JP2017031310A - Poly(ether imide-siloxane)copolymer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a poly(ether imide-siloxane)copolymer resin composition low in an elastic modulus, flexible, expressing a high extensibility, further excellent in thermal aging resistance and continuously usable at high temperature.SOLUTION: There is provided a poly(ether imide-siloxane)copolymer resin composition, which is obtained by blending (c) a silane coupling agent of 0.1 to 10 pts.wt. having one or more kinds of groups selected from an epoxy group, an amino group and an isocyanate group to 100 pts.wt. of a resin composition made of (a) a poly(ether imido-siloxane)copolymer of 99 to 51 wt.% and (b) a polyphenylene sulfide resin of 1 to 49 wt.%, with the total of (a) and (b) as 100 wt%. Upon observation of the cross-section of a molding made of the resin composition by a transmission electron microscope, (a) the poly(ether imido-siloxane)copolymer forms a continuous phase (sea phase), (b) the polyphenylene sulfide resin forms a dispersion phase (island phase), and, in the dispersion phase (island phase), the area of the dispersion phase in which the ratio obtained by dividing the major axis with the minor axis is 2.8 or higher is 4% or higher of the whole area.SELECTED DRAWING: None

Description

  The present invention relates to a poly (ether imide-siloxane) copolymer resin composition that is excellent in heat aging resistance and can be continuously used at a high temperature while being flexible with a low elastic modulus.

  Poly (ether imide-siloxane) copolymer resin has excellent properties such as flexibility, flame retardancy, processability, and low specific gravity compared to fluororesin, so it needs special flexibility such as various electric wires and tubes. It is used as an extrusion application. However, due to the low glass transition temperature compared to polyether imide, etc., it cannot be used continuously for a long period of time, such as around the engine of automobiles, reaching a high temperature of around 200 ° C, and it has poor chemical resistance. was there.

  On the other hand, polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has excellent properties as engineering plastics such as excellent heat resistance, chemical resistance, flame retardancy, electrical insulation and moisture and heat resistance. Widely used in electrical / electronic parts, communication equipment parts, automobile parts, etc. However, since there are relatively hard and brittle weaknesses, many improvements have been reported so far by blending an elastomer with a PPS resin to impart flexibility, but sufficient flexibility has been limited. In addition, the heat resistance and chemical resistance inherent in the PPS resin are sacrificed due to the elastomer, and there are other disadvantages that cause new problems such as significant deterioration in mechanical properties after high-temperature heat treatment.

  Thus, some attempts have been reported to incorporate a PPS resin into a poly (etherimide-siloxane) copolymer. For example, Patent Document 1 discloses a polymer blend composed of a poly (imide-siloxane) block copolymer and an engineering thermoplastic such as polyetherimide and polysulfone. Patent Document 2 reports a resin composition with improved compatibility comprising a polyetherimide resin and a polyphenylene sulfide resin not copolymerized with polyorganosiloxane. Patent Document 3 discloses a resin composition comprising a polyphenylene sulfide resin and a poly (etherimide-siloxane) copolymer, and the blending ratio of the polyphenylene sulfide resin is larger than that of the poly (etherimide-siloxane) copolymer. A resin composition is disclosed. Patent Document 4 discloses a resin composition comprising a polyetherimide resin not copolymerized with a polyorganosiloxane and a polyphenylene sulfide resin, in which the polyphenylene sulfide resin is dispersed with a number average dispersed particle size of 1000 nm or less.

JP-A 63-199737 JP-A-5-86293 JP 2012-46721 A JP 2009-46641 A

  However, the resin compositions described in Patent Documents 1 to 4 have a problem that sufficient flexibility and heat aging resistance cannot be imparted.

  The present invention is a relatively high use environment temperature that has been difficult in the past due to its low glass transition temperature without impairing the characteristics of the poly (ether imide-siloxane) copolymer that are flexible but excellent in heat aging resistance. However, an object is to provide a poly (ether imide-siloxane) copolymer resin composition that can be used continuously.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that the polyphenylene sulfide resin is dispersed as a dispersed phase in a continuous phase composed of a poly (ether imide-siloxane) copolymer, and is not spherical. The presence of a certain amount or more of a polyphenylene sulfide dispersed phase that exists as a specific ellipsoid or spheroid makes it possible to simultaneously achieve flexibility, excellent heat aging resistance, and high continuous use temperature, which were difficult in the past. The headline, the present invention has been reached.

