JP5277513B2 - Thermoplastic resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent mechanical characteristics, for further detail, a thermoplastic resin composition having excellent chemical and wet heat resistances possessed by a polyphenylene sulfide resin and imparted thereto while maintaining excellent toughness possessed by a polyester resin. <P>SOLUTION: The thermoplastic resin composition comprises at least two components of thermoplastic resins. In the resin phase separated structure observed under an electron microscope in the thermoplastic resin composition, any one thermoplastic resin forms a continuous phase and the remainder thermoplastic resins form a dispersed phase. The dispersion particle diameter of the dispersed phase is 1-100 nm. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a thermoplastic resin composition having excellent mechanical properties. Further, as a preferred embodiment, the thermoplastic resin composition comprising a polyester resin and a polyphenylene sulfide resin has excellent mechanical properties, chemical resistance, hydrolysis resistance and molding processability obtained by having a specific dispersion structure. Is a thermoplastic resin composition.

  In recent years, resins are being used in many applications as an alternative to metal parts from the viewpoints of light weight, rust prevention, recyclability, and the like. Polyester resins typified by polyethylene terephthalate and polybutylene terephthalate are also used in various electrical / electronic parts, machine parts and automobile parts because of their excellent characteristics. However, polyester resins are not sufficiently resistant to gas and durable against chemicals, and various improvements have been studied. Polyester resins have a problem of poor hydrolysis resistance, and their use is often limited due to problems such as a decrease in mechanical strength at high temperatures and high humidity.

  On the other hand, polyphenylene sulfide (hereinafter abbreviated as PPS) resin has properties suitable for engineering plastics such as excellent heat resistance, barrier properties, chemical resistance, electrical insulation properties, and heat and humidity resistance, and is mainly used for injection molding. It is used for various electric / electronic parts, machine parts and automobile parts. However, PPS resin has lower toughness than other engineering plastics such as nylon and polyester resin, and its application is limited at present, and its improvement is strongly desired.

Patent Document 1 discloses means capable of complementing each defect by controlling the resin phase separation structure in the resin composition of the polyester resin and the PPS resin so that the PPS resin is in a band-like dispersion state. Even in this case, the toughness is not sufficient, and further improvement is required. Patent Document 2 discloses a method of controlling the resin phase separation structure in a fine order in a resin composition of a resin other than PPS resin and PPS. In this case, the two components are once uniformly mixed. The two components of the polyester resin and the PPS resin are not sufficient in practical use because of restrictions on molecular weight and the like, and further improvements are required.
JP 2002-69273 A (Claims) JP 2003-113307 A (Claims)

  An object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties. In particular, in a thermoplastic resin composition comprising a polyester resin and a PPS resin, a thermoplastic resin composition having the excellent chemical resistance and wet heat resistance of the PPS resin while maintaining the excellent toughness of the polyester resin is obtained. This is a problem.

  As a result of investigations to solve the above problems, the present inventors have identified a thermoplastic resin that forms a specific resin phase separation structure and is dispersed in a thermoplastic resin composition composed of at least two thermoplastic resins. The present inventors have found that the above-mentioned problems can be solved by dispersing with a dispersed particle size, and that remarkable effects can be obtained in mechanical properties, chemical resistance, hydrolysis resistance, moldability and the like, and the present invention has been achieved.

That is, the present invention comprises the following items.
(1) Heat of at least two components comprising any combination selected from polyester resin and polyphenylene sulfide resin, polyester resin and polyetherimide resin, polyester resin and polyolefin resin, polyester resin and polyamide resin, and polyester resin and polycarbonate resin A thermoplastic resin composition containing a thermoplastic resin, wherein in the resin phase separation structure observed with an electron microscope in the thermoplastic resin composition, any one thermoplastic resin serves as a continuous phase and the remaining thermoplastic resin. resin forms a dispersed phase, the dispersed phase Ri dispersed particle diameter der of 1 to 100 nm, the thickness of the interfacial phase of the thermoplastic resin forming the dispersed phase, characterized in 30~70nm der Rukoto heat A plastic resin composition,
(2) The at least two thermoplastic resins have different melting points, and the thermoplastic resin composition is melted and retained for 5 minutes at a temperature between the melting point of one thermoplastic resin having a high melting point and the melting point + 30 ° C. (1) The thermoplastic resin composition according to (1), wherein the dispersed phase in the resin composition cooled in (1) has a dispersed particle diameter of 1 to 100 nm ,
(3) pre-Symbol least two components of the thermoplastic resin is a polyester resin (a) and polyphenylene sulfide resin (b), a polyester resin (a) and polyphenylene sulfide resin (b) a polyester resin total of 100 wt% ( a) a thermoplastic resin composition comprising 50 to 99% by weight of polyphenylene sulfide resin (b) and 50 to 1% by weight of a polyester in a resin phase separation structure observed with an electron microscope in the thermoplastic resin composition The thermoplastic resin composition according to (1) or (2) , wherein the resin (a) forms a continuous phase and the polyphenylene sulfide resin (b) is a dispersed phase,
( 4 ) The thermoplastic resin composition according to ( 3 ), wherein the polyester resin (a) is 70 to 95% by weight and the polyphenylene sulfide resin (b) is 30 to 5% by weight,
(5) Po Riesuteru resin (a), a polyphenylene sulfide resin (b) a thermoplastic resin composition containing the polyether imide resin (g), the polyester resin (a), polyphenylene sulfide resin (b) and poly Polyester resin (a) 50 to 98.5% by weight, polyphenylene sulfide resin (b) 30 to 1% by weight, polyetherimide resin (g) 20 to 0.5, based on 100% by weight of the total of etherimide resin (g). Ri thermoplastic resin composition der consisting wt%, the thermoplastic resin composition polyester resin in the resin phase separation structure is observed by an electron microscope in (a) forms a continuous phase, the polyphenylene sulfide resin (b) polyetherimide resin (g) forms a dispersed phase and, you characterized in that said dispersed phase is a dispersed particle size of 1~100nm The thermoplastic resin composition,
( 6 ) Heat of ( 5 ), characterized in that the polyester resin (a) is 70 to 93% by weight, the polyphenylene sulfide resin (b) is 15 to 5 % by weight, and the polyetherimide resin (g) is 15 to 2% by weight. A plastic resin composition,
( 7 ) The thermoplastic resin according to any one of (1) to ( 6 ), wherein 0.01 to 10 parts by weight of the compatibilizer (c) is contained with respect to 100 parts by weight of the thermoplastic resin composition. Resin composition,
( 8 ) Compatibilizer (c) is composed of an organic silane compound having an epoxy group or an isocyanate group, a bisphenol-glycidyl ether epoxy compound, a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. ( 7 ) the thermoplastic resin composition, which is at least one selected from the group;
( 9 ) The polyester resin (a) is at least one selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and copolymers thereof ( 3 ) to the thermoplastic resin composition of any one of ( 8 ),
( 10 ) When the polyester resin (a) is polyethylene terephthalate, and measured in a differential scanning calorimetric measurement at 300 ° C. to 20 ° C./minute after holding the thermoplastic resin composition 8 mg at 300 ° C. for 5 minutes. The thermoplastic resin composition according to any one of ( 3 ) to ( 9 ), wherein the exothermic peak temperature observed in 1 is 190 ° C to 220 ° C,
( 11 ) The kneading energy of 0.3 kWh / kg or more is imparted to the molten mixture containing at least two thermoplastic resins while being controlled at a resin temperature of 200 ° C. to 330 ° C. (1) to ( 10 ) the process for producing a thermoplastic resin composition according to any one of
Is to provide.

