JP2011127061A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which comprises a thermoplastic resin composition having excellent regularity and finely controlled in structure and a hollow filler, is lightweight, has mechanical characteristics excellent in strength, rigidity, and the like, gives molded products, and is high in practicality as a general molding material. <P>SOLUTION: The thermoplastic resin composition is characterized by comprising (A) 100 pts.wt. of the thermoplastic resin composition comprising at least two components, and (B) 0.1 to 50 pts.wt. of a hollow filler, wherein the thermoplastic resin composition comprising at least two components forms a diphasic continuous structure having a structural cycle of 0.001 to <1 μm or a dispersion structure having an interparticle distance of 0.001 to <1 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition capable of structural control from nanometer order to micron order that can be usefully used as a structural material by making use of excellent mechanical properties and a functional material making use of excellent regularity. It is.

  In recent years, by combining two or more types of materials, the development of composite materials having excellent properties and functions that cannot be obtained with a single material by taking advantage of the individual materials and making up for the disadvantages, has been actively conducted, Such composite materials are used in various fields. Among these, thermoplastic composite resins obtained by filling thermoplastic resins with various inorganic reinforcing materials, inorganic fillers, etc. are excellent in molding processability, rigidity, strength, heat resistance, dimensional stability, etc. It is used in a wide range of fields including the above.

  However, in the conventional thermoplastic composite resin, the specific gravity of the reinforcing material such as the inorganic material and inorganic filler to be filled is large. Therefore, when these are filled in the thermoplastic resin, the mechanical properties such as rigidity and strength of the resulting thermoplastic composite resin are obtained. Although it is possible to improve the physical characteristics, there is a problem that even the weight thereof is significantly increased. When the thermoplastic composite resin having increased weight as described above is used in various molded articles in, for example, automobiles, the fuel efficiency is not sufficiently improved.

  Therefore, it is conceivable to use hollow inorganic particles having a small specific gravity as an inorganic material, an inorganic filler or the like to be filled in the thermoplastic resin, mainly for weight reduction. For example, Patent Documents 1 and 2 disclose resin compositions obtained by adding a specific hollow glass to a polycarbonate resin. However, in such a case, the thermoplastic resin has a remarkably high viscosity, so the fluidity is not sufficient, and it is difficult to mold when the molded product size is large, and the resulting molded product has a remarkably low impact strength, There is a problem that it becomes impractical.

  On the other hand, a polymer alloy technique using two or more kinds of resins is widely used as a method for achieving various properties such as impact properties and mechanical properties. Among them, as a polymer alloy obtained by phase-separating two or more kinds of resins once in a single phase, those composed of nucleation and growth and those composed of spinodal decomposition are known, It can be usefully used as a structural material utilizing its excellent mechanical properties and as a functional material utilizing its excellent regularity.

  For example, Patent Document 3 discloses a polymer alloy having at least two components phase-separated by spinodal decomposition, and Patent Document 4 discloses a polymer alloy formed by blending a polybutylene terephthalate resin and a polycarbonate resin with a filler. The added resin composition is shown. All of the above publications show that excellent strength and rigidity are exhibited by controlling the resin structure period to a biphasic continuous structure of 0.01 to 1 μm or a dispersed structure having a distance between particles of 0.01 to 1 μm. However, a method for reducing the weight is not disclosed.

Japanese Patent Laid-Open No. 6-345593 JP 7-258528 A JP 2003-286414 A JP 2005-336410 A

  An object of the present invention is to solve the above-mentioned problems and to provide a thermoplastic resin composition that is lightweight and excellent in mechanical properties such as strength and rigidity.

  As a result of intensive studies to provide a thermoplastic resin composition that is lightweight and excellent in mechanical properties such as strength and rigidity, the present inventors have determined that (A) at least two-component thermoplastic resin in the thermoplastic resin composition. (B) A hollow filler is blended with the composition, and (A) a thermoplastic resin composition of at least two components is a two-phase continuous structure having a structural period of less than 0.001 to 1 μm, or a distance between particles of 0.001 to 0.001. It has been found that by forming a dispersion structure of less than 1 μm, a lightweight thermoplastic resin composition having excellent strength and rigidity can be obtained, and the present invention has been completed.

