JP5050728B2 - Polyetherimide resin composition - Google Patents

Description

  The present invention relates to a polyetherimide resin composition having extremely excellent toughness, a method for producing the same, and a molded article.

  Polyetherimide (hereinafter abbreviated as PEI) resin is a super engineering plastic excellent in heat resistance, mechanical strength, flame retardancy and the like. In particular, mechanical strength shows tensile strength that cannot be obtained with general-purpose engineering plastics, and PEI resin has the characteristics of maintaining the same strength as general-purpose engineering plastics even at high temperatures around 190 ° C. It is used in various fields such as automobile parts.

  However, PEI resin has lower toughness than general-purpose engineering plastics such as nylon and PBT, and its improvement is strongly desired.

  A composition comprising a PEI resin and a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has been studied. For example, Patent Document 1 discloses a resin composition comprising polyarylene sulfide, polyetherimide, and an organic silane compound. However, there is no description of a phase structure composition comprising a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups. In addition, there is no description that excellent toughness can be obtained by forming an island phase in which the PPS resin is finely dispersed. Patent Document 2 discloses a resin composition containing a polyphenylene sulfide-based resin, a polyetherimide-based resin, and a silane coupling agent having an amino group or an epoxy group. However, there is no description of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups. In addition, there is no description that excellent toughness can be obtained by finely dispersing the PPS resin. Patent Document 3 discloses a composition comprising a polyetherimide resin, a poly (arylene sulfide) resin, and a compound containing two or more epoxy groups. However, it is not described at all that excellent toughness can be obtained by forming an island phase and finely dispersing the PPS resin. Patent Document 4 discloses a resin composition comprising a polyphenylene sulfide resin, a polyetherimide resin, and an aminoalkoxysilane. However, there is no description of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups. Moreover, it is not described at all that excellent toughness can be obtained by forming an island phase and finely dispersing the PPS resin. Patent Document 5 discloses a composition comprising a polyetherimide resin and a polyphenylene sulfide resin. However, there is no description of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups. In addition, there is no description that excellent toughness can be obtained by finely dispersing the PPS resin.

Thus, in any patent document, a resin composition having high tensile elongation (toughness) can be obtained by forming an island phase in a PPS resin and finely dispersing the number average dispersed particle diameter to 1000 nm or less. There was no mention of what was obtained.
Japanese Patent Laid-Open No. 4-130158 (Claims) JP-A-5-86293 (Claims) JP-A-8-176439 (Claims) Japanese Patent Laid-Open No. 10-46028 (Claims) Japanese Patent Laid-Open No. 11-80545 (Claims)

  An object of the present invention is to obtain a polyetherimide resin composition having excellent toughness and a molded product thereof.

  Therefore, as a result of investigations to solve the above problems, the present inventors used (c) a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups, and (a) in the PEI resin ( b) It was found that high tensile elongation can be obtained by finely dispersing the PPS resin so that the number average dispersed particle diameter is 1000 nm or less, and the above-mentioned problems can be solved.

That is, the present invention
1. The total of (a) and (b) is 100% by weight, with respect to 100 parts by weight of a resin composition comprising (a) a polyetherimide resin 99 to 60% by weight and (b) a polyphenylene sulfide resin 1 to 40% by weight. And (c) a polyetherimide resin composition comprising 0.1 to 10 parts by weight of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups, and having a morphology (phase) Structure), the (a) polyetherimide resin forms a continuous phase (sea phase), and the (b) polyphenylene sulfide resin forms a dispersed phase (island phase) dispersed with a number average dispersed particle size of 1000 nm or less. A polyetherimide resin composition characterized by having a sea-island structure;
2. (C) The polyetherimide resin composition according to the above 1, wherein the compound containing one or more isocyanate groups and / or the compound containing two or more epoxy groups is an isocyanate group-containing alkoxysilane,
3. (B) The polyetherimide resin composition according to any one of the above 1-2, wherein the number average dispersed particle size of the polyphenylene sulfide resin is 500 nm or less,
4). Further, (d) the inorganic filler is added to 0.0001 to 50 parts by weight with respect to a total of 100 parts by weight of the (a) polyetherimide resin and (b) polyphenylene sulfide resin. The polyetherimide resin composition according to the description,
5. The tensile elongation (measured at a distance between chucks of 64 mm and a tensile speed of 10 mm / min according to ASTM D638 method) of ASTM No. 4 dumbbell molded pieces (thickness 1.6 mm) obtained by injection molding exceeds 40%. The polyetherimide resin composition according to any one of 1 to 4 above,
6). The total of (a) and (b) is 100% by weight, with respect to 100 parts by weight of a resin composition comprising (a) a polyetherimide resin 99 to 60% by weight and (b) a polyphenylene sulfide resin 1 to 40% by weight. (C) a method for producing a polyetherimide resin composition comprising 0.1 to 10 parts by weight of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups, 6. The polyetherimide according to any one of 1 to 5 above, wherein the polyetherimide resin composition comprising (a), (b) and (c) is melt-kneaded and then melt-kneaded once more. Production method of resin composition,
7). A molded article comprising the polyetherimide resin composition according to any one of 1 to 5 above,
It is.