That is, the present invention is as follows.
1. A resin composition comprising (a) 99 to 51% by weight of a poly (ether imide-siloxane) copolymer and (b) 1 to 49% by weight of a polyphenylene sulfide resin, where the total of (a) and (b) is 100% by weight. Poly (ether imide-siloxane) obtained by blending 0.1 to 10 parts by weight of a silane coupling agent having one or more groups selected from (c) an epoxy group, an amino group and an isocyanate group with respect to 100 parts by weight When the cross section of a molded product made of the resin composition is observed with a transmission electron microscope, the (a) poly (ether imide-siloxane) copolymer is a continuous phase (sea (B) a dispersion in which the polyphenylene sulfide resin forms a dispersed phase (island phase), and the ratio of the major axis divided by the minor axis in the dispersed phase (island phase) is 2.8 or more. Phase Poly wherein the product is at least 4% of the total area (etherimide - siloxane) copolymer resin composition,
2. 2. The poly (ether imide-siloxane) copolymer resin composition according to 1, wherein the (a) poly (ether imide-siloxane) copolymer is 80 to 60% by weight,
3. The poly (ether imide-siloxane) copolymer resin composition according to any one of 1 and 2, wherein the (c) silane coupling agent contains an epoxy group,
4). It further comprises (d) 1-50 parts by weight of an olefin-based elastomer with respect to a total of 100 parts by weight of the (a) poly (etherimide-siloxane) copolymer and the (b) polyphenylene sulfide resin. The poly (ether imide-siloxane) copolymer resin composition according to any one of 1 to 3,
5. A method for producing a poly (ether imide-siloxane) copolymer resin composition according to any one of 1 to 4, wherein the ratio L / D of the screw length L to the screw diameter D is 20 or more, And a poly (ether imide-siloxane) copolymer resin composition characterized by being melt kneaded using a twin screw extruder comprising a stirring screw having a notch in 5 to 20% of the screw length L Manufacturing method,
6.1 A molded product comprising the poly (ether imide-siloxane) copolymer resin composition according to any one of 1 to 4,
It is.

  According to the present invention, it is possible to obtain a poly (ether imide-siloxane) copolymer resin composition that has a low elastic modulus and is flexible, has excellent heat aging resistance, and can be used continuously at a higher temperature than before. . These characteristics enable the development of various parts around automobile engines that reach high temperatures up to around 200 ° C.

It is a schematic diagram when the cross section of the molded article which consists of a resin composition of this invention is observed with the transmission electron microscope.

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

(A) Poly (ether imide-siloxane) copolymer The poly (ether imide-siloxane) copolymer used in the present invention is a generally known copolymer comprising a polyether imide repeating unit and a polysiloxane repeating unit. A polymer is mentioned. Preferably, it consists of a repeating unit represented by the following structural formula (Chemical Formula 1) and a repeating unit represented by the following structural formula (Chemical Formula 6).

  Note that T in the above structural formulas (Chemical Formulas 1 and 2) is —O— or —O—Z—O—, and the divalent bonds are 3, 3′-, 3, 4′-, 4 , 3′-, 4,4′-position, and Z is composed of a divalent group represented by the following structural formula (Formula 3) and a divalent group represented by the following structural formula (Formula 4). Selected from the group.

X in the structural formula (Formula 4) is selected from the group consisting of a C _1-5 alkylene group or a halogenated derivative thereof, —CO—, —SO ₂ —, —O—, and —S—.

R in the above structural formulas (Chemical Formula 1, Chemical Formula 2) is an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, an alkylene group having 2 to 20 carbon atoms, 3 to 20 A divalent organic group selected from the group consisting of a cycloalkylene group having one carbon atom and a group represented by the following structural formula (Formula 5). Here, Q is selected from the group consisting of a C _1-5 alkylene group or a halogenated derivative thereof, —CO—, —SO ₂ —, —O—, —S—.

M and n in the above structural formula (Formula 2) are each an integer of 1 to 10, and g is an integer of 1 to 40.

  Particularly preferably, the structure represented by the structural formula (Chemical Formulas 1 and 2) further contains a repeating unit represented by the following structural formula (Chemical Formula 6).

  M in the structural formula (Chemical Formula 6) is selected from the group represented by the following structural formula (Chemical Formula 7) (B in the formula is —S— or —CO—), and R ′ is defined above. It is the same as R or a divalent group represented by the following structural formula (Formula 8) (wherein m and n are each an integer of 1 to 10, and g is an integer of 1 to 40). .

  As a manufacturing method of the above-mentioned poly (ether imide-siloxane) copolymer, aromatic bis (ether anhydride) represented by the following structural formula (Chemical Formula 9) and organic diamine represented by the following structural formula (Chemical Formula 10) In a known method for producing a polyetherimide from the above, it is produced by replacing a part or all of the organic diamine of the above structural formula (Chemical Formula 10) with an amine-terminated organosiloxane represented by the following structural formula (Chemical Formula 11). .

  T in the structural formula (Chemical Formula 9), R in the structural formula (Chemical Formula 10), and n, m, and g in the structural formula (Chemical Formula 11) are the same as those defined above.

  The poly (ether imide-siloxane) copolymer used in the present invention may be a random copolymer, an alternating copolymer, or a block copolymer, but the block copolymer is particularly flexible and exhibits excellent toughness. This is preferable. Examples of the poly (ether imide-siloxane) block copolymer include chemical structures represented by the following structural formula (Formula 10).