That is, the present invention
(1) (A) A resin composition obtained by blending 0.1 to 30 parts by weight of a hollow filler with respect to 100 parts by weight of at least two thermoplastic resin compositions, wherein (A) at least 2. A thermoplastic resin characterized in that the two-component thermoplastic resin composition forms a biphasic continuous structure having a structural period of less than 0.001 to 1 μm or a dispersed structure having an interparticle distance of less than 0.001 to 1 μm. Composition,
(2) (A) The thermoplastic resin composition according to (1), wherein the thermoplastic resin composition of at least two components comprises a polybutylene terephthalate resin and a polycarbonate resin,
(3) The thermoplastic resin composition according to any one of (1) to (2), wherein the (B) hollow filler is a glass balloon,
(4) The thermoplastic resin composition according to any one of (1) to (3), wherein the pressure resistance of the hollow filler (B) is 100 MPa or more,
(5) A molded product formed by molding the thermoplastic resin composition according to any one of (1) to (4),
Is to provide.

  The thermoplastic resin composition of the present invention can provide a thermoplastic resin composition that is lightweight and excellent in strength and rigidity. In addition, the above thermoplastic composition can be suitably used as various molded articles.

  Hereinafter, the present invention will be described in detail.

  The thermoplastic resin composition comprising at least two components of the present invention has a two-phase continuous structure having a specific structural period or a dispersed structure having a specific interparticle distance.

  The thermoplastic resin composition having such a structure is formed by phase separation by specific spinodal decomposition, specifically, after forming a biphasic continuous structure having a structural period of 0.001 to 0.1 μm in the initial stage of spinodal decomposition, It can be obtained by developing a biphasic continuous structure having a period of 0.001 to 1 μm or a dispersed structure having a distance between particles of 0.01 to 1 μm.

  In general, a thermoplastic resin composition composed of a two-component resin is compatible with these compositions in a practically compatible range of glass transition temperature or higher and thermal decomposition temperature or lower. There are incompatible systems that are incompatible with each other, and partial compatible systems that are compatible in one region and phase separated in another region. In addition, this partially compatible system is spinodal depending on the conditions of the phase separated state. Some are phase-separated by decomposition and others are phase-separated by nucleation and growth.

  Furthermore, in the case of a thermoplastic resin composition comprising three or more components, a system in which all three or more components are compatible with each other, a system in which all three or more components are incompatible, and a two or more compatible phases And a system in which the remaining one or more phases are incompatible, a two component is a partially compatible system, and a remaining component is distributed to a partially compatible system composed of the two components. The thermoplastic resin composition comprising three or more components preferred in the present invention is a system in which two components are partially compatible and the remaining components are distributed into the partially compatible system consisting of these two components. In this case, the thermoplastic resin composition Since the structure of the product can be replaced by a partially compatible structure composed of two components, the following description will be made representatively using a thermoplastic resin composition composed of a two-component resin.

  Phase separation by spinodal decomposition refers to phase separation that occurs in an unstable state inside the spinodal curve in phase diagrams for different two-component resin compositions and temperatures, and phase separation by nucleation and growth refers to the phase separation. In the figure, it refers to phase separation that occurs in the metastable state inside the binodal curve and outside the spinodal curve.

  The spinodal curve refers to the difference (ΔGmix) between the free energy when compatibilized and the sum of the free energies in two phases that are not compatible (ΔGmix) when two different resins are mixed with respect to the composition and temperature. φ) is a curve in which the partial differential twice (∂2ΔGmix / ∂φ2) is 0, and inside the spinodal curve is an unstable state of ∂2ΔGmix / ∂φ2 <0, and outside is ∂ 2ΔGmix / ∂φ2> 0.

  The binodal curve is a boundary curve between the region where the system is compatible and the region where the system is separated with respect to the composition and temperature.

  Here, the case of being compatible in the present invention is a state in which they are uniformly mixed at the molecular level. Specifically, both phases having different two-component resins as main components are 0.001 μm or more. The case where the phase structure is not formed is indicated, and the case where the phase is incompatible is the case where the phase is not in a compatible state, that is, the phases mainly composed of two different resin components are 0.001 μm or more. It refers to the state of forming a phase structure. Whether or not they are compatible is determined by, for example, an electron microscope, a differential scanning calorimeter (DSC), and various other methods as described in Polymer Alloys and Blends, Leszek A Utracki, hanser Publishers, Munich Viema New York, P64. can do.

