to finely disperse the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group, It is preferable that the shear force is relatively strong. Specifically, L / D (L: screw length, D: screw diameter) is 20 or more, a twin screw extruder having two or more kneading parts is used, and the screw rotation speed is 100 to 500 rotations. As the / min, a method of kneading such that the resin temperature at the time of mixing is (a) the melting peak temperature of the PPS resin +10 to 70 ° C. can be preferably used.

  In order to obtain the PPS resin composition having the excellent characteristics of the present invention as described above, the mixing order of the raw materials is important, and (a) the PPS resin and (c) have two or more epoxy groups in one molecule. A compound (excluding an olefin resin) is blended and melt kneaded in advance, and (b) melt kneaded with an olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group. is necessary.

  At this time, after blending all (a) PPS resin and (c) a compound having two or more epoxy groups in one molecule (however, excluding olefin-based resin), pre-melting and kneading, and pelletizing, (B) It can be blended with an olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group and further melt-kneaded, or a part of (a) PPS resin and (c) After compounding with a compound having two or more epoxy groups in one molecule (excluding olefin resin), pre-melting and kneading, and pelletizing, (b) at least selected from carboxyl group and acid anhydride group It is also possible to blend an olefin resin having one kind of functional group and the remaining (a) PPS resin and further melt-knead. In addition, all (a) PPS resin and (c) a compound having two or more epoxy groups in one molecule (excluding olefin-based resins) are blended and melt-kneaded in advance, and then used with a side feeder ( b) It is also possible to supply an olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group and melt-knead, or (a) a PPS resin and (c) one molecule After compounding with a compound having two or more epoxy groups therein (excluding olefin resin) and melt-kneading in advance, at least one kind selected from (b) carboxyl group and acid anhydride group using a side feeder It is also possible to supply the olefin resin having a functional group and the remaining (a) PPS resin and melt-knead them.

  In the case of the former two, all or part of (a) PPS resin and (c) a compound having two or more epoxy groups in one molecule (however, excluding olefin resin) are blended and melt-kneaded in advance. In this case, it is preferable to make the shearing force relatively strong. 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. And a method of kneading at a screw rotation speed of 100 to 500 rotations / minute, preferably 200 to 500 rotations / minute, can be preferably used.

  In the latter two cases, (b) all or a part of (a) PPS is supplied before supplying the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group by the side feeder. It is preferable to melt-knead the resin and (c) a compound having two or more epoxy groups in one molecule (excluding the olefin resin) with a relatively strong shearing force.

  Specifically, L / D (L: screw length, L / D of an extruder part in which all or part of (a) PPS resin and (c) a compound having two or more epoxy groups in one molecule are previously melt-kneaded. D: screw diameter) is 20 or more, preferably 30 or more, using a twin screw extruder having two or more kneading portions, preferably three or more, and the screw rotation speed is preferably 100 to 500 rotations / minute, preferably Is preferably used a method of kneading at 200 to 500 revolutions / minute.

Inorganic filler Although not an essential component, the PPS 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 30 parts by weight or less with respect to 100 parts by weight in total of (a) polyphenylene sulfide resin and (b) olefin-based resin having at least one functional group selected from carboxyl group and acid anhydride group. Is selected, preferably less than 10 parts by weight, more preferably less than 1 part by weight, and even more preferably 0.8 parts by weight or less. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. While the blending of the inorganic filler is effective for improving the elastic modulus of the material, a large amount of blending exceeding 30 parts by weight is not preferable because it causes a large decrease in toughness. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

Other additives Furthermore, in the PPS resin composition of the present invention, within the range not impairing the effects of the present invention, (b) other than the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group A resin may be added and blended. 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.

  Since the PPS resin composition of the present invention is excellent in impact resistance and low temperature toughness, it is useful for various injection-molded product applications, containers, electrical and electronic parts, automobile parts, machine-related parts, office electrical product parts, and the like.

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

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

[Injection molding (first time)]
Using an Sumitomo-Nestal injection molding machine SG75, an ASTM No. 1 dumbbell test piece and an Izod impact test piece having a length of 60 mm, a width of 12.7 mm, and a thickness of 3.2 mm were molded at a resin temperature of 310 ° C. and a mold temperature of 130 ° C. .

[Injection molding (second time)]
The ASTM No. 1 dumbbell specimen once injection molded was pulverized to a size of about 1 to 5 mm square using a pulverizer. Using this as a raw material, an ASTM No. 1 dumbbell test piece was molded at a resin temperature of 310 ° C. and a mold temperature of 130 ° C. using a Sumitomo-Nestal injection molding machine SG75.