  According to the present invention, a polyetherimide resin composition having extremely excellent toughness represented by tensile elongation can be obtained.

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

(A) PEI resin The (a) polyetherimide resin used in the present invention is a polymer containing an aliphatic, alicyclic or aromatic ether unit and a cyclic imide group as a repeating unit, and is melt moldable. If it is a polymer which has, it will not specifically limit. Further, as long as the effect of the present invention is not impaired, the main chain of the polyetherimide is a cyclic imide, a structural unit other than an ether bond, such as an aromatic, aliphatic, alicyclic ester unit, oxycarbonyl unit, etc. May be contained.

  As a specific polyetherimide, a polymer represented by the following general formula is preferably used.

Wherein R1 is a divalent aromatic residue having 6 to 30 carbon atoms, R2 is a divalent aromatic residue having 6 to 30 carbon atoms, 2 to 20 2 selected from the group consisting of an alkylene group having 2 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polydiorganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms As R1 and R2, for example, those having an aromatic residue represented by the following formula group are preferably used.

  In the present invention, from the viewpoint of melt moldability and cost, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride and m-phenylene having a structural unit represented by the following formula Diamine or a condensate with p-phenylenediamine is preferably used. This polyetherimide is commercially available from General Electric Company under the trademark “Ultem”.

(B) PPS resin (b) 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, (b) 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.

  The melt viscosity of the (b) PPS resin used in the present invention is not particularly limited, but is preferably 600 Pa · s (310 ° C., shear rate 1000 / s) or less from the viewpoint of maintaining melt fluidity. For example, a range of 400 Pa · s or less is preferable, 300 Pa · s or less is more preferable, and 200 Pa · s or less is more preferable.

  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 (b) PPS resin used for this invention is demonstrated below, if (b) 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 (b) 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]
(B) 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 (b) PPS resin in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means (b) 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 (b) 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]
(B) In the method for producing a PPS resin, the sulfidizing agent is usually used in the form of a hydrate. Before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidizing 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]
(B) 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]
(B) 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. (B) Any known recovery method may be employed for the PPS resin.

  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. There is no need for slow cooling at the same rate in the entire process of the slow cooling step, and a method of slow cooling at a rate of 0.1 to 1 ° C./minute until the polymer particles crystallize and then 1 ° C./minute or more is used. 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]
(B) 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. (B) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have the action of decomposing the (B) 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 (b) those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method such as (b) immersing the PPS resin in an acid or an aqueous solution of the acid, and if necessary, stirring or heating can be appropriately performed. 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 (b) PPS resin is preferably washed several times with water or warm water in order to remove residual 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 (b) PPS resin by acid treatment.

  When performing hot water treatment, it is as follows. (B) 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 (b) 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 (b) PPS resin by hot water washing. There is no particular limitation on the operation of the hot water treatment, and a predetermined amount of (b) PPS resin is charged into a predetermined amount of water, heated and stirred in a pressure vessel, or a continuous hydrothermal treatment method. Is called. (B) The ratio of the PPS resin to water is preferably higher, but usually a bath ratio of (b) 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 preferably an inert atmosphere in order to avoid this. Further, the (b) PPS resin that has finished this hot water treatment operation is preferably washed several times with warm water in order to remove the remaining components.