  According to detailed theory, in spinodal decomposition, once the temperature of a mixed system that has been uniformly mixed at the temperature of the compatible region is rapidly increased to the temperature of the unstable region, the system will rapidly phase-separate toward the coexisting composition. To start. At that time, the concentration is monochromatized at a constant wavelength, and a two-phase continuous structure is formed in which both separated phases are continuously intertwined regularly with a structure period (Λm). After the formation of the two-phase continuous structure, the process in which only the concentration difference between the two phases increases while keeping the structure period constant is called the initial process of spinodal decomposition.

Furthermore, the structural period (Λm) in the initial process of the above-mentioned spinodal decomposition has a thermodynamic relationship as shown in the following equation.
[Lambda] m- [| Ts-T | / Ts] -1/2
(Where Ts is the temperature on the spinodal curve).

  Here, the two-phase continuous structure referred to in the present invention refers to a structure in which both components of the resin to be mixed each form a continuous phase and are entangled three-dimensionally. A schematic diagram of this two-phase continuous structure is described, for example, in “Polymer Alloy Fundamentals and Applications (Second Edition) (Chapter 10.1)” (edited by the Society of Polymer Science: Tokyo Kagaku Dojin).

  In spinodal decomposition, after going through such an initial process, it goes through a medium-term process in which an increase in wavelength and an increase in concentration difference occur simultaneously, and a later process in which an increase in wavelength occurs in a self-similar manner after the concentration difference reaches the coexisting composition. In the present invention, the structure is fixed when the desired structure period is reached before the separation into the macroscopic two phases. Good. In addition, in the process of increasing the wavelength from the mid-stage process to the late-stage process, depending on the influence of the composition and the interfacial tension, the continuity of one phase may be interrupted and the above-described biphasic continuous structure may be changed to a dispersed structure. In this case, the structure may be fixed when the desired interparticle distance is reached.

  Here, the dispersion structure referred to in the present invention is a so-called sea-island structure in which particles mainly composed of the other resin component are interspersed in a matrix mainly composed of one resin component. Point.

  In the present invention, by controlling the structural period of the initial process of spinodal decomposition in the range of 0.001 to 0.1 μm, the structural period of 0.01 to The structure can be controlled to have a two-phase continuous structure in the range of 1 μm or a dispersed structure in the range of a distance between particles of 0.01 to 1 μm. In order to obtain more excellent mechanical properties, after the structure is developed, a biphasic continuous structure with a structural period in the range of 0.01 to 0.5 μm, or a dispersed structure with a distance between particles of 0.01 to 0.5 μm. It is preferable to control to a two-phase continuous structure with a structural period of 0.01 to 0.3 μm or a dispersed structure with a distance between particles of 0.01 to 0.3 μm. .

  On the other hand, in the nucleation and growth, which is the phase separation in the metastable region described above, a dispersed structure that is a sea-island structure is formed from the initial stage, and it grows. It is difficult to form a biphasic continuous structure in the range of 0.01 to 1 μm or a dispersed structure in the range of a distance between particles of 0.01 to 1 μm.

Further, in order to confirm the biphasic continuous structure or the dispersed structure by spinodal decomposition, it is important to confirm a regular periodic structure. For example, in addition to confirming that a biphasic continuous structure is formed by observation with an optical microscope or a transmission electron microscope, the scattering maximum in a scattering measurement performed using a light scattering device or a small-angle X-ray scattering device Confirmation of appearing is necessary. Note that the light scattering device and the small-angle X-ray scattering device have different optimum measurement regions, so that they are appropriately selected according to the size of the structure period. The existence of the scattering maximum in this scattering measurement is a proof that it has a regular phase separation structure with a certain period, and its period Λm corresponds to the structure period in the case of the biphasic continuous structure, and the interparticle distance in the case of the dispersion structure. Correspond. Further, the value is expressed by the following equation Λm = (λ / 2) / sin (θm / 2) using the wavelength λ of the scattered light in the scatterer and the scattering angle θm that gives the scattering maximum.
Can be calculated.

  In order to realize the spinodal decomposition, it is necessary to make the resin composed of two or more components into a compatible state and then to make the unstable state inside the spinodal curve.