Here, a in the structural formula (Chemical Formula 12) is an integer of 1 to 10,000, n is an integer of 1 to 50, m is an integer of 2 to 40, and R ₁ is a tetravalent aromatic group having the following structure. It is selected from the formula (Formula 13).

T in the above formula (Chem. 13) is a C _1-5 alkylene group or a halogenated derivative thereof, —CO—, —SO ₂ —, —O—, —S—, and —O—Z—O—. Selected from divalent groups. Z is the same as described above.

R ₂ is the same as R described above.

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

  As a method for producing the poly (ether imide-siloxane) block copolymer described above, a hydroxyl group-terminated polyimide oligomer having the following structural formula (Chemical Formula 14) is reacted with a siloxane oligomer having the following structural formula (Chemical Formula 15) under etherification conditions. A well-known method can be illustrated.

However, n, m, and R _{1 to} R ₄ are as defined above. Further, x in the structural formula (Chemical Formula 15) is a halogen or dialkylamino which can be substituted by a reaction with a hydroxyl group in the hydroxyl group-terminated polyetherimide oligomer of the structural formula (Chemical Formula 14) to form an ether bond. Group, acyl group, alkoxy group and hydrogen atom.

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

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

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

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula is preferred. In addition, (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.

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

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

  Although the manufacturing method of (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. 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]
(B) The PPS resin may be subjected to acid treatment, hot water treatment, washing with an organic solvent, alkali metal or alkaline earth metal treatment after being produced through the above polymerization and recovery steps.

  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 desirably 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 / 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 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.

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

  In the present invention, from the viewpoint of obtaining a poly (ether imide-siloxane) copolymer resin composition excellent in toughness and heat aging resistance, organic solvent cleaning and warm water of about 80 ° C. or hot water cleaning are repeated several times. After removing residual oligomers and residual salts, an acid treatment or a treatment with an alkali metal salt or an alkaline earth metal salt is preferred, and a treatment with an alkali metal salt or an alkaline earth metal salt is particularly preferred.

  The poly (ether imide-siloxane) copolymer resin composition of the present invention is extremely flexible and excellent in toughness, and retains high mechanical properties even after being exposed for a long time under high temperature conditions. In order to express such characteristics, the total amount of (b) alkali metal and / or alkaline earth metal contained in the PPS resin is preferably 200 ppm or more, more preferably 500 ppm or more, and further 700 ppm. The above is preferable.

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

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

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

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

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

(C) Silane coupling agent having one or more groups selected from an epoxy group, an amino group, and an isocyanate group In the present invention, a poly (ether imide-siloxane) copolymer having greatly improved toughness and heat aging resistance. In order to obtain a resin composition, it is necessary to add (c) a silane coupling agent having one or more groups selected from an epoxy group, an amino group, and an isocyanate group as a compatibilizing agent. However, the compatibilizer mentioned here does not include (d) an olefin-based elastomer containing a reactive functional group described later.

  Examples of the silane coupling agent having an epoxy group include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Examples thereof include alkoxysilane compounds.

  Examples of the silane coupling agent having an amino group include γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. .

  Examples of the silane coupling agent having an isocyanate group include γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylethyldimethoxy. Examples include silane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, and the like.

  Among them, in order to achieve excellent toughness and heat aging resistance, a silane coupling agent having an isocyanate group or an epoxy group is preferable, and further, a silane coupling agent having an epoxy group has a high elongation. This is more preferable.

(D) Olefin Elastomer The (d) olefin elastomer used in the present invention may be either an olefin polymer or an olefin copolymer.

Examples of olefin polymers or copolymers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 dimethyl-1-hexene, 4,4 dimethyl-1-pentene, 4-ethyl-1-hexene, Α-Oleph such as 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene Polymers obtained by polymerizing single or two or more kinds, such as α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Copolymers of α, β-unsaturated carboxylic acids and alkyl esters thereof, and the like. Among them, ethylene / α-olefin copolymer obtained by copolymerizing ethylene and α-olefin having 3 to 20 carbon atoms The coalescence is preferable in terms of imparting excellent flexibility and high toughness.
Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 -Hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof To be mentioned. Among these α-olefins, copolymers using α-olefins having 4 to 12 carbon atoms are even more preferable.

  In addition, an olefin polymer or copolymer containing a reactive functional group is also included.

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

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

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

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

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

  The α, β-unsaturated carboxylic acid glycidyl ester is

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

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

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

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

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

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

  The blending ratio of (a) poly (etherimide-siloxane) copolymer and (b) PPS resin in the poly (etherimide-siloxane) copolymer resin composition of the present invention is the ratio of (a) and (b). When the total is 100% by weight, (b) the PPS resin needs to be 1 to 49% by weight with respect to 99 to 51% by weight of the poly (ether imide-siloxane) copolymer. (A) When the poly (ether imide-siloxane) copolymer is less than 51% by weight, sufficient flexibility and toughness are not exhibited, and heat aging resistance is remarkably lowered. (A) As a more preferable blending amount of the poly (ether imide-siloxane) copolymer, 90 to 55% by weight is mentioned from the viewpoint of not only flexibility and toughness, but also excellent heat aging resistance. 80 to 60% by weight is more preferable, and 75 to 65% by weight is most preferable from the viewpoint of improving the temperature at which continuous use is possible.