  According to the present invention, a thermoplastic resin composition having excellent mechanical properties can be obtained. In particular, in a thermoplastic resin composition comprising a polyester resin and a PPS resin, a thermoplastic resin composition having the excellent chemical resistance and wet heat resistance of the PPS resin while maintaining the excellent toughness of the polyester resin is obtained. It is done. Moreover, in the thermoplastic resin composition which consists of a polyester resin, PPS resin, and polyetherimide resin, the thermoplastic resin composition which provided the further outstanding moisture-heat resistance and chemical-resistance can be obtained.

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

The thermoplastic resin composition of the present invention is composed of at least two components of the thermoplastic resin, the combination of the thermoplastic resin constituting, Po Riesuteru resin and the PPS resin, polyester resin and polyether imide resin, a polyester resin A polyolefin resin, a polyester resin and a polyamide resin, a polyester resin and a polycarbonate resin, more preferably a combination of a polyester resin and a PPS resin, or a polyester resin, a PPS resin, and a polyetherimide resin.

  The thermoplastic resin composition of the present invention is composed of at least two thermoplastic resins, and any one thermoplastic resin forms a continuous phase, the remaining thermoplastic resin forms a dispersed phase, and the dispersed phase is 1 to 100 nm. It is necessary to disperse with a dispersed particle diameter in the range of. As used herein, the dispersed particle size refers to the molding of ASTM No. 1 dumbbell pieces at a molding temperature of the melting point of the thermoplastic resin forming the continuous phase + 20 ° C., and a thin piece having a thickness of 80 nm is cut from the center in the cross-sectional area direction of the dumbbell pieces. Then, for any 100 dispersed particles observed with a transmission electron microscope (magnification: 10,000 times), first, the maximum diameter and the minimum diameter are measured to obtain an average value, and then the average of the 100 particles is obtained. It is the number average particle diameter obtained from the average value. A particularly preferable range of the dispersed particle size is 30 to 80 nm. When the dispersed particle diameter of the dispersed phase is outside the range of 1 to 100 nm, it is not possible to obtain a thermoplastic resin composition having excellent mechanical properties, which is the subject of the present invention.

  The thermoplastic resin composition of the present invention is not produced by spinodal decomposition which is compatible under shear during melt kneading and phase-separated under non-shear after discharge, but is compatible even under shear during melt kneading. It is preferable to prepare from an incompatible state.

  The dispersion structure in the thermoplastic resin composition of the present invention does not change greatly even when melted and retained. The particle size of the dispersed phase when melted and retained is measured as follows. After the thermoplastic resin composition of the present invention is charged into a melt indexer, the thermoplastic resin constituting the thermoplastic resin composition is melted and retained for 5 minutes at a temperature of one melting point to the melting point + 30 ° C., which has a high melting point. Then, the molten resin composition is discharged and the dispersed particle size of the dispersed phase in the sample cooled in the water bath is observed with a transmission electron microscope according to the above method. The dispersed particle size of the dispersed phase is preferably 1 to 100 nm, more preferably 30 to 80 nm. As described above, since the thermoplastic resin composition of the present invention does not have a large change in the dispersed particle size even after the melt residence, the molded product obtained without being melted and retained even in the molded product obtained after being melted and retained for a long time In comparison, the mechanical properties are not significantly reduced. When the dispersed particle size of the dispersed phase after melt residence is outside the range of 1 to 100 nm, depending on the melt residence conditions, it becomes impossible to obtain a thermoplastic resin composition having excellent mechanical properties, which is the subject of the present invention. It is not preferable.

Here, the melting point referred to in the present invention is a temperature increase rate of 20 ° C./min after the temperature is lowered from the molten state to 30 ° C. at a temperature decrease rate of 20 ° C./min in an inert gas atmosphere using a differential scanning calorimeter. It indicates the endothermic peak temperature that appears when the temperature is raised at. For an amorphous thermoplastic resin in which no endothermic peak temperature is observed by the measurement method, the melting point is defined as follows:
Melting point = glass transition temperature + 100 ° C.
The glass transition temperature mentioned here is a stepwise endotherm that appears when the temperature is increased at a rate of temperature increase of 20 ° C./min after quenching with dry ice from a molten state in an inert gas atmosphere using a differential scanning calorimeter. Points to the midpoint of the peak.