  As a method for realizing a compatible state with a resin composed of two or more components, it can be obtained by a method such as spray drying, freeze drying, coagulation in a non-solvent substance, or film formation by solvent evaporation after dissolving in a common solvent. And a melt kneading method by melting and kneading a partially compatible system under compatible conditions. Among these, compatibilization by melt kneading, which is a dry process that does not use a solvent, is preferably used in practice.

  For compatibilization by melt kneading, an ordinary extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing step of the injection molding machine. The temperature for compatibilization needs to be a condition in which the partially compatible resin is compatible.

  Next, when the thermoplastic resin composition made into a compatible state by melt-kneading is regarded as an unstable state inside the spinodal curve, and the spinodal decomposition is performed, the temperature for making the unstable state and other conditions vary depending on the combination of the resins. Although it cannot be generally stated, it can be set by performing a simple preliminary experiment based on the phase diagram. In the present invention, as described above, after the structural period of the initial process is controlled to a specific range, the structure is further developed after the intermediate process to obtain a specific biphasic continuous structure or a dispersed structure defined in the present invention. preferable.

  There is no particular limitation on the method for controlling the specific structural period defined in the present invention in this initial process, but it is at least the lowest temperature among the glass transition temperatures of the individual resin components constituting the thermoplastic resin composition, In addition, it is preferable to perform the heat treatment at a temperature that reduces the above-described thermodynamically defined structural period. Here, the glass transition temperature can be obtained from an inflection point generated at the time of temperature increase from room temperature at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC).

  The method for developing the structure from the initial process is not particularly limited, but a method of heat-treating at the lowest temperature or higher among the glass transition temperatures of the individual resin components constituting the thermoplastic resin composition is usually preferably used. Furthermore, when the thermoplastic resin composition has a single glass transition temperature in a compatibilized state or when the phase decomposition is proceeding, the glass transition temperature in the thermoplastic resin composition is When it is between the glass transition temperatures of the individual resin components that constitute, it is more preferable to perform heat treatment at a temperature equal to or higher than the lowest temperature among the glass transition temperatures in the thermoplastic resin composition. In addition, when a crystalline resin is used as the individual resin component constituting the thermoplastic resin composition, it is preferable that the heat treatment temperature be equal to or higher than the crystal melting temperature of the crystalline resin because the structural development by the heat treatment can be effectively obtained. The heat treatment temperature is preferably within the crystal melting temperature ± 20 ° C. of the crystalline resin in order to facilitate the control of the structure development, and more preferably within the crystal melting temperature ± 10 ° C. Here, when two or more crystalline resins are used as the resin component, the heat treatment temperature is preferably within the crystal melting temperature ± 20 ° C. based on the highest temperature among the crystal melting temperatures of the crystalline resin. Furthermore, it is more preferable that the crystal melting temperature is within ± 10 ° C. However, when the heat treatment is performed during stretching of the film and / or sheet described below, the heat treatment temperature is preferably set to be equal to or lower than the temperature rising crystallization temperature of the crystalline resin. Here, the crystal melting temperature of the crystalline resin can be determined from the peak temperature of the melting curve generated at the time of temperature increase from room temperature at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC). The temperature rising crystallization temperature of the fluorinated resin is a temperature rising rate of 20 ° C./min from room temperature with a differential scanning calorimeter (DSC) using a sample obtained by quenching a sample melted at a temperature higher than the crystal melting temperature. It can obtain | require from the peak temperature of the crystallization curve produced at the time of temperature rising.

  In addition, as a method of immobilizing the structure product by spinodal decomposition, the structure fixation of one or both components of the phase-separated phase in a short time by rapid cooling or the like, and when one is a thermosetting component, a thermosetting component Structural fixation using the fact that the phase of the resin cannot freely move due to the reaction, and structural fixation using the fact that the crystalline resin phase cannot be freely moved by crystallization when the other is a crystalline resin. However, when a crystalline resin is used, structural fixation by crystallization is preferably used.

  The resin used in the present invention is not particularly limited as long as it is used in combination with at least two components that are phase-separated by spinodal decomposition. However, such a two-component system generally has a solubility of the resin constituting the two components. This is realized by selecting the parameter difference to be small or by using one having a low molecular weight as one of the resins.

  Examples of the combination of at least two components that are phase-separated by spinodal decomposition include a combination of partially compatible systems.