  When washing with an organic solvent, it is as follows. (B) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing (b) 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 of immersing (b) the PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning (b) 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.

  (B) The PPS resin can be used after having been polymerized by heating in an oxygen atmosphere and a 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, it is preferable that the (b) PPS resin is a substantially linear PPS which does not undergo high molecular weight by thermal oxidation crosslinking treatment in order to achieve the toughness target. Preferred (b) 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.

(C) Compound containing at least one isocyanate group and / or compound containing at least two epoxy groups In the present invention, (c) a compound containing at least one isocyanate group and / or an epoxy for the purpose of exhibiting stable high toughness. It is necessary to add a compound containing two or more groups 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.

  Examples of the compound containing at least one isocyanate group include isocyanate compounds such as 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, polymethylene polyphenyl polyisocyanate, and γ-isocyanate. Propyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanate An isocyanate group-containing alkoxysilane compound such as propyltrichlorosilane can be exemplified.

  (C) Among compounds containing one or more isocyanate groups and / or compounds containing two or more epoxy groups, a compound having one or more isocyanate groups is preferred in order to obtain a stable and high toughness effect. More preferred is an alkoxysilane containing an isocyanate group.

  The blending ratio of (a) PEI resin and (b) PPS resin in the present invention is (a) / (b) = 99 to 60% by weight / 1 to 100% by weight of the sum of (a) and (b). The range is 40% by weight, preferably (a) / (b) = 97 to 70% by weight / 2 to 30% by weight, and (a) / (b) = 95 to 80% by weight / 2 to 20% by weight. % Range is more preferred. When (a) the PEI resin exceeds 99% by weight, the effect of improving toughness is poor, and when the (A) PEI resin is less than 60% by weight, the mechanical strength such as creep properties is deteriorated.

  The blending amount of the component (c) in the present invention is in the range of 0.05 to 10 parts by weight and 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of (a) PEI resin and (b) PPS resin. Is preferable, and the range of 0.2 to 3 parts by weight is more preferable. When the amount of the component (c) is less than 0.05 parts by weight, it is difficult to obtain a stable high toughness, and when the amount of the component (c) exceeds 10 parts by weight, the melt fluidity is significantly inhibited. This is not preferable.

  The PEI resin composition of the present invention has excellent toughness in addition to (a) the excellent heat resistance, mechanical strength, and flame retardancy inherently possessed by the PEI resin. In order to develop such characteristics, in the phase structure, it is necessary that (a) the PEI resin forms a sea phase (continuous phase or matrix) and (b) the PPS resin forms an island phase (dispersed phase). It is. Furthermore, it is essential that (b) the number average dispersed particle size of the PPS resin is 1000 nm or less, preferably 700 nm or less, more preferably 500 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) If the number average dispersed particle size of the PPS resin is in a range exceeding 1000 nm, the toughness improving effect is remarkably impaired.

  In addition, the PEI resin composition of the present invention desirably has stable and excellent toughness even when recycled. 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) PEI resin forms a sea phase (continuous phase or matrix). (B) The PPS resin preferably forms an island phase (dispersed phase). Further, (b) the number average dispersed particle size of the PPS resin is desirably 1000 nm or less, preferably 700 nm or less, more preferably 500 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) If the number average dispersed particle size of the PPS resin is in a range exceeding 1000 nm, the toughness improving effect is remarkably impaired.

  As a method for measuring the number average dispersed particle size, an arbitrary molded product was cut at -20 ° C. from a central portion of a thin piece of 0.1 μm or less and an H-7100 transmission electron microscope (resolution (resolution ( (Particle image) With respect to the dispersion part of 100 (b) PPS resin at the time of magnifying to 10,000 to 20,000 times at 0.38 nm and magnification of 500 to 600,000, first, It can be obtained by measuring the maximum diameter and the minimum diameter, setting the average value as the dispersed particle diameter, and then calculating the average value.