  In the thermoplastic resin composition of the present invention, any one thermoplastic resin forms a continuous phase, the remaining thermoplastic resin forms a dispersed phase, and the dispersed phase is dispersed with a dispersed particle diameter in the range of 1 to 100 nm. Furthermore, when the thickness of the interfacial phase in which both components coexist at the boundary between the two resins is 30 to 70 nm, the chemical resistance and moist heat resistance, which are the objects of the present invention, are remarkably improved, and more preferably 35 to 60 nm. . The thickness of the interfacial phase as used in the present invention means that a thin piece having a thickness of 80 nm is cut from the center of the injection-molded piece in the direction of the cross-sectional area of the dumbbell piece, and any 10 dispersed particles are attached using a field emission electron microscope. As shown in Fig. 1, EDX ray analysis (energy dispersive X-ray spectroscopic analysis) on the line crossing the particle, the atomic concentration present in the resin constituting the thermoplastic resin and the atomic concentration in the staining agent used during electron microscope observation Means the average value of the values obtained by measuring the length of the region where the value continuously changes. In particular, when measuring the interfacial phase thickness of the PPS resin dispersed in the polyester resin continuous phase, the sulfur atom concentration of the PPS resin is measured by EDX ray analysis, and the interfacial phase thickness of the polyamide resin dispersed in the polyester resin continuous phase is determined. When measuring, the polyamide resin was dyed with a dye (phosphotungstic acid) used for dyeing the polyamide resin during electron microscope observation, and the tungsten atom concentration selectively present in the polyamide resin was measured by EDX ray analysis. . When the thickness of the interface phase is less than 30 nm, the chemical resistance is deteriorated, which is not preferable. On the other hand, if the thickness of the interfacial phase exceeds 70 nm, the fluidity decreases and the workability deteriorates, which is not preferable. Further, in order to control the thickness of the interfacial phase as described above, it is important to appropriately select (c) a compatibilizing agent, and the compatibilizing agent and the resin constituting the thermoplastic resin react with each other to form a graft type or A star-type compatibilizing component is preferably formed.

  The polyester resin (a) preferably used in the present invention is a polymer having an ester bond in the main chain. Preferred examples include thermoplastic polyesters having an aromatic ring in the chain unit of the polymer. Specifically, usually, an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) and Examples thereof include a polymer or copolymer obtained by a condensation reaction mainly containing hydroxycarboxylic acid.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl Examples include dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid and ester-forming derivatives thereof. Two or more of these aromatic dicarboxylic acids can be used in combination. Also used in combination with aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and ester-forming derivatives thereof You can also

  As the diol, an aliphatic diol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, And cyclohexanedimethanol, cyclohexanediol, and the like, and ester-forming derivatives thereof. Two or more of these diols can be used in combination.

  Specific examples of the polyester preferably used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyalkylene terephthalate such as polyhexylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, Polybutylene-2,6-naphthalene dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / Decane dicarboxylate, poly (ethylene terephthalate / cyclohexanedimethylene terephthalate), polyethylene Non-liquid crystal polyester, and mixtures thereof, such as down-4,4'-dicarboxylate / terephthalate, and the like.

  More preferable examples include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate, and particularly preferable is polyethylene terephthalate, but these polyester resins have moldability, heat resistance, toughness, surface It is also practically suitable to use it as a mixture depending on necessary properties such as properties.

  There is no restriction | limiting in particular in the manufacturing method of the polyester resin (a) used by this invention, It manufactures by the conventionally well-known direct polymerization method or transesterification method. The direct polymerization method referred to here is a method for producing a polyester resin by carrying out an esterification reaction with a dicarboxylic acid and a diol as main components, followed by a polycondensation reaction under reduced pressure. The transesterification method is a method for producing a polyester resin by carrying out an ester exchange reaction using an ester-forming derivative of a dicarboxylic acid and a diol as main components, followed by a polycondensation reaction under reduced pressure.

  When the direct polymerization method is used, first, an esterification reaction is performed to form an oligomer, and then a polycondensation reaction is performed to produce a polyester. The method of this esterification reaction is not particularly limited, and may be a batch method or a continuous method, and the esterification conditions used for normal polyester production can be applied as they are. For example, the reaction temperature is 180 to 300 ° C. In particular, it is preferable to carry out under the condition of 200 to 280 ° C. Further, the reaction rate of the oligomer after the esterification reaction is preferably 97% or more.

  When the transesterification method is used, a polyester is produced by first performing an ester exchange reaction to obtain an oligomer and then performing a polycondensation reaction. The method of this transesterification is not particularly limited, and may be a batch method or a continuous method, and the transesterification conditions used for normal polyester production can be applied as they are. For example, the reaction temperature is 120 to 300 ° C. In particular, it is preferable to carry out under the condition of 140 to 280 ° C. Moreover, it is preferable that the reaction rate of the oligomer after transesterification is 80% or more.

  The oligomer obtained from the esterification reaction or transesterification reaction is then subjected to a polycondensation reaction, but the method is not particularly limited, and may be a batch method or a continuous method, and the polymerization conditions used for normal polyester production For example, the reaction temperature is 230 to 300 ° C., preferably 240 to 280 ° C., and the pressure is 667 Pa or less, preferably 133 Pa or less under reduced pressure.

  Moreover, when the thermoplastic resin composition of the present invention contains the polyester resin (a) and the PPS resin (b), the polyester resin (a) used in the present invention is an m-cresol solution in an alkaline solution. It is preferable that the amount of carboxyl end groups determined by potentiometric titration is 10 to 50 eq / t (the amount of end groups per ton of polymer). Especially preferably, it is 10-40 eq / t. If the carboxyl end group amount is less than 10 eq / t, it is difficult to control the PPS resin to a specific dispersion structure, and if it is more than 50 eq / t, hydrolysis is increased, which is not preferable.