  Partially compatible systems are known that have a low-temperature compatible phase diagram that facilitates compatibility at the low-temperature side in the same composition, and that that has a high-temperature compatible phase diagram that facilitates compatibility at the high-temperature side. ing. The lowest temperature between the miscible and incompatible branching temperatures in this low-temperature compatible phase diagram is called the lower critical solution temperature (LCST for short). The highest temperature among the incompatible branch temperatures is called the upper critical solution temperature (UCST for short). In the case of a low-temperature compatible phase diagram, a resin of two or more components that have become compatible using a partially compatible system can be brought to a temperature higher than the LCST and a temperature inside the spinodal curve. In the case of the figure, spinodal decomposition can be performed by setting the temperature below UCST and the temperature inside the spinodal curve.

  Examples of combinations of resins having the above high-temperature compatible phase diagram include polycarbonate and styrene-methacrylic acid copolymer, polyethylene terephthalate-polyethylene naphthalate copolymer and polyetherimide, polyethylene terephthalate / poly-p-hydroxybenzoic acid. Copolyester and polyetherimide, polyethylene terephthalate-polyethylene naphthalate copolymer and chlorinated polyethylene, polystyrene and poly-ε-caprolactone, polyvinylidene fluoride and polymethyl methacrylate, chlorinated polybutadiene and chlorinated polyethylene, polyphenylene ether and ortho Chlorostyrene-parachlorostyrene copolymer, polyphenylene ether and orthofluorostyrene-parafluorostyrene copolymer, etc. Resin combinations having a solution phase diagram include polyvinyl chloride and poly (n-alkyl methacrylate), poly (vinyl chloride) and poly (n-alkyl acrylate), poly (vinylphenol) and poly (n-alkyl methacrylate), polydimethylsiloxane and polystyrene, Polyvinylidene fluoride and polymethyl methacrylate, polyvinylidene fluoride and polyvinyl acetate, polyvinylidene fluoride and polymethyl acrylate, polyvinylidene fluoride and polyethyl acrylate, polyvinyl acetate and polymethyl acrylate, polystyrene and polyvinyl methyl ether, Polymethyl methacrylate and styrene-acrylonitrile copolymer, Polymethyl methacrylate and vinylphenol-styrene copolymer, Polyvinyl acetate and vinylidene fluoride-hexafluoroacetone copolymer, Tetramethyl Chill polycarbonate and styrene-methyl methacrylate copolymer, tetramethyl polycarbonate and styrene-acrylonitrile copolymer, polyvinylphenol and ethylene-methyl methacrylate copolymer, polyvinylphenol and ethylene-vinyl acetate copolymer, poly-ε- Caprolactone and styrene-acrylonitrile copolymer, polyisoprene and butadiene-vinylethylene copolymer, styrene-acrylonitrile copolymer and styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer and styrene-N-phenylmaleimide, Examples thereof include an ethylene-vinyl acetate copolymer and a vinylidene fluoride-hexafluoroacetone copolymer.

  In addition to spinodal decomposition by this partially compatible system, spinodal decomposition is also induced by melt kneading in non-compatible systems, for example, once compatible under shearing during melt kneading, etc., and then in an unstable state again under non-shearing. Phase separation by spinodal decomposition is also possible by so-called shear field-dependent phase dissolution / phase decomposition in which phase decomposition occurs. Has a continuous structure. Furthermore, this shear field-dependent phase dissolution / phase decomposition is the same as the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the shear field and the unstable region expands. The substantial degree of supercooling (| Ts−T |) also increases in the temperature change range, and as a result, it is easy to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, so that it is preferably used. It is done.

  In order to achieve compatibilization by shearing during such melt kneading, a normal extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing step of the injection molding machine. The temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions differ depending on the combination of the resins, and cannot be said unconditionally. Based on the phase diagram below, conditions can be set by a simple preliminary experiment. Also, as a method of reliably realizing the compatibilization in the plasticizing process of the injection molding machine, it is melt-kneaded with a twin-screw extruder in advance and compatibilized. A preferred example is a method of injection molding using the selected material.