  In addition, the poly (ether imide-siloxane) copolymer resin composition of the present invention includes (a) a poly (ether imide-siloxane) copolymer and (b) a total of 100 parts by weight of the PPS resin. c) It is necessary to mix | blend 0.1-10 weight part of silane coupling agents which have 1 or more types of groups chosen from an epoxy group, an amino group, and an isocyanate group. (C) When the silane coupling agent is less than 0.1 part by weight, sufficient compatibilization does not proceed and the interfacial adhesion is lowered. As a result, excellent toughness is hardly exhibited. On the other hand, if it exceeds 10 parts by weight, the melt viscosity is remarkably increased, resulting in a decrease in molding processability. (C) The preferable compounding quantity of a silane coupling agent is 0.2-5 weight part, 0.4-3 weight part is more preferable, and 0.6-2 weight part can be illustrated as a still more preferable range.

  Furthermore, the poly (ether imide-siloxane) copolymer resin composition of the present invention has (a) a poly (ether imide-siloxane) copolymer and (b) PPS for the purpose of imparting further excellent flexibility. It is also preferable to blend 1 to 50 parts by weight of (d) the olefin elastomer with respect to 100 parts by weight of the total resin. (D) The more preferable compounding quantity of an olefin type elastomer is 5-40 weight part, and 10-30 weight part is the most preferable.

  The poly (ether imide-siloxane) copolymer resin composition of the present invention is obtained by observing the cross section of a molded article comprising the poly (ether imide-siloxane) copolymer with a transmission electron microscope. The continuous phase (sea phase) is a dispersed phase in which the (b) PPS resin forms a dispersed phase (island phase) and the ratio of the major axis divided by the minor axis is 2.8 or more. Must be 4% or more of the total area. Thus, when the ratio of the (b) PPS resin that is elongated and dispersed in an ellipsoid or spheroid rather than spherical shape becomes a certain amount or more, the blending amount of (b) PPS resin is relatively at least ( a) The continuous usable temperature can be improved up to a region exceeding the glass transition temperature of the poly (ether imide-siloxane) copolymer. Here, (b) the major axis and the minor axis of the disperse phase composed of the PPS resin are the cross sections of the molded product composed of the poly (ether imide-siloxane) copolymer resin composition of the present invention, as shown in FIG. When observed with a transmission electron microscope, (b) the maximum diameter of the dispersed phase made of PPS resin is defined as the major axis, and the largest diameter among the diameters orthogonal to the major axis is defined as the minor axis. The ratio obtained by dividing the major axis of the (b) PPS resin dispersed phase by the minor axis is more preferably 3.2 or more, and still more preferably 4.0 or more. In addition, among the (b) PPS resin dispersed phases, the area ratio of the dispersed phase in which the ratio of the major axis divided by the minor axis is 2.8 or more is preferably 5% or more, preferably 10% or more with respect to the total photographing area. Is more preferable, and 15% or more is still more preferable. The upper limit of the area ratio of the dispersed phase in which the ratio of the major axis divided by the minor axis in the (b) PPS resin dispersed phase is 2.8 or more is not particularly limited, but is preferably 40% or less, more preferably 30% or less. It can be illustrated as a preferred range.

  In addition, the area ratio of the dispersed phase in which the ratio of the major axis divided by the minor axis is 2.8 or more in the (b) PPS resin dispersed phase can be obtained by the following method. First, about the pellet or molded article of the poly (ether imide-siloxane) copolymer resin composition of the present invention, a thin piece of 0.1 μm or less from the center is cut in the cross-sectional area direction, and then 1000 to 1000 using a transmission electron microscope. The phase structure is photographed at a magnification of about 5000 times. Next, for the 100 or more dispersed particles of (b) PPS resin in the photograph, a ratio obtained by dividing the major axis by the minor axis is calculated. And it can obtain | require by calculating the 100 fraction which divided the sum total of the area part of the disperse phase whose ratio is 2.8 or more by the total imaging area.

  The poly (ether imide-siloxane) copolymer resin composition of the present invention is excellent in heat aging resistance without impairing the toughness and flexibility inherent in the poly (ether imide-siloxane) copolymer, and is continuously used. The temperature is improved. The term “flexibility” as used herein refers to the bending when a bending test piece of (length) 125 mm × (width) 12 mm × (thickness) 6 mm is measured under the conditions of a distance between tests of 100 mm and a crosshead speed of 3 mm / min. It can be quantified by the elastic modulus. The flexural modulus is preferably 1.5 GPa or less, more preferably 1.2 GPa or less, and even more preferably 0.7 GPa or less.

  The toughness as used herein can be quantified by the tensile elongation at break when an ASTM No. 1 dumbbell test piece is measured under the conditions of a distance between tests of 100 mm and a crosshead speed of 10 mm / min. The tensile elongation is preferably 40% or more, more preferably 60% or more, and still more preferably 100% or more.