  Although there is no restriction | limiting in the polymerization degree of these polyester resins, For example, the intrinsic viscosity measured at 25 degreeC in the 0.5% o-chlorophenol solution is the range of 0.35-2.00, More preferably, it is 0.00. The thing of the range of 50-1.50 is preferable.

  As the PPS resin (b) preferably used in the present invention, a polymer having a repeating unit represented by the following structural formula can be used.

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the structural formula is preferable. Moreover, about 30 mol% or less of the repeating units of the PPS resin may be composed of repeating units having any of the following structures. Of these, a p-phenylene sulfide / m-phenylene sulfide copolymer (m-phenylene sulfide unit of 20% or less) can be preferably used because it has both moldability and barrier properties.

  Such a PPS resin can be produced in a high yield by recovering and post-treating a PPS resin obtained by reacting a polyhalogen aromatic compound and a sulfidizing agent in a polar organic solvent. Specifically, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or a relatively molecular weight described in JP-B-52-12240 and JP-A-61-7332 is disclosed. It can also be produced by a method for obtaining a large polymer. Crosslinking / high molecular weight of the PPS resin obtained as described above by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, etc., acid anhydride It can also be used after being subjected to various treatments such as activation with functional group-containing compounds such as amines, isocyanates, and functional group-containing disulfide compounds.

  As a specific method for crosslinking / high molecular weight of PPS resin by heating, under an oxidizing gas atmosphere such as air or oxygen or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Examples of the method include heating in a heating container at a predetermined temperature until a desired melt viscosity is obtained. The heat treatment temperature is usually 170 to 280 ° C, preferably 200 to 270 ° C. The heat treatment time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both of these, the target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. It is preferable to use an apparatus.

  As a specific method for heat-treating the PPS resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200 to 200 ° C. under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at 270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. More preferably, an apparatus is used.

  The PPS resin (b) used in the present invention is preferably a PPS resin that has been subjected to a cleaning treatment. Specific examples of the cleaning treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment. These treatments may be used in combination of two or more methods.

  The following method can be illustrated as a specific method when the PPS resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethyl sulfoxide Sulfoxides such as dimethylsulfone, sulfone solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane , Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol Lumpur, phenol, cresol, alcohols such as polyethylene glycol, phenolic solvents, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is 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 a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning 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. The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method when the PPS resin is washed with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to express the preferable chemical modification effect of the PPS resin by hot water washing. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  Further, when washing with hot water, it is preferable to use an aqueous solution containing a Group II metal element of the periodic table. The aqueous solution containing a Group II metal element of the periodic table is obtained by adding a water-soluble salt containing a Group II metal element of the periodic table to the water. The concentration of the water-soluble salt having a Group II metal element in the periodic table with respect to water is preferably in the range of about 0.001 to 5% by weight.

Examples of preferable metal elements among Group II metal elements of the periodic table used herein include Ca, Mg, Ba and Zn. Other anions include acetate ions, halide ions, hydroxide ions, and the like. Examples include carbonate ions. More specific and preferred compounds include Ca acetate, Mg acetate, Zn acetate, CaCl ₂ , CaBr ₂ , ZnCl ₂ , CaCO ₃ , Ca (OH) ₂ and CaO, and particularly preferably Ca acetate. is there.

  The temperature of the aqueous solution containing a Group II metal element in the periodic table is preferably 130 ° C. or higher, more preferably 150 ° C. or higher. Although there is no restriction | limiting in particular about the upper limit of washing | cleaning temperature, When using a normal autoclave, about 250 degreeC is a limit.

  The bath ratio of the aqueous solution containing the Group II metal element in the periodic table is preferably selected in the range of 2 to 100, more preferably 4 to 50, and 5 to 15 with respect to the dry polymer 1 by weight. More preferably, it is in the range.

  The following method can be illustrated as a specific method when the PPS resin is washed with an acid aqueous solution. That is, there is a method of immersing a PPS resin in an acid or an aqueous solution of an acid, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing PPS resin, and is saturated with aliphatic monocarboxylic acid such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as saturated carboxylic acid, acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, sulfuric acid Inorganic acid compounds such as phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. It is preferable to wash the acid-treated PPS resin several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by acid treatment is not impaired.

  The amount of ash content of the PPS resin (b) used in the present invention is preferably in a relatively large range of 0.1 to 2% by weight from the viewpoint of imparting characteristics such as fluidity during processing and molding cycle, and is preferably 0.2 to The range of 1% by weight is more preferable, and the range of 0.3 to 0.8% by weight is further preferable.

Here, the amount of ash refers to the amount of inorganic components in the PPS resin determined by the following method.
(1) Weigh 5-6 g of PPS resin in a platinum dish fired and cooled at 583 ° C.
(2) The PPS resin is pre-fired at 450 to 500 ° C. together with the platinum dish.
(3) Put a PPS sample pre-fired with a platinum pan in a muffle furnace set at 583 ° C., and fire it for about 6 hours until it completely incinerates.
(4) Weigh after cooling in a desiccator.
(5) Calculate the ash content by the formula: ash content (% by weight) = (weight of ash content (g) / sample weight (g)) × 100.

The melt viscosity of the PPS resin (b) used in the present invention is 1 to 2000 Pa · s (300 ° C., shear rate 1000 sec ⁻¹ ) from the viewpoint of imparting characteristics such as improved chemical resistance and fluidity during processing. The range of 1 to 200 Pa · s is more preferable, and the range of 1 to 50 Pa · s is more preferable. Here, the melt viscosity is a value measured by a Koka flow tester using a nozzle having a nozzle diameter of 0.5 mmφ and a nozzle length of 10 mm under conditions of a shear rate of 1000 sec ⁻¹ .