[Dispersed particle size]
The center part of ASTM No. 1 dumbbell test piece was cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less was cut from the center part of the cross section at −20 ° C. to make an H-7100 type manufactured by Hitachi, Ltd. 100 disperse parts of (b) olefin-based resin when observed at a magnification of 10,000 times with a transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) First, each maximum diameter and minimum diameter were measured, and the average value was used as the dispersed particle diameter, and then the number average dispersed particle diameter, which was the average value thereof, was obtained.

[-10 ° C cut notched Izod impact test]
The injection molded Izod impact test piece having a length of 60 mm, a width of 12.7 mm, and a thickness of 3.2 mm was notched with a notch cutter, cooled in an ultra-low temperature thermostatic bath at −10 ° C. for 120 minutes, and in accordance with ASTM D256. The Izod impact strength with a 10 ° C. cut notch was measured.

[-40 ° C cut notched Izod impact test]
The injection molded Izod impact test piece having a length of 60 mm, a width of 12.7 mm, and a thickness of 3.2 mm was notched with a notch cutter, cooled in an ultra-low temperature thermostatic bath at −40 ° C. for 120 minutes, and in accordance with ASTM D256. The Izod impact strength with a cut notch at 40 ° C. was measured.

[Reference Example 1] (a) Polymerization of PPS resin (PPS-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 stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

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

[Reference Example 2] (a) Polymerization of PPS resin (PPS-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 PPS-2 had a melt viscosity of 250 Pa · s (310 ° C., shear rate of 1000 / s).

[Reference Example 3] (b) Olefin resin having at least one functional group selected from carboxyl group and acid anhydride group b-1: ethylene / 1-butene copolymer modified with maleic anhydride (Mitsui Chemicals) "Tuffmer" MH5020 manufactured by
b-2: Ethylene / propylene copolymer modified with maleic anhydride (“Tuffmer” MP0610 manufactured by Mitsui Chemicals, Inc.)
b-3: Acid group-containing olefin copolymer comprising 2.0% by weight of maleic anhydride, 31% by weight of ethyl acrylate and 67% by weight of ethylene

[Reference Example 4] (c) Compound having two or more epoxy groups in one molecule (excluding olefin resin)
c-1: Epoxy cresol novolak resin (EOCN-104S manufactured by Nippon Kayaku Co., Ltd.)
c-2: Special multifunctional bisphenol A type epoxy resin ("Epicoat" 1031S manufactured by Japan Epoxy Resin Co., Ltd.)
c-3: Epoxy cresol novolak resin having a biphenyl skeleton (NC-7000L manufactured by Nippon Kayaku Co., Ltd.)
c-4: Bisphenol A type epoxy resin ("Epicoat" 1004 manufactured by Japan Epoxy Resin Co., Ltd.)

[Reference Example 5] Polyfunctional isocyanate compound c′-1: Diphenylmethane diisocyanate-based polyfunctional isocyanate compound (“Millionate” MR-400, manufactured by Nippon Polyurethane Industry Co., Ltd.).

[Examples 1-7]
After dry blending the (a) PPS resin and (c) epoxy compound shown in Table 1 at the ratio shown in Table 1, a TEX30α type twin screw extruder (L / D = 45) manufactured by Nippon Steel Works, Inc. equipped with a vacuum vent. 5 and 5 kneading portions), the cylinder temperature was set so that the die removal resin temperature was 330 ° C. or less at a screw rotation speed of 300 rpm, and the mixture was melt-kneaded and pelletized with a strand cutter. The obtained pellets and (b) olefin resin shown in Table 1 were dry blended so as to have the ratio shown in Table 1, and then a TEX30α type twin screw extruder (L / D = 45.5, 5 kneading sections), 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 the mixture was melt-kneaded and pelletized by a strand cutter. .
The pellets dried at 130 ° C. overnight are subjected to injection molding, and each molded piece has −10 ° C. cut-notched Izod impact strength, −40 ° C. cut-notched Izod impact strength, and (b) number average dispersed particle diameter of olefin resin. Was measured. The results were as shown in Table 1.

[Comparative Examples 1, 3, 5, 7, 8, 10]
After dry blending (a) PPS resin, (b) olefin resin, and (c) epoxy compound shown in Table 2 at the ratio shown in Table 2, TEX30α type twin screw extrusion manufactured by Nippon Steel Works Co., Ltd. equipped with a vacuum vent Machine (L / D = 45.5, 5 kneading sections), melt kneading at a screw rotation speed of 300 rpm, setting the cylinder temperature so that the resin temperature at which the die is discharged is 330 ° C. or less, and a strand cutter Pelletized.
The pellets dried at 130 ° C. overnight are subjected to injection molding, and each molded piece has −10 ° C. cut-notched Izod impact strength, −40 ° C. cut-notched Izod impact strength, and (b) number average dispersed particle diameter of olefin resin. Was measured. The results were as shown in Table 2.