(D) Inorganic filler Although not an essential component, the PEI resin composition of the present invention can be used by blending (d) an inorganic filler as long as the effects of the present invention are not impaired. Specific examples of the inorganic filler (d) 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, Fibrous fillers such as silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal fiber, or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, Silicates such as asbestos and alumina silicate, 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 Sulfates such as calcium sulfate 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, Non-fibrous fillers such as graphite are used, among which 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 (d) inorganic fillers may be hollow, and two or more kinds may be used in combination. These (d) inorganic fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the anticorrosive material, the lubricant, and the effect of imparting conductivity.

  The blending amount of the inorganic filler is selected from the range of 50 parts by weight or less with respect to the total of 100 parts by weight of (a) PEI resin and (b) PPS resin, preferably less than 10 parts by weight. The range is 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. The blending of the inorganic filler is effective for improving the elastic modulus of the material, but a large amount of blending exceeding 50 parts by weight is not preferable because the toughness is greatly lowered. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

(E) Other Additives In addition, a resin other than the PPS resin may be added and blended in the PEI resin composition of the present invention as long as the effects of the present invention are not impaired. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyether sulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone. Resin, Polythioetherketone resin, Polyetheretherketone resin, Polyimide resin, Polyamideimide resin, Polytetrafluoroethylene resin, Ethylene / butene copolymer and other olefin-based polymers and copolymers that do not contain epoxy groups It is done.

  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 polycondensate, release agents such as silicone compounds, anti-coloring agents such as hypophosphite, water, lubricants, UV protection agents, coloring agents, foaming A usual additive such as an agent can be blended. If any of the above compounds exceeds 20% by weight of the total composition, (a) the inherent properties of the PEI resin are impaired, and therefore, the addition is preferably not more than 10% by weight, more preferably not more than 1% by weight.

Kneading process method Melt kneading is performed by supplying to a generally known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. (B) Processing at a melting peak temperature of the PPS resin +5 to 100 ° C A typical example is a method of kneading at a temperature, but (b) In order to further disperse the PPS resin, it is preferable to use a twin-screw extruder and relatively increase the shearing force. 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 (b) the melting peak temperature of the PPS resin +10 to 70 ° C. can be preferably used. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt kneaded by the above method, a part of the raw materials are blended and melt kneaded by the above method, and further the remaining raw materials Any method may be used, such as a method of blending and melt-kneading a part of the raw materials, or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt-kneading by a twin-screw extruder. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.

  In order to further finely disperse the (b) PPS resin, (a) a PEI resin, (b) a PPS resin and (c) a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups After melt-kneading, further melt-kneading at least once is a preferred method for producing the PEI resin composition of the present invention. The upper limit of the number of kneading is not particularly limited, but after melt-kneading once, it is preferable to melt and knead once to three times from the viewpoint of toughness improvement effect and economy.

  In addition, (b) the ratio of PPS resin is set to a high concentration, and (a) PEI resin, (b) PPS resin and (c) a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups are melted. After obtaining the PEI resin composition by kneading, it is also possible to mix (a) the PEI resin and (b) dilute the PPS resin to a desired ratio when melt-kneading once or more. In this case, (b) the amount of the PPS resin is once melt-kneaded without increasing the concentration, and then melted and kneaded at least once to obtain a PPS resin composition having the same composition. Therefore, it is preferable in terms of economy. In addition, when melt-kneading once or more, the fluidity of the PEI resin composition to be finally produced can be freely controlled by blending (a) PEI resin having different melt viscosities. .

  Moreover, when melt-kneading, adding 0.02 part or more of water with respect to a total of 100 weight part of (a) PEI resin and (b) PPS resin is mentioned as a more preferable manufacturing method. When 0.02 part or more of water is added, impurities derived from oligomers and by-products contained in the PEI resin composition of the present invention are easily removed. In addition, in the case of a PEI resin composition containing an isocyanate group-containing alkoxysilane as a compatibilizing agent component (c), hydrolysis of the alkoxysilane is promoted by water addition, which occurs when the resulting resin composition is melt processed. The amount of alcohol can be reduced. Accordingly, the melt moldability to various processed bodies such as injection molded products, extrusion molded products such as films and sheets is improved.