  Chloroform extraction amount (calculated from the residual amount at the time of 5 hours treatment with Soxhlet extraction) is used as an index of the amount of the organic low polymerization component (oligomer) of the PPS resin (b) used in the present invention. A relatively high range of 1 to 5% by weight is preferable from the viewpoint of imparting characteristics such as improvement in chemical properties and fluidity during processing, more preferably 1.5 to 4% by weight, and 2 to 4% by weight. More preferably, it is in the range.

  When the thermoplastic resin composition of the present invention contains a polyester resin (a) and a PPS resin (b), the thermoplastic resin composition exhibits excellent effects such as chemical resistance and wet heat resistance while having excellent toughness. . In this case, the blending ratio of the polyester resin (a) and the PPS resin (b) is 50 to 99% by weight of the polyester resin (a), with the total of the polyester resin (a) and the PPS resin (b) being 100% by weight, The PPS resin (b) is 50 to 1% by weight, preferably 70 to 95% by weight of the polyester resin (a) and 30 to 5% by weight of the PPS resin (b). If the PPS resin (b) is less than 1% by weight, it is difficult to obtain an effect of improving chemical resistance and moist heat resistance, and conversely if it is more than 50% by weight, the toughness of the polyester resin is impaired, which is not preferable.

  Further, the polyester resin (a) forms a continuous phase, the PPS resin (b) forms a dispersed phase, and the PPS resin (b) needs to be dispersed with a dispersed particle size in the range of 1 to 100 nm. A particularly preferable range of the dispersed particle size is 30 to 80 nm. When the dispersed particle size of the PPS resin (b) is outside the range of 1 to 100 nm, the excellent chemical resistance and moisture resistance of the PPS resin are maintained while maintaining the excellent toughness of the polyester resin which is the subject of the present invention. A thermoplastic resin composition imparted with heat cannot be obtained.

The polyetherimide resin (g) used in the present invention is not particularly limited as long as it is a polymer having an ether bond and an imide bond repeatedly in the main chain, but 2,2-bis [4- (2,3 -Dicarboxyphenoxy) phenyl] propane dianhydride and m-phenylenediamine or p-phenylenediamine and a polycondensate of a mixture of m-phenylenediamine and p-phenylenediamine are preferred. This polyetherimide is available from GE Plastics under the trade name “Ultem” (registered trademark).
When the thermoplastic resin composition of the present invention contains a polyester resin (a), a PPS resin (b), and a polyetherimide resin (g), it exhibits an improvement effect such as excellent moisture and heat resistance characteristics. In this case, the blending ratio of the polyester resin (a), the PPS resin (b) and the polyetherimide resin (g) is the sum of the polyester resin (a), the PPS resin (b) and the polyetherimide resin (g). As 100% by weight, polyester resin (a) 50 to 98.5% by weight, PPS resin (b) 30 to 1% by weight, polyetherimide resin (g) 20 to 0.5% by weight, preferably polyester The resin (a) is 70 to 93% by weight, the PPS resin (b) is 15 to 5% by weight, and the polyetherimide resin (g) is 15 to 2% by weight. If the polyetherimide resin (g) is less than 0.5% by weight, it is difficult to obtain the effect of improving the heat and moisture resistance. On the other hand, if it is more than 20% by weight, the crystallinity of the polyester resin is impaired.

When the present invention contains a polyester resin (a), a PPS resin (b) and a polyetherimide resin (g), the polyester resin (a) is a continuous phase, the PPS resin (b) and the polyetherimide resin ( g) forms a dispersed phase, and the PPS resin (b) and the polyetherimide resin (g) need to be dispersed with a dispersed particle diameter in the range of 1 to 100 nm. Particularly preferable ranges of the dispersed particle diameter are PPS resin (b) 30 to 80 nm and polyetherimide resin (g) 1 to 50 nm. When the dispersed particle size of the PPS resin (b) and the polyetherimide resin (g) is outside the range of 1 to 100 nm, while maintaining the excellent toughness of the polyester resin that is the subject of the present invention, A thermoplastic resin composition imparted with the excellent chemical resistance and wet heat resistance of the polyetherimide resin cannot be obtained.
As the polyolefin resin used in the present invention, high-density polyethylene resins, low density polyethylene resins, linear low-density polyethylene resins, polypropylene resins, positive Li 1-butene resins, poly-1-pentene resins, polymethyl pentene resins, Copolymer of ethylene / α-olefin copolymer, (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), (ethylene and / or propylene) and (unsaturated carboxylic acid) and / or at least a portion of the polyolefin obtained by the metal chloride, vinyl chloride / ethylene copolymer of the carboxyl groups of the copolymer of an unsaturated carboxylic acid ester, d styrene / vinyl acetate copolymer, and ethylene / Examples thereof include a saponified product of a vinyl acetate copolymer.
Further, a modified high density polyethylene resin, a modified low density polyethylene resin, a modified linear low density polyethylene resin, a modified polypropylene resin, etc. modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof, etc. Can also be used.

  A compatibilizing agent (c) can be added to the thermoplastic resin composition of the present invention for the purpose of improving the compatibility between the thermoplastic resins. Specific examples of the compatibilizer (c) include organic silanes such as alkoxysilanes having at least one functional group selected from an epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and ureido group. A compound, a polyfunctional epoxy compound, etc. are mentioned, These can also be used simultaneously 2 or more types. Here, the polyfunctional epoxy compound contains two or more epoxy groups in the molecule, and a liquid or solid one can be used. For example, a copolymer of an α-olefin such as ethylene, propylene, and 1-butene and an α, β-unsaturated glycidyl ester such as glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, having an unsaturated double bond Epoxy group-containing polymer compound obtained by epoxidizing the double bond part of the polymer, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyl Bisphenol-glycidyl ether type epoxy compounds such as dimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, phthalate Glycidyl ester type epoxy compounds such as glycidyl esters, N- glycidyl amine-based epoxy compound glycidyl aniline, novolac type phenolic resin novolak type epoxy resins obtained by reacting epichlorohydrin and the like. Preferably, a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester, an organic silane compound having an epoxy group or an isocyanate group, or a bisphenol-glycidyl ether epoxy compound is used. In particular, the use of an organosilane compound having an isocyanate group is particularly preferable because the interfacial phase thickness is increased.