  As a combination of the above-mentioned shear field-dependent phase dissolving / phase-decomposing resin, it is a combination in which even in an incompatible system, it is compatible under shearing and spinodal decomposition under non-shearing. Acrylonitrile copolymer, polycarbonate and polybutylene terephthalate, polystyrene and polyvinyl methyl ether, polystyrene and polyisoprene, polystyrene and polyphenylmethylsiloxane, ethylene / vinyl acetate copolymer and chlorinated polyethylene, polybutyl acrylate and chlorinated polyethylene, Polymethyl methacrylate and styrene / acrylonitrile copolymer, polypropylene and high density polyethylene, polypropylene and ethylene / α-olefin copolymer, polypropylene and ethylene / polypropylene copolymer, Pyrene and styrene / butadiene copolymer, polypropylene and styrene / butadiene copolymer hydrogenated, polycarbonate and styrene / butadiene copolymer, polycarbonate and styrene / butadiene copolymer hydrogenated, polybutylene terephthalate and styrene Examples include butadiene copolymers, hydrogenated products of polybutylene terephthalate and styrene / butadiene copolymers, among which polycarbonate and styrene / acrylonitrile copolymer, polycarbonate and polybutylene terephthalate, polypropylene and high-density polyethylene, polypropylene and ethylene. An α-olefin copolymer, polypropylene, and ethylene / polypropylene copolymer are preferred because they have excellent mechanical properties. In particular, a thermoplastic resin composition comprising a polybutylene terephthalate resin and a polycarbonate resin, and the thermoplastic resin composition having a biphasic continuous structure having a structural period of 0.01 to 1 μm has excellent strength and It is preferable at the point which has toughness.

  Furthermore, even in a compatible system, phase separation by spinodal decomposition is possible by so-called reaction-induced phase decomposition in which an unstable state is caused by a change in molecular weight accompanying a chemical reaction and the like, and phase decomposition occurs. For example, the resin component raw material, oligomer or low molecular weight material (resin component precursor) constituting the thermoplastic resin composition is compatible with the remaining resin component, and the above monomer, oligomer or low molecular weight material is highly polymerized. In the case where phase separation with other resin components occurs when the resin to be alloyed is made to be alloyed, at least one precursor of the resin components constituting the thermoplastic resin composition is used together with the remaining resin components Below, it is possible to induce spinodal degradation by reacting chemically. Also in this case, the decomposition proceeds in a spinodal decomposition manner as in the case of the partially compatible system, and a regular biphasic continuous structure is obtained. Furthermore, this reaction-induced phase decomposition has the same temperature change range as compared with the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the molecular weight change and the unstable region expands. Is more preferably used since the substantial degree of supercooling (| Ts−T |) increases, and as a result, it becomes easy to reduce the structural period in the initial stage of the spinodal decomposition in the above relational expression. In this case, the glass transition temperature and the crystal melting temperature in the case of a crystalline resin change along with the molecular weight change due to polymerization and crosslinking, and the change from phase dissolution to phase decomposition due to the molecular weight change varies depending on the system. The temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions cannot be generally stated, but the phase diagram in combination with various molecular weights Based on the above, conditions can be set by performing a simple preliminary experiment.

  In addition, the combination of the above resins that undergo reaction-induced phase decomposition is such that the precursor and the remaining resin components are once in a compatible state before the chemical reaction, and spinodal decomposition is induced by using the precursor as a resin through a chemical reaction. This chemical reaction is not particularly limited as long as it causes an increase in molecular weight, and includes polycondensation, addition polymerization such as radical polymerization, cationic polymerization, anionic polymerization, and ionic copolymerization. In addition to polymerization reactions such as polyaddition, addition condensation, and ring-opening polymerization, preferred examples include a crosslinking reaction and a coupling reaction. Usually, such chemical reactions are carried out in the presence of the remaining resin to be alloyed, resulting in reaction-induced phase decomposition. As a specific example of reaction-induced phase decomposition, for example, a resin such as polyethersulfone or phenoxy resin is compatible with an epoxy resin monomer and / or oligomer such as a bisphenol type epoxy resin, a tetrafunctional type epoxy resin, or a biphenyl type epoxy resin. A method of phase decomposition by curing an epoxy resin, or a thermosetting polyallyl ether oligomer, polyethersulfone, polysulfone, polyetherimide, polyarylate, polyamideimide, polyetheretherketone, polyetherketone, polyether One or more thermoplastic resins selected from ketone ketone are compatibilized, a thermosetting polyallyl ether oligomer is polymerized and phase decomposed, acrylic rubber is once dissolved in polyester resin, and then a crosslinking agent is added. Add the active Method of phase decomposition with increasing molecular weight by crosslinking rubber, polyester oligomer and rubbery polymer are once dissolved, and then phase decomposition is performed with increasing molecular weight by adding a chain extender and crosslinking the polyester oligomer Methods and the like.