  Moreover, heat aging resistance said here is 100 fraction which remove | divided the tensile breaking elongation of the ASTM No. 1 dumbbell test piece after processing for 500 hours or more at 150-200 degreeC in air by the tensile breaking elongation before a process. The tensile elongation retention rate defined by The tensile break elongation of the ASTM No. 1 dumbbell test piece after being treated at 150 to 200 ° C. in air for 500 hours or more is preferably 40% or more, more preferably 60% or more, and further preferably 80% or more. The tensile rupture elongation retention is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more. In addition, about the measuring method of tensile fracture elongation, it conforms to the quantitative determination method of toughness mentioned above.

Production method of poly (ether imide-siloxane) copolymer resin composition As a method of producing the poly (ether imide-siloxane) copolymer resin composition of the present invention, production in a molten state or production in a solution state However, from the viewpoint of simplicity, production in a molten state can be preferably used. For production in a molten state, melt kneading with an extruder, melt kneading with a kneader, or the like can be used. From the viewpoint of productivity, melt kneading with an extruder that can be continuously produced can be preferably used. For melt kneading by an extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improvement in productivity, reactivity, and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt kneading with a twin-screw extruder is most preferable.

  A more specific method for producing the poly (ether imide-siloxane) copolymer resin composition of the present invention is not necessarily limited to this, but (a) a poly (ether imide-siloxane) copolymer, (b As a representative example, a method of supplying a PPS resin and (c) a silane coupling agent to a twin-screw extruder and melt-kneading at a processing temperature of (b) the melting point of the PPS resin +5 to 100 ° C. can be given as a representative example. . Among them, (b) among the PPS resin dispersed phases, in order to increase the area ratio of the dispersed phase having a ratio of the major axis divided by the minor axis of 2.8 or more to 4% or more, the number of kneading may be repeated three or more times. It can be illustrated as a more preferable method.

  In order to refine the number average dispersed particle size of (b) PPS resin and (d) olefin-based elastomer, it is preferable to make the shearing force relatively strong. In the screw arrangement configuration of the twin screw extruder, the kneading part Is more preferably 3 or more, more preferably 4 or more kneading portions. The upper limit of the kneading portion may vary depending on the length of the kneading portion per location and the interval between the kneading portions, but is preferably 10 or less, and more preferably 8 or less. Moreover, the ratio of the total length of the kneading part with respect to the screw full length of an extruder has the preferable range of 10-60%, More preferably, it is 15-55%, Furthermore, the range of 20-50% is preferable.

  L / D, which is the ratio between the screw length L and the screw diameter D of the twin screw extruder, is desirably 20 or more, more preferably 30 or more, and further preferably 40 or more. The upper limit of L / D of a twin screw extruder is usually 60. As the peripheral speed at this time, a range of 15 to 100 m / min is selected, and 20 to 80 m / min is more preferably selected. When the L / D of the twin-screw extruder is less than 20, the kneading part is insufficient, so that (b) the dispersibility of the PPS resin and (d) the olefin elastomer is reduced, and (b) the PPS resin dispersed phase Of these, it is difficult to make the area of the dispersed phase having a ratio of the major axis divided by the minor axis of 2.8 or more 4% or more.

  Furthermore, a method of melt kneading by setting a screw arrangement incorporating a stirring screw having a notch can also be exemplified as a preferred method. Here, the “notch” means that a part of the mountain portion of the screw flight is cut away. A stir screw with a notch can increase the resin filling rate and, unlike conventional kneading methods for grinding resin, it not only suppresses resin decomposition due to heat generation, but also stirs and stirs. However, it is easy to increase the area ratio of the dispersed phase in which the ratio of the major axis divided by the minor axis is 2.8 or more to 4% or more by passing through the notch.

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

  Moreover, it is preferable that the ratio of the total length of the stirring screw part which has a notch part with respect to the screw full length of an extruder is 5 to 20% of the said screw length L, and is 10 to 15%. Is more preferable.

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

  The mixing order of the raw materials is not particularly limited, and a method in which all the raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and melt-kneaded by the above method, and this and the remaining raw materials are further blended and melt-kneaded Any method may be used, such as a method of mixing a part of raw materials, or a method of mixing the remaining raw materials using a side feeder during melt kneading with a twin-screw extruder.

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

Inorganic filler Although not an essential component, the poly (ether imide-siloxane) copolymer resin composition of the present invention can be used by blending an inorganic filler as long as the effects of the present invention are not impaired. Specific examples of such inorganic fillers include glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber. , Ceramic filler, asbestos fiber, stone fiber, metal fiber, etc., or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina Silicates such as silicates, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfuric acid Sulfates such as lucium and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite Non-fibrous fillers such as glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of the anticorrosive material and the lubricant. These inorganic fillers may be hollow, and two or more kinds may be used in combination. Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the anticorrosive material, the lubricant, and the effect of imparting conductivity.