  The blending ratio of the compatibilizing agent (c) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. When the addition amount is 0.01 parts by weight or less, a sufficient compatibility improving effect cannot be obtained, and when it exceeds 10 parts by weight, the melt viscosity of the thermoplastic resin composition is remarkably increased and the fluidity is lowered.

  The thermoplastic resin composition of the present invention can further contain an antioxidant or other additives as described below.

  Furthermore, in the present invention, in order to maintain high heat resistance and thermal stability, it is preferable to include one or more antioxidants selected from phenolic and phosphorus compounds. The blending amount of the antioxidant is preferably 0.01 parts by weight or more, particularly 0.02 parts by weight or more with respect to a total of 100 parts by weight of the thermoplastic resin composition in terms of heat resistance improvement effect, From the viewpoint of the gas component generated sometimes, it is preferably 5 parts by weight or less, particularly 1 part by weight or less. In addition, the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance, thermal stability and fluidity retention effect.

  As the phenolic antioxidant, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4 Hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, ester type polymer hindered phenol type is preferable. Specifically, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityl. Tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like are preferably used.

  Next, phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl). ) Pentaerythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphite Examples include phonate diethyl ester. Among them, those having a high melting point of the antioxidant are preferably used in order to reduce the volatilization and decomposition of the antioxidant in the polyester resin compound.

  Moreover, the following compounds can be added for the purpose of modification. Coupling agents such as isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds, epoxy compounds, polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, etc. , Talc, kaolin, organic phosphorus compound, crystal nucleating agent such as polyether ether ketone, montanic acid wax, metal soap such as lithium stearate, aluminum stearate, ethylenediamine / stearic acid / sebacic acid heavy compound, silicone Conventional additives such as release agents such as compounds, anti-coloring agents such as hypophosphite, and other lubricants, UV inhibitors, colorants, flame retardants, and foaming agents can be blended. Any of the above compounds is not preferred if the amount exceeds 20 parts by weight of the entire thermoplastic resin composition of the present invention, because the original properties of the thermoplastic resin forming the continuous phase are impaired, and is preferably 10 parts by weight or less, more preferably 1 part by weight. The following addition is good.

  The thermoplastic resin composition obtained by the method of the present invention can be used by blending a filler as long as the effects of the present invention are not impaired. Specific examples of such fillers include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, Fibrous fillers such as stone kou fiber, metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide , Metal compounds such as alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide and hydroxide Non-fibrous fillers such as hydroxides such as luminium, glass beads, glass flakes, glass powders, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite are used, and these may be hollow Further, two or more kinds of these fillers can be used in combination. These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

  When the polyethylene resin terephthalate is used for the polyester resin (a) in order to improve the molding processability and molding cycle during molding, the thermoplastic resin composition of the present invention is 300 ° C. in the differential calorimetry of the resulting resin composition. It is preferable that the exothermic peak temperature (Tmc) derived from polyethylene terephthalate observed when measured under a temperature drop condition of 300 ° C. to 20 ° C./min after holding for 5 minutes is 190 to 220 ° C., more preferably 195 to 220 ° C.

  The kneading machine used for the production of the thermoplastic resin composition of the present invention is a heat that forms a continuous phase by supplying it to a generally known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. A typical example is a method of kneading at a processing temperature equal to or higher than the melting point of the plastic resin. In order to control the morphology of the present invention and the particle size of the dispersed phase as described above, the kneading energy during extrusion (discharge) It is necessary to increase the extruder work amount per unit (kW / (kg / h)). The kneading energy is preferably 0.30 or more, particularly preferably 0.35 or more. However, if the kneading energy is increased, the resin temperature rises due to heat generated by shearing, causing thermal decomposition of the thermoplastic resin, making it difficult to form the desired phase separation structure. Therefore, the resin temperature during extrusion is preferably 200 ° C to 330 ° C. When the components constituting the thermoplastic resin composition of the present invention are the polyester resin (a) and the PPS resin (b), both the thermoplastic resins are melted and the thermal decomposition is suppressed. The resin temperature is preferably 280 ° C to 330 ° C. Further, when the components constituting the thermoplastic resin composition of the present invention are the polyester resin (a), the PPS resin (b) and the polyetherimide resin (g), the three-component thermoplastic resin is melted. And in order to suppress thermal decomposition, it is preferable that the resin temperature at the time of extrusion is 280 degreeC-330 degreeC.

  By controlling the kneading energy and the resin temperature in this way, it is possible to form a target resin phase separation structure. Specifically, the cylinder configuration of a normal twin screw extruder can be divided into a plasticizing part that plasticizes the charged resin and a kneading part that melts and kneads the plasticized molten resin. As for the cylinder temperature at the time of melt kneading using 100, the plasticizing portion is set to a temperature of the melting point of the thermoplastic resin having a high melting point to the melting point + 20 ° C., and the cylinder temperature of the kneading portion is set to 100 to 250 ° C. in order to suppress heat generation. The said conditions can be achieved by setting it as a range. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended. Any method such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or biaxial extruder may be used. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.

  The thermoplastic resin composition of the present invention is particularly useful for injection molding applications because of its excellent mechanical properties, chemical resistance, and molding processability. Further, taking advantage of this feature, it is particularly suitable for use in general equipment, structures for automobiles, structures such as cases, and metal insert molded articles for electric and electronic use.

  The present invention will be described more specifically with reference to the following examples. About the material characteristic, it carried out by the following method.