[Comparative Examples 2, 4, 6]
After dry blending (a) PPS resin, (b) olefin resin, and (c) epoxy compound shown in Table 2 at the ratio shown in Table 2, TEX30α type twin screw extrusion manufactured by Nippon Steel Works Co., Ltd. equipped with a vacuum vent Machine (L / D = 45.5, 5 kneading sections), melt kneading at a screw rotation speed of 300 rpm, setting the cylinder temperature so that the resin temperature at which the die is discharged is 330 ° C. or less, and a strand cutter Pelletized. The obtained pellets were melt-kneaded under the same conditions as described above and pelletized with a strand cutter.
The pellets dried at 130 ° C. overnight are subjected to injection molding, and each molded piece has −10 ° C. cut-notched Izod impact strength, −40 ° C. cut-notched Izod impact strength, and (b) number average dispersed particle diameter of olefin resin. Was measured. The results were as shown in Table 2.

[Comparative Example 9]
(C) Melt-kneading, injection molding, and evaluation were performed in the same manner as in Example 5 except that the epoxy compound was diphenylmethane diisocyanate polyfunctional isocyanate compound c′-1.

  The results of Examples 1-7 and Comparative Examples 1-10 will be compared and described. In any of Examples 1 to 7, (a) PPS resin and (c) epoxy compound were previously melt-kneaded, and then (b) olefin-based resin was further melt-kneaded, whereby (b) olefin-based resin was 500 nm or less. (The first injection molding). Also, when the first injection molded piece was pulverized and then injection molded again, (b) the olefin resin was finely dispersed with a particle size of 500 nm or less (second injection molding). As described above, in Examples 1 to 7, (b) the olefin resin is finely dispersed to 500 nm or less, and even if the melt molding process is repeated, the (b) olefin resin is finely dispersed to 500 nm or less, and the phase structure is Since it was very stable, the Izod impact strength with a −10 ° C. cut notch exhibited a high value of 300 J / m or more.

  On the other hand, when all the raw materials are kneaded all together as in Comparative Examples 1, 3, 5, 7, 8, 10, or after kneading the raw materials all together as in Comparative Examples 2, 4, 6 Even when the method of repeating kneading was employed, (b) the olefin resin was roughly dispersed in a size exceeding 500 nm. In addition, the dispersion particle size of the second injection-molded piece that was injection-molded again after pulverizing the injection-molded piece was significantly larger than that of the first injection-molded piece. Unlike Example 5, in Comparative Example 9 in which an epoxy compound is a polyfunctional isocyanate compound, (a) a PPS resin and a polyfunctional isocyanate are previously melt-kneaded, and then (b) an olefin-based resin is melt-kneaded. (B) The olefin resin was not finely dispersed at a particle size of 500 nm or less, and the Izod impact strength with a cut notch at −10 ° C. was low.

Claims (20)