  The blending amount of the inorganic filler is selected within a range of 30 parts by weight or less with respect to a total of 100 parts by weight of (a) poly (ether imide-siloxane) copolymer and (b) PPS resin, and less than 10 parts by weight. The range is preferable, the range of less than 1 part by weight is more preferable, and the range of 0.8 part by weight or less is still more preferable. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. While the blending of the inorganic filler is effective for improving the elastic modulus of the material, a large amount of blending exceeding 30 parts by weight is not preferable because it causes a large decrease in toughness. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

Other Additives Further, the poly (ether imide-siloxane) copolymer resin composition of the present invention contains (b) a resin other than the PPS resin and (d) an olefin-based elastomer within a range not impairing the effects of the present invention. You may add and mix. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, polyether imide resins, polyether sulfone resins, polyamide imide resins, and tetrafluoropolyethylene resins.

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

  The poly (ether imide-siloxane) copolymer resin composition of the present invention can be molded by various molding methods such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, among others, injection molding and extrusion. Useful for molding applications. In addition, the poly (ether imide-siloxane) copolymer resin composition of the present invention is flexible and extremely excellent in tensile rupture elongation, and is also excellent in heat aging resistance. It is also useful for long extrusion applications.

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

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

[injection molding]
Using a Sumitomo Heavy Industries injection molding machine SE75-DUZ, under the conditions of a resin temperature of 320 ° C. and a mold temperature of 150 ° C., an ASTM No. 1 dumbbell test piece and (length) 125 mm × (width) 12 mm × (thickness) A 6 mm bending test piece was formed.

[Phase structure observation]
The central part of the injection-molded ASTM No. 1 dumbbell test piece was cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less was cut from the central part of the cross section at −20 ° C. This is magnified 1000 to 5000 times with a H-7100 type transmission electron microscope (resolution (particle image) 0.38 nm, magnification 500 to 600,000 times) manufactured by Hitachi, Ltd., and the phase structure is formed. confirmed.

  Each of (a) poly (etherimide-siloxane) copolymer, (b) PPS resin, and (d) olefin elastomer is distinguished from each other by (a) poly (etherimide-siloxane) copolymer and (b) PPS resin. The composition comprising only (a) poly (ether imide-siloxane) copolymer and (d) the olefin-based elastomer was judged from the contrast when the phase structure was observed in the same manner as described above.

  (B) Of the PPS resin dispersed phase, the area ratio of the dispersed phase having a value obtained by dividing the major axis by the minor axis is 2.8 or more was estimated by the following method. That is, as described above, for 100 or more (b) PPS resin-derived dispersed particles in an arbitrary photograph in which the phase structure was observed, select dispersed particles having a value obtained by dividing the major axis by the minor axis is 2.8 or more. After that, the total of the area portion was calculated as a 100 fraction divided by the total area taken.

[Dry heat treatment]
The ASTM No. 1 dumbbell test piece and the bending test piece obtained by injection molding are put in a gear oven set at 170 ° C., treated for 700 hours, allowed to cool at room temperature for 24 hours or more, visually checked, and placed on a micrometer. Then, the thickness and width of the test piece were measured to confirm whether there was any deformation or shrinkage.

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

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

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

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

[Reference Example 2] Polyetherimide (a) ′-1 not copolymerized with siloxane
A commercially available polyetherimide ("ULTEM 1010" manufactured by SABIC Innovative Plastics) was used. The glass transition temperature was 217 ° C.

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

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

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

[Reference Example 4] Silane coupling agent (c) -1
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent having an epoxy group.

[Reference Example 5] Silane coupling agent (c) -2
As a silane coupling agent having an isocyanate group, 3-isocyanatopropyltriethoxysilane (Shin-Etsu Chemical KBE9007) was used.

[Reference Example 6] Olefin Elastomer (d) -1
An ethylene / glycidyl methacrylate / methyl acrylate copolymer (Sumitomo Chemical “Bond First” 7M, ethylene: glycidyl methacrylate: methyl acrylate = 67 wt%: 6 wt%: 27%) was used.