  [Resin temperature] The temperature at which the molten resin discharged from the extruder die was measured with a thermometer when melt-kneaded in the twin-screw extruder.

[Morphological Observation] ASTM No. 1 dumbbell piece was formed by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.), and a 80 nm thick piece was cut from the center to transmit transmission electron It observed with the microscope and evaluated as follows.
○: One of the thermoplastic resins forms a continuous phase, and the other thermoplastic resin forms a dispersed phase.
X: Co-continuous phase formation between thermoplastic resins.

  [Dispersed particle size] The dispersed particle size of the dispersed phase is measured by the image processing software “Scion Image” for a dispersed portion of 100 arbitrary dispersed particles in an injection molded product observed at a magnification of 10,000 as in the above-described morphology observation. (Scion Corporation) was used to determine the average value by measuring the maximum and minimum diameters of each particle, and then the number average value (average particle diameter) of the 100 average values.

  [Dispersed particle size after melt residence] The dispersion particle size of the dispersed phase after melt residence was measured by charging a thermoplastic resin composition dried at 130 ° C. for 3 hours into a Toyo Seiki melt indexer at 300 ° C. After melting and staying for 5 minutes, the molten resin was discharged and the sample cooled in a water bath was measured in the same manner as the average particle diameter measurement.

  [Lower molding pressure] Injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) can be prepared in the ATSM family mold without any short shots. The minimum filling pressure was determined.

  [Exothermic peak temperature (Tmc)] Using DSC-7 manufactured by Perkin Elmer, the sample polymer amount was about 8 mg, held at 300 ° C. for 5 minutes, and then scanned at a temperature decreasing rate of 20 ° C./min. (Tmc) was measured.

  [Molding cycle] Sink marks of molded product when preparing ASTM No. 1 dumbbell piece by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C., two ASTM No. 1 dumbbell pieces) Maximum number of injections per hour (shot / hr) that yields good molded products with no deformation. However, the polybutylene terephthalate resin system was performed at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C.

  [Tensile Breaking Elongation] The tensile breaking elongation was measured according to ASTM-D638 using an ASTM No. 1 dumbbell prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.).

[Chemical resistance] The surface of the dumbbell piece after the ASTM No. 1 dumbbell piece was immersed in hexafluoroisopropanol at 23 ° C. for 1 hour was observed with an optical microscope, and the presence or absence of a rough surface portion (such as a void) was measured.
A: Almost no rough surface.
○: Surface rough portion is 30% or less.
X: Surface roughening part 100%.
XX: The dumbbell is dissolved and the dumbbell shape cannot be maintained.

[Hydrolysis resistance] ASTM No. 1 dumbbell pieces were subjected to a tensile test in accordance with ASTM-D638 after measuring for 5000 hours in a constant temperature and high humidity bath at 60 ° C. and 95% RH, and the elongation at break was measured. And the tensile rupture elongation retention rate.
A: Retention ratio (post-treatment tensile elongation at break / untreated tensile elongation at break) = 80 to 100%
○: Retention rate = 50-80%
X: Retention rate = 0 to 50%.

[Interfacial phase thickness] The interfacial phase thickness of the resin in the dispersed phase was measured as follows. A thin piece having a thickness of 80 nm is cut in the direction of the cross-sectional area of the dumbbell piece from the center of the ASTM No. 1 dumbbell piece produced by the above method, and about 10 dispersed particles with a field emission electron microscope, as shown in FIG. EDX ray analysis (energy dispersive X-ray spectroscopic analysis) of the atomic concentration on the line across the substrate, Examples 5 to 9 and Comparative Example 2 measure the length of the region where the sulfur atom concentration of the PPS resin continuously changes The average value was obtained. In Examples 10 to 11 and Comparative Example 3 , the length of the region where the tungsten atom concentration of the staining agent (phosphotungstic acid) selectively present in the polyamide resin used at the time of observation with an electron microscope continuously changes was measured. The average value was obtained.

[Examples 1 to 4 ]
Each component shown below was dry blended in the proportions shown in Table 5 and then melt kneaded with a TEX30 twin screw extruder manufactured by Nippon Steel Works, with the cylinder temperature and screw rotation set to the conditions shown in Table 5. And pelletized with a strand cutter. A test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) using pellets dehumidified and dried at 120 ° C. overnight. The results of measuring the chemical resistance and morphology of each sample are shown in Table 5. This example was excellent in elongation at break, chemical resistance, hydrolysis resistance and moldability.

[Examples 5 to 11 and Comparative Examples 1 to 3 ]
Each component shown below was dry blended in the proportions shown in Table 6 and then melt kneaded by setting the cylinder temperature and screw rotation to the conditions shown in Table 6 using a TEX30 twin screw extruder manufactured by Nippon Steel Works. And pelletized with a strand cutter. A test piece was prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 280 ° C., mold temperature 130 ° C.) using pellets dehumidified and dried at 120 ° C. overnight. The results of measuring the chemical resistance and morphology of each sample are shown in Table 6. This example was excellent in elongation at break, chemical resistance, hydrolysis resistance and moldability.

The polyester resin (a) used in the examples and comparative examples is as follows.
(A-1): Polyethylene terephthalate resin having a melting point of 260 ° C., an intrinsic viscosity of 1.27, and a carboxyl end group amount of 14 eq / t.
(A-2): Polyethylene terephthalate resin having a melting point of 260 ° C., an intrinsic viscosity of 0.85, and a carboxyl end group amount of 26 eq / t.
(A-3): Polybutylene terephthalate resin having a melting point of 220 ° C., an intrinsic viscosity of 0.70, and a carboxyl end group amount of 35 eq / t.
(A-4): Polyethylene-2,6-naphthalenedicarboxylate resin having a melting point of 262 ° C., an intrinsic viscosity of 0.62, and a carboxyl end group amount of 33 eq / t.