  About the addition amount of water, 0.02 part or more is preferable, More preferably, it is 0.5 part or more, Furthermore, 1.0 part or more is preferable. The upper limit of the amount of water added is not particularly limited, but is preferably less than 5 parts from the viewpoint of kneadability and pressure increase in the extruder due to water vapor.

  The timing of adding water is not particularly limited, but after (c) a compound containing one or more isocyanate groups or a compound containing two or more epoxy groups reacts with (a) PEI resin or (b) PPS resin. It is particularly preferable to add it once melt-kneading and then melt-kneading once more. The method of adding water is not particularly limited, but a method of side-feeding water using a liquid feeding device such as a gear pump or a plunger pump from the middle of the extruder, or once melting and kneading and further melting once or more. When kneading, a method of blending water or side-feeding from the middle of the extruder is preferred.

  Further, the PEI resin composition of the present invention is a resin composition having excellent toughness. As a guide, the tensile elongation of a dumbbell molded piece of ASTM No. 4 (distance between chucks of 64 mm according to ASTM D638 method, tensile speed of 10 mm / min) ) Is preferably over 40%, more preferably 50% or more, and even more preferably 60% or more.

  The PEI resin composition of the present invention can be molded into various products by known molding methods such as injection molding, extrusion molding of films and sheets, transfer molding and the like. In addition, the PEI resin composition of the present invention is excellent in toughness as well as mechanical strength such as high heat resistance, thermal stability, weld strength and creep characteristics, which are the characteristics of PEI resin. It is useful as an automobile part.

  The present invention will be described more specifically with reference to the following examples.

  In the following examples, material characteristics were measured by the following method.

[injection molding]
An ASTM No. 4 dumbbell piece (thickness: 1.6 mm) was molded using a Sumitomo-Nestal injection molding machine SG75 at a resin temperature of 350 ° C. and a mold temperature of 150 ° C.

[Tensile test]
A Tensilon UTA2.5T tensile tester was used for the measurement, and the distance between chucks was 64 mm and the tensile speed was 10 mm / min according to the ASTM D638 method.

[Observation of morphology]
The center part of 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 was cut from the center part of the cross section at −20 ° C. to make an H-7100 type manufactured by Hitachi, Ltd. The dispersion particle size of the PPS resin was measured by magnifying the image to 10,000 to 20,000 times with a transmission electron microscope (resolution (particle image) 0.38 nm, magnification of 500 to 600,000 times).

[Reference Example 1] (a) PEI resin (PEI-1)
“Ultem” 1010 Made by GE

[Reference Example 2] (b) 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 had a melt viscosity of 200 Pa · s (310 ° C., shear rate of 1000 / s).

[Reference Example 3] (b) PPS resin polymerization (PPS-2)
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 861.00 g (10.5 mol), and ion-exchanged water 10500 g, and gradually heated to 245 ° C. over about 3 hours while passing 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 (a) PPS resin had a melt viscosity of 60 Pa · s (310 ° C., shear rate 1000 / s).

[Examples 1 to 3]
Each component shown in Examples 1 to 3 in Table 1 was dry blended in the proportions shown in Table 1, and then a TEX30α twin screw extruder (L / D = 45.5, manufactured by Nippon Steel Works) equipped with a vacuum vent. Using 5 kneading parts), the cylinder temperature was set so that the resin resin temperature at the die was 330 ° C. at a screw rotation speed of 300 rpm, 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 the tensile elongation at break of each molded piece and the dispersion diameter of the island component were measured. The results were as shown in Table 1.

[Example 4]
Each component shown in Example 4 of Table 1 was dry blended at the ratio shown in Example 4 of Table 1, and then a TEX30α type twin screw extruder (L / D = 45. 5 and 5 kneading parts) at a screw rotation speed of 300 rpm, the cylinder temperature was set so that the resin temperature at which the die was discharged was 330 ° C., and the mixture was melt-kneaded and pelletized with a strand cutter. Subsequently, this pellet was again melt-kneaded under the same conditions as described above, and pelletized with a strand cutter. About the obtained pellet, it used for injection molding similarly to Example 1, and implemented the tensile fracture elongation of the molded piece, and the dispersion diameter of the island component. The results were as shown in Table 1.