[Examples 1-2, 4]
(A) Poly (ether imide-siloxane) copolymer shown in Table 1, (b) PPS resin, and (c) silane coupling agent were dry blended in the ratio shown in Table 1, and then a vacuum vent was provided. Using a TEX30α twin screw extruder manufactured by Nippon Steel (L / D = 45, 5 kneading parts, 10% ratio of screw with notch to screw length L), and dicing at a screw speed of 300 rpm The cylinder temperature was set so that the resin exit temperature would be 330 ° C. or lower, and the mixture was melt-kneaded and pelletized with a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Example 3]
(A) Poly (ether imide-siloxane) copolymer shown in Table 1, (b) PPS resin, and (c) silane coupling agent were dry blended in the ratio shown in Table 1, and then a vacuum vent was provided. Using a TEX30α twin screw extruder manufactured by Nippon Steel (L / D = 45, 5 kneading parts, 15% ratio of screw with notch to screw length L), die at a screw speed of 300 rpm The cylinder temperature was set so that the resin exit temperature would be 330 ° C. or lower, and the mixture was melt-kneaded and pelletized with a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Example 5]
(A) Poly (ether imide-siloxane) copolymer shown in Table 1, (b) PPS resin, and (c) silane coupling agent were dry blended in the ratio shown in Table 1, and then a vacuum vent was provided. Using a TEX30α twin screw extruder manufactured by Nippon Steel (L / D = 45, kneading part: 5 points, ratio of screw having notch to screw length L: 0%), at a screw rotation speed of 300 rpm, die The cylinder temperature was set so that the resin exit temperature would be 330 ° C. or lower, and the mixture was melt-kneaded and pelletized with a strand cutter. This operation was further repeated twice to obtain a pellet that was melt-kneaded three times in total. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Example 6]
(A) Poly (ether imide-siloxane) copolymer shown in Table 1, (b) PPS resin, (c) silane coupling agent, and (d) olefin-based elastomer were dry blended in the ratio shown in Table 1. After that, using a TEX30α type twin screw extruder (L / D = 45, kneading part 5 locations, ratio of screw having notch to screw length L 10%) manufactured by Nippon Steel Works equipped with vacuum vent, screw At a rotation speed of 300 rpm, the cylinder temperature was set so that the die removal resin temperature would be 330 ° C. or less, melt kneading, and pelletized by a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Comparative Example 1]
Only (a) poly (ether imide-siloxane) copolymer shown in Table 1 was prepared by using a TEX30α type twin screw extruder (L / D = 45, kneading part 5 locations, screw length) provided with a vacuum vent. The ratio of the screw having a notch with respect to the length L is 10%), the screw temperature is 300 rpm, the die temperature is set to a temperature of 250 ° C. or less, the melt temperature is kneaded, and the pellet is pelletized by a strand cutter. Turned into. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Comparative Example 2]
The mixture was melt-kneaded in the same manner as in Examples 3 and 4 except that the ratio of the screw having a notch to the screw length L of the twin-screw extruder was 0%, and pelletized with a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Comparative Example 3]
Except for the screw rotation speed of the twin screw extruder being 450 rpm, the mixture was melt kneaded in the same manner as in Comparative Example 2 and pelletized with a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Comparative Example 4]
(A) Instead of the poly (ether imide-siloxane) copolymer, melt kneading was performed in the same manner as in Example 4 except that a polyether imide not copolymerized with siloxane was used, and pelletized with a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The results were as shown in Table 1.

[Comparative Example 5]
(A) 20% by weight of a poly (ether imide-siloxane) copolymer, (b) 80% by weight of a PPS resin, and (c) 8 parts by weight of a silane coupling agent, and then Nippon Steel Corporation equipped with a vacuum vent. Using a TEX30α type twin screw extruder (L / D = 45, 5 kneading parts, 0% ratio of screw with notch to screw length L), at a screw rotation speed of 300 rpm, a die discharging resin The cylinder temperature was set so that the temperature would be 330 ° C. or less, and the mixture was melt-kneaded and pelletized with a strand cutter.

Next, (a) a poly (ether imide-siloxane) copolymer was added to the obtained pellets, diluted 4 times, dry blended, melt-kneaded under the same conditions, and pelletized with a strand cutter. The pellets dried at 130 ° C. overnight were subjected to injection molding, and the phase separation structure of the molded pieces, the tensile breaking elongation before and after the heat treatment, the tensile breaking elongation retention rate, the bending elastic modulus, and the specimen shape were evaluated. The final composition and evaluation results of the resin composition were as shown in Table 1.
The results of the above examples and comparative examples will be compared and described.

In Examples 1 and 2, (b) of the PPS resin dispersed phases, the area ratio of the dispersed phase having a major axis / minor axis ratio of 2.8 or more was 19 and 18%, respectively, and 170 ° C. × 700 hr after heat treatment No deformation was observed in the specimen shape. Moreover, the tensile elongation retention before and after the heat treatment was very high, and it was a material that could withstand continuous use at high temperatures.
In Example 4, the area ratio of the disperse phase in which the ratio of major axis / minor axis is 2.8 or more in the (b) PPS resin dispersed phase is 6%, and there are few test pieces after heat treatment at 170 ° C. × 700 hr. Although warpage occurred, there was no significant deformation, and the tensile elongation retention before and after heat treatment was also high.
In Example 3, as compared with Example 4, the ratio of the notched screw was increased from 10% to 15% with respect to the screw length L, whereby (b) the long diameter / short diameter of the PPS resin dispersed phase was increased. The area ratio of the dispersed phase having a diameter ratio of 2.8 or more also increased from 6% to 10%, and no warpage or deformation was observed in the test piece after heat treatment at 170 ° C. × 700 hours. Moreover, the tensile elongation retention before and after the heat treatment was also high.