Olefin resin having at least one functional group selected from (a) 99 to 60% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight 0.1 to 10 parts by weight of (c) a compound having 2 or more epoxy groups in one molecule (excluding olefinic resins) is added to 100 parts by weight of a resin composition comprising 1 to 40% by weight. A method for producing a polyphenylene sulfide resin composition comprising: (a) a polyphenylene sulfide resin and (c) a compound having two or more epoxy groups in one molecule (excluding an olefin resin) previously melted After kneading, a method for producing a polyphenylene sulfide resin composition, further comprising melt-kneading the olefin resin having a functional group (b). (B) The olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is an ethylene / butene copolymer having a carboxyl group and / or an acid anhydride group. Item 2. A method for producing a polyphenylene sulfide resin composition according to Item 1. (C) A compound having two or more epoxy groups in one molecule (excluding olefinic resins) is a compound having four or more epoxy groups in one molecule. The manufacturing method of the polyphenylene sulfide resin composition in any one of. The method for producing a polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein (a) the polyphenylene sulfide resin is an acid-treated polyphenylene sulfide resin. Olefin resin having at least one functional group selected from (a) 99 to 85% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight It consists of 1 to 15 weight%, The manufacturing method of the polyphenylene sulfide resin composition in any one of Claims 1-4 characterized by the above-mentioned. Olefin resin having at least one functional group selected from (a) 99 to 60% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight 0.1 to 10 parts by weight of (c) a compound having 2 or more epoxy groups in one molecule (excluding olefinic resins) is added to 100 parts by weight of a resin composition comprising 1 to 40% by weight. A polyphenylene sulfide resin composition comprising: (a) a polyphenylene sulfide resin forming a continuous phase (sea phase), and (b) a number of olefin-based resins having a functional group. It had a sea-island structure in which a dispersed phase (island phase) dispersed with an average dispersed particle size of 500 nm or less was formed. After injection molding, this was pulverized and injection molded again. Also in the form piece, wherein (b) the polyphenylene sulfide resin composition characterized in that the olefin resin is dispersed in the following number-average dispersed particle diameter 500nm having a functional group. The polyphenylene sulfide resin composition according to claim 6, wherein the resin molded article has an Izod impact strength with a cut notch at -10 ° C (measured according to ASTM D256) of 300 J / m or more. Olefin resin having at least one functional group selected from (a) 99 to 60% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight 0.1 to 10 parts by weight of (c) a compound having 2 or more epoxy groups in one molecule (excluding olefinic resins) is added to 100 parts by weight of a resin composition comprising 1 to 40% by weight. A polyphenylene sulfide resin composition comprising: (a) a polyphenylene sulfide resin forming a continuous phase (sea phase), and (b) a number of olefin-based resins having a functional group. It has a sea-island structure in which a dispersed phase (island phase) dispersed with an average dispersed particle diameter of 500 nm or less is formed, and a cut-notched Izo of a resin molded product at −10 ° C. Polyphenylene sulfide resin composition Doo impact strength (measured according to ASTM D256) is characterized in that it is 300 J / m or more. The polyphenylene sulfide resin composition according to any one of claims 7 to 8, wherein the resin molded article has an Izod impact strength with a cut notch at -40 ° C (measured in accordance with ASTM D256) of 300 J / m or more. . (B) The number average dispersed particle diameter of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is 300 nm or less. A polyphenylene sulfide resin composition. (B) The olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is an ethylene / butene copolymer having a carboxyl group and / or an acid anhydride group. Item 11. The polyphenylene sulfide resin composition according to any one of Items 6 to 10. The polyphenylene sulfide resin composition according to any one of claims 6 to 11, wherein (a) the polyphenylene sulfide resin is an acid-treated polyphenylene sulfide resin. (C) A compound having two or more epoxy groups in one molecule (excluding an olefin resin) is a compound having four or more epoxy groups in one molecule. The polyphenylene sulfide resin composition according to any one of the above. Olefin resin having at least one functional group selected from (a) 99 to 85% by weight of polyphenylene sulfide resin, (b) carboxyl group, and acid anhydride group, with the total of (a) and (b) being 100% by weight The polyphenylene sulfide resin composition according to claim 6, comprising 1 to 15% by weight. Olefinic resin having at least one functional group selected from (a) 93 to 85% by weight of (a) polyphenylene sulfide resin, (b) carboxyl group and acid anhydride group, with the total of (a) and (b) being 100% by weight The polyphenylene sulfide resin composition according to claim 14, comprising 7 to 15% by weight. A polyphenylene sulfide resin composition obtained by the production method according to claim 1, wherein in the morphology (phase structure), (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), b) A molded piece having a sea-island structure in which a dispersed phase (island phase) in which an olefin-based resin is dispersed with a number average dispersed particle size of 500 nm or less is formed, which is pulverized after injection molding and injection molded again. The polyphenylene sulfide resin composition is characterized in that (b) the olefin resin having a functional group is dispersed with a number average dispersed particle diameter of 500 nm or less. The polyphenylene sulfide resin composition according to claim 16, wherein the resin molded article has an Izod impact strength with a cut notch at -10 ° C (measured in accordance with ASTM D256) of 300 J / m or more. A polyphenylene sulfide resin composition obtained by the production method according to claim 1, wherein in the morphology (phase structure), (a) the polyphenylene sulfide resin forms a continuous phase (sea phase), b) Izod impact strength with cut notch (ASTM D256) at −10 ° C. of a resin molded product having a sea-island structure in which a dispersed phase (island phase) in which an olefin resin is dispersed with a number average dispersed particle size of 500 nm or less is formed. The polyphenylene sulfide resin composition is characterized in that the measurement is 300 J / m or more. 19. The polyphenylene sulfide resin composition according to claim 17, wherein the resin molded article has an Izod impact strength with a cut notch at −40 ° C. (measured according to ASTM D256) of 300 J / m or more. . (B) The number average dispersed particle diameter of the olefin resin having at least one functional group selected from a carboxyl group and an acid anhydride group is 300 nm or less. A polyphenylene sulfide resin composition.