[Example 5]
After dry blending PPS-1 (70% by weight), PEI-1 (30% by weight) and compatibilizer C-1 (3 parts by weight with respect to 100 parts by weight in total of PPS-1 and PEI-1), Using a TEX30α-type twin screw extruder (L / D = 45.5, 5 kneading sections) manufactured by Nippon Steel Works, equipped with a vacuum vent, the resin temperature of the die is 330 ° C. at a screw speed of 300 rpm. Thus, the cylinder temperature was set and melt-kneaded, and pelletized with a strand cutter. Next, PEI-1 was blended in this pellet so that each component shown in Example 5 of Table 1 was in the ratio shown in Example 5 of Table 1, and then melt-kneaded under the same conditions as described above. Pelletized with a cutter. Other than that, it used for injection molding similarly to Example 1, and measured the tensile breaking elongation of the molded piece, and the dispersion diameter of the island component. The results were as shown in Table 1.

[Example 6]
After dry blending PPS-1 (70% by weight), PEI-1 (30% by weight) and compatibilizer C-1 (3 parts by weight with respect to 100 parts by weight in total of PPS-1 and PEI-1), Using a TEX30α-type twin screw extruder (L / D = 45.5, 5 kneading sections) manufactured by Nippon Steel Works, equipped with a vacuum vent, the resin temperature of the die is 330 ° C. at a screw speed of 300 rpm. Thus, the cylinder temperature was set and melt-kneaded, and pelletized with a strand cutter. Next, PEI-1 was blended with the pellets so that each component shown in Example 6 in Table 1 had the ratio shown in Example 6 in Table 1, and then melt-kneaded under the same conditions as described above, and then the strand. Pelletized with a cutter. Other than that, it used for injection molding similarly to Example 1, and measured the tensile breaking elongation of the molded piece, and the dispersion diameter of the island component. The results were as shown in Table 1.

[Example 7]
After dry blending PPS-2 (70% by weight), PEI-1 (30% by weight) and compatibilizer C-1 (3 parts by weight with respect to 100 parts by weight in total of PPS-1 and PEI-1), Using a TEX30α-type twin screw extruder (L / D = 45.5, 5 kneading sections) manufactured by Nippon Steel Works, equipped with a vacuum vent, the resin temperature of the die is 330 ° C. at a screw speed of 300 rpm. Thus, the cylinder temperature was set and melt-kneaded, and pelletized with a strand cutter. Next, PEI-1 was blended with the pellets so that each component shown in Example 7 of Table 1 was in the ratio shown in Example 7 of Table 1, and then melt-kneaded under the same conditions as described above. Pelletized with a cutter. Other than that, it used for injection molding similarly to Example 1, and measured the tensile breaking elongation of the molded piece, and the dispersion diameter of the island component. The results were as shown in Table 1.

[Comparative Example 1]
As shown in Table 1, (b) PPS, (c) Japan having a vacuum vent as in Example 1 except that a compound containing one or more isocyanate groups or a compound containing two or more epoxy groups was not blended. Using a TEX30α type twin screw extruder (L / D = 45.5, 5 kneading sections) manufactured by Steel Works, the cylinder temperature was set so that the resin temperature at which the die was released was 330 ° C at a screw speed of 300 rpm. And kneaded and pelletized with a strand cutter. The pellet dried overnight at 130 ° C. was subjected to injection molding, and the tensile elongation at break of the molded piece was measured. As a result, as shown in Table 1, the tensile elongation was lower than that of Example 1.

[Comparative Example 2]
As shown in Table 1, (C) Nippon Steel Works' TEX30α equipped with a vacuum vent was used in the same manner as in Example 1 except that a compound containing one or more isocyanate groups or a compound containing two or more epoxy groups was not blended. Using a mold twin screw extruder (L / D = 45.5, 5 kneading sections), melt kneading at a screw rotation speed of 300 rpm and a cylinder temperature of 330 ° C. And pelletized with a strand cutter. The pellet dried overnight at 130 ° C. was subjected to injection molding, and the tensile breaking elongation of the molded piece and the dispersion diameter of the island component were measured. As shown in Table 1, the results were such that the dispersion diameter of the island component was larger and the tensile elongation was significantly lower than in Examples 1 and 2.