In Example 5, unlike Examples 3 and 4, it was melt-kneaded without providing a notch screw, but by performing melt-kneading a total of 3 times, (b) the major axis / minor axis of the PPS resin dispersed phase. The area ratio of the dispersed phase having a ratio of 2.8 or more was 5%, and the test piece after heat treatment at 170 ° C. × 700 hours had only slight warpage.
In Example 6, (d) an olefin elastomer was further blended. As a result, even if the blending proportion of (b) PPS resin is increased as compared with Examples 1 to 5, a tensile material having a low tensile elasticity and a flexible material can be obtained, and deformation of the test piece after heat treatment at 170 ° C. × 700 hr. The tensile elongation retention was also high.

  On the other hand, in Comparative Example 1, (a) only a poly (ether imide-siloxane) copolymer was melt-kneaded in the same manner as in Example 1. As a result, the tensile elongation before heat treatment was high, and the tensile modulus was the smallest and the soft material. However, the test piece after heat treatment at 170 ° C. × 700 hr was significantly shrunk and deformed, and it was no longer possible to perform a tensile test and a bending test, and the practicality was poor.

  In Comparative Example 2, unlike Examples 3 and 4, as a result of not providing any notch screw, (b) Among the PPS resin dispersed phases, the dispersed phase having a major axis / minor axis ratio of 2.8 or more The area ratio was less than 4%. For this reason, the test piece after heat treatment at 170 ° C. × 700 hours was significantly shrunk and deformed, and it was no longer possible to carry out a tensile test and a bending test, and the practicality was poor.

  In Comparative Example 3, as in Comparative Example 2, no notched screw was provided, but the screw rotation speed was increased. Even when such a method was adopted, the area ratio of the dispersed phase having a ratio of major axis / minor axis of 2.8 or more in the (b) PPS resin dispersed phase was less than 4%. For this reason, the test piece after heat treatment at 170 ° C. × 700 hours was significantly shrunk and deformed, and it was no longer possible to carry out a tensile test and a bending test, and the practicality was poor.

  In Comparative Example 4, unlike Example 4, polyether imide not copolymerized with siloxane was used. In this case, a tensile elastic modulus and a bending elastic modulus were high, and a material excellent in flexibility could not be obtained. Further, the tensile elongation after heat treatment at 170 ° C. × 700 hours was remarkably lowered, and the long-term durability was extremely poor.

  In Comparative Example 5, as in Comparative Example 4, a polyetherimide that was not copolymerized with siloxane was used, but after melt-kneading as PPS 80 wt% and polyetherimide 20 wt% in advance, while diluting with a large amount of polyetherimide Once again melt-kneaded, the same resin composition as in Comparative Example 4 was compounded. Even when such a method was adopted, among the (b) PPS resin dispersed phases, the area ratio of the dispersed phase having a major axis / minor axis ratio of 2.8 or more was less than 4%. The tensile modulus and flexural modulus were high and a material excellent in flexibility could not be obtained, and the tensile elongation after heat treatment at 170 ° C. × 700 hours was significantly reduced.

1 (a) poly (ether imide-siloxane) copolymer continuous phase 2 (b) PPS resin dispersed phase 3 major axis 4 minor axis

Claims (6)

A resin composition comprising (a) 99 to 51% by weight of a poly (ether imide-siloxane) copolymer and (b) 1 to 49% by weight of a polyphenylene sulfide resin, where the total of (a) and (b) is 100% by weight. Poly (ether imide-siloxane) obtained by blending 0.1 to 10 parts by weight of a silane coupling agent having one or more groups selected from (c) an epoxy group, an amino group and an isocyanate group with respect to 100 parts by weight When the cross section of a molded product made of the resin composition is observed with a transmission electron microscope, the (a) poly (ether imide-siloxane) copolymer is a continuous phase (sea (B) a dispersion in which the polyphenylene sulfide resin forms a dispersed phase (island phase), and the ratio of the major axis divided by the minor axis in the dispersed phase (island phase) is 2.8 or more. Phase Poly wherein the product is at least 4% of the total area (etherimide - siloxane) copolymer resin composition. 2. The poly (ether imide-siloxane) copolymer resin composition according to claim 1, wherein the (a) poly (ether imide-siloxane) copolymer is 80 to 60 wt%. The poly (ether imide-siloxane) copolymer resin composition according to claim 1, wherein the (c) silane coupling agent contains an epoxy group. It further comprises (d) 1-50 parts by weight of an olefin-based elastomer with respect to a total of 100 parts by weight of the (a) poly (etherimide-siloxane) copolymer and the (b) polyphenylene sulfide resin. The poly (ether imide siloxane) copolymer resin composition in any one of Claims 1-3. It is a manufacturing method of the poly (ether imide siloxane) copolymer resin composition in any one of Claims 1-4, Comprising: Ratio L / D of screw length L and screw diameter D is 20 or more, A poly (ether imide-siloxane) copolymer resin composition characterized by being melt kneaded using a twin screw extruder in which 5 to 20% of the screw length L is composed of a stirring screw having a notch Manufacturing method. A molded article comprising the poly (ether imide-siloxane) copolymer resin composition according to any one of claims 1 to 4.