Similarly, the PPS resin (b) is as follows.
(B-1): Melting point 280 ° C., ash content 0.6% by weight, melt viscosity 40 Pa · s (orifice 0.5φ × 10 mm, 300 ° C., shear rate 1000 sec ⁻¹ ), chloroform extraction amount 3.8%, PFR resin with MFR = 1000 g / 10 min (315.5 ° C., 5 kg load).
(B-2): Melting point 280 ° C., ash content 0.02% by weight, melt viscosity 200 Pa · s (orifice 0.5φ × 10 mm, 300 ° C., shear rate 1000 sec ⁻¹ ), chloroform extract amount 0.4%, PFR resin with MFR = 100 g / 10 min (315.5 ° C., 5 kg load).

Similarly, the compatibilizer (c) is as follows.
(C-1): A bisphenol A type epoxy resin having an epoxy equivalent of 875 to 975 and a molecular weight of 1600.
(C-2): γ-glycidoxypropyltrimethoxysilane (SH6040 manufactured by Toray Dow Corning Silicone).
(C-3): MFR = 3 g / 10 min (190 ° C., 2.16 kg load) ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer.
(C-4): Epoxy group-containing styrenic thermoplastic elastomer (Epofriend AT501 manufactured by Daicel Chemical Industries)
(C-5): 3-isocyanatopropyltriethoxysilane (Shin-Etsu Silicone KBE-9007 )

Similarly, the polyamide resin is as follows.
(E-1): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 2.75 at 98 g sulfuric acid 1 g / dl.

Similarly, polyetherimide resin (g) is as follows.
(G-1): Polyetherimide resin (manufactured by GE Plastics, “Ultem” 1010).

It is a model figure which shows an example of a field emission type electron microscope-EDX-ray analysis when the interface phase thickness of the PPS resin or polyamide resin disperse | distributed to the polyester resin continuous phase is measured.

Claims (11)

A polyester resin and a polyphenylene sulfide resin, a polyester resin and a polyetherimide resin, a polyester resin and a polyolefin resin, a polyester resin and a polyamide resin, and a combination of at least two thermoplastic resins selected from a polyester resin and a polycarbonate resin A thermoplastic resin composition containing a resin phase-separated structure observed with an electron microscope in the thermoplastic resin composition, wherein any one of the thermoplastic resins has a continuous phase and the remaining thermoplastic resin is dispersed. A thermoplastic resin composition characterized in that a phase is formed, the dispersed phase has a dispersed particle diameter of 1 to 100 nm, and the thickness of the interface phase of the thermoplastic resin forming the dispersed phase is 30 to 70 nm. The at least two thermoplastic resins have different melting points, and the thermoplastic resin composition is melted and retained for 5 minutes at a temperature ranging from the melting point of one thermoplastic resin having a high melting point to the melting point + 30 ° C., and cooled in a water bath. The thermoplastic resin composition according to claim 1, wherein the dispersed phase in the resin composition has a dispersed particle diameter of 1 to 100 nm. The at least two thermoplastic resins are a polyester resin (a) and a polyphenylene sulfide resin (b), and the total amount of the polyester resin (a) and the polyphenylene sulfide resin (b) is 100% by weight. A thermoplastic resin composition comprising 99% by weight of polyphenylene sulfide resin (b) and 50 to 1% by weight of a polyester resin (a) in a resin phase separation structure observed with an electron microscope in the thermoplastic resin composition Forms a continuous phase, and the polyphenylene sulfide resin (b) is a dispersed phase. The thermoplastic resin composition according to claim 1 or 2, wherein The thermoplastic resin composition according to claim 3, wherein the polyester resin (a) is 70 to 95% by weight and the polyphenylene sulfide resin (b) is 30 to 5% by weight. A thermoplastic resin composition comprising a polyester resin (a), a polyphenylene sulfide resin (b) and a polyetherimide resin (g), wherein the polyester resin (a), the polyphenylene sulfide resin (b) and the polyetherimide resin ( The total of g) is 100% by weight, and the polyester resin (a) is 50 to 98.5% by weight, the polyphenylene sulfide resin (b) is 30 to 1% by weight, and the polyetherimide resin (g) is 20 to 0.5% by weight. A polyester resin (a) forms a continuous phase in a resin phase separation structure observed with an electron microscope in the thermoplastic resin composition, and a polyphenylene sulfide resin (b) and a polyetherimide resin. (G) forms a dispersed phase, and the dispersed phase has a dispersed particle diameter of 1 to 100 nm. Resin composition. The thermoplastic resin according to claim 5, wherein the polyester resin (a) is 70 to 93% by weight, the polyphenylene sulfide resin (b) is 15 to 5% by weight, and the polyetherimide resin (g) is 15 to 2% by weight. Resin composition. The thermoplastic resin composition according to any one of claims 1 to 6, comprising 0.01 to 10 parts by weight of a compatibilizer (c) with respect to 100 parts by weight of the thermoplastic resin composition. . The compatibilizer (c) is selected from the group consisting of an organic silane compound having an epoxy group or an isocyanate group, a bisphenol-glycidyl ether epoxy compound, and a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester. The thermoplastic resin composition according to claim 7, wherein the thermoplastic resin composition is at least one kind. The polyester resin (a) is at least one selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate and copolymers thereof. The thermoplastic resin composition according to any one of 8. The polyester resin (a) is polyethylene terephthalate, and is observed when measured under a temperature drop condition of 300 ° C. to 20 ° C./min after holding the thermoplastic resin composition 8 mg in differential scanning calorimetry at 300 ° C. for 5 minutes. The thermoplastic resin composition according to any one of claims 3 to 9, wherein the exothermic peak temperature is 190 ° C to 220 ° C. The kneading energy of 0.3 kWh / kg or more is given to the molten mixture containing the thermoplastic resin of at least two components while controlling the resin temperature at 200 ° C to 330 ° C. The manufacturing method of the thermoplastic resin composition as described in any one of.

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