[Comparative Example 3]
Except that the melt kneading was performed at a set temperature of 300 ° C. and a screw rotation speed of 80 rpm using a 40 mmφ single screw extruder manufactured by Tanabe Plastics Machine Co., Ltd. equipped with a vacuum vent, and pelletized in the same manner as in Example 1. Evaluation was performed. The results were as shown in Table 1. Compared to Example 1, the tensile elongation was remarkably low, and the dispersion diameter of the island component was large.

[Comparative Examples 4 and 5]
As shown in Table 1, (c) As in Example 1, except that C-3 and C-4 were selected instead of the compound containing one or more isocyanate groups or the compound containing two or more epoxy groups, respectively. Using a TEX30α type twin screw extruder (L / D = 45.5, 5 kneading sections) manufactured by Nippon Steel Works, equipped with a vacuum vent, the die extrusion resin temperature was 330 ° C. at a screw speed of 300 rpm. The cylinder temperature was set so as to be melt-kneaded and pelletized with a strand cutter. The pellet dried overnight at 130 ° C. was subjected to injection molding, and the tensile breaking elongation of the molded piece and the dispersion diameter of the island component were measured. As shown in Table 1, the tensile elongation was lower than those in Examples 1 and 2, and the dispersion diameter of the island component was large.

[Example 8]
Except that the addition amount of the inorganic filler D-1 was 60 parts by weight, as in Example 3, a TEX30α twin screw extruder (L / D = 45.5, knee) equipped with a vacuum vent was provided. 5 portions of the ding part), the cylinder temperature was set so that the die removal resin temperature was 330 ° C. at a screw rotation speed of 300 rpm, and the mixture was melt-kneaded and pelletized by a strand cutter. The pellet dried overnight at 130 ° C. was subjected to injection molding, and the tensile breaking elongation of the molded piece and the dispersion diameter of the island component were measured. As a result, as shown in Table 1, the tensile elongation was lower than that of Example 3.

Claims (7)

The total of (a) and (b) is 100% by weight, with respect to 100 parts by weight of a resin composition comprising (a) a polyetherimide resin 99 to 60% by weight and (b) a polyphenylene sulfide resin 1 to 40% by weight. And (c) a polyetherimide resin composition comprising 0.1 to 10 parts by weight of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups, and having a morphology (phase) Structure), the (a) polyetherimide resin forms a continuous phase (sea phase), and the (b) polyphenylene sulfide resin forms a dispersed phase (island phase) dispersed with a number average dispersed particle size of 1000 nm or less. A polyetherimide resin composition having a sea-island structure. (C) The polyetherimide resin composition according to claim 1, wherein the compound containing one or more isocyanate groups and / or the compound containing two or more epoxy groups is an isocyanate group-containing alkoxysilane. (B) The polyetherimide resin composition according to claim 1, wherein the number average dispersed particle size of the polyphenylene sulfide resin is 500 nm or less. Furthermore, (d) inorganic filler is mix | blended 0.0001-50 weight part with respect to a total of 100 weight part of said (a) polyetherimide resin and (b) polyphenylene sulfide resin, The any one of Claims 1-3 The polyetherimide resin composition described in 1. The tensile elongation (measured at a distance between chucks of 64 mm and a tensile speed of 10 mm / min according to ASTM D638 method) of ASTM No. 4 dumbbell molded pieces (thickness 1.6 mm) obtained by injection molding exceeds 40%. The polyetherimide resin composition according to any one of claims 1 to 4. The total of (a) and (b) is 100% by weight, with respect to 100 parts by weight of a resin composition comprising (a) a polyetherimide resin 99 to 60% by weight and (b) a polyphenylene sulfide resin 1 to 40% by weight. (C) a method for producing a polyetherimide resin composition comprising 0.1 to 10 parts by weight of a compound containing one or more isocyanate groups and / or a compound containing two or more epoxy groups, The polyether according to any one of claims 1 to 5, wherein the polyetherimide resin composition comprising (a), (b) and (c) is melt-kneaded and then melt-kneaded one or more times. A method for producing an imide resin composition. A molded article comprising the polyetherimide resin composition according to any one of claims 1 to 5.