  In addition, a third component which is a copolymer such as a block copolymer, a graft copolymer or a random copolymer containing a component constituting the thermoplastic resin composition is further added to the thermoplastic resin composition comprising the two component resins constituting the present invention. This is preferably used in order to reduce the free energy of the interface between the phase-decomposed phases and to facilitate the control of the structural period in the two-phase continuous structure and the distance between the dispersed particles in the dispersed structure. In this case, since the third component such as the copolymer is usually distributed to each phase of the thermoplastic resin composition composed of the two-component resin excluding the third component, it is handled in the same manner as the thermoplastic resin composition composed of the two-component resin. be able to.

  Although there is no restriction | limiting in particular about the composition of the resin component which comprises the (A) at least 2 component thermoplastic resin composition in this invention, (A) It is 2 with respect to 100 weight part of the at least 2 component thermoplastic resin composition. In the case of a component, the range of usually 95 parts by weight / 5 parts by weight to 5 parts by weight / 95 parts by weight is preferably used, more preferably 90 parts by weight / 10 parts by weight to 10 parts by weight / 90 parts by weight, In particular, a range of 75 parts by weight / 25 parts by weight to 25 parts by weight / 75 parts by weight is preferred because a two-phase continuous structure can be obtained relatively easily.

  The inorganic filler (B) used in the present invention may be either inorganic or organic. Examples of the inorganic hollow filler include shirasu balloon, pearlite, glass balloon, silica balloon, fly ash balloon, alumina balloon, zirconia balloon, and carbon balloon. Examples of the organic hollow filler include a phenol resin balloon, an epoxy resin balloon, a urea resin balloon, a Saran balloon, a polystyrene balloon, a polymethacrylate balloon, a polyvinyl alcohol balloon, and a styrene / acrylic balloon.

  From the viewpoint of rigidity and impact resistance, the (B) hollow filler used in the present invention is preferably an inorganic hollow filler, and more preferably a glass balloon.

  The average particle diameter of the (B) hollow filler used in the present invention is preferably 1 to 100 μm, more preferably 5 to 80 μm, and most preferably 10 to 50 μm. When the average particle diameter is less than 1 μm, the effect of weight reduction may not be obtained because the thickness of the empty sphere is thin and the pressure strength is reduced. When it exceeds 100 μm, the surface appearance of the molded product may be deteriorated. In addition, the average particle diameter of a hollow filler uses the D50 value measured by the dry measurement method using the laser diffraction type particle size distribution measuring apparatus, and makes it an average particle diameter.

  The specific gravity of the (B) hollow filler used in the present invention is preferably 0.1 to 1.0, more preferably 0.3 to 0.8. If the specific gravity is less than 0.1, the thickness of the hollow sphere is thin and the pressure-resistant strength is lowered, so that the effect of weight reduction may not be obtained during the molding process. It may be necessary to add a small amount in large quantities, and the impact resistance of the molded product may be impaired. The specific gravity is measured in accordance with ASTM-D2840 (using an air comparison pycnometer).

  The (B) hollow filler used in the present invention preferably has a pressure strength (hydrostatic pressure at which the volume reduction rate is 10% by weight or less) of 5 MPa or more, more preferably 100 MPa or more, and even more preferably 150 MPa or more. When the pressure strength is less than 5 MPa, it may be difficult to prevent the hollow filler from being destroyed by the pressure of the resin during extrusion molding by a general extruder. The pressure strength is a value of average pressure strength measured in accordance with ASTM-D3102 (using glycerol).

  As the (B) hollow filler in the present invention, those subjected to surface treatment using a silane coupling agent can be used.

  Examples of the silane coupling agent include an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a mercapto group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.

  Examples of the silane coupling agent having an amino group include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and N-2 (aminoethyl). 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3- Aminopropyltrimethoxysilane or the like can be used.

  Examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycoxypropylmethyldiethoxysilane, and 3-glycidoxy. Propyltriethoxysilane can be used.

  As the silane coupling agent having a mercapto group, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like can be used.

  As the silane coupling agent having an isocyanate group, 3-isocyanatopropyltriethoxysilane or the like can be used.

  The method for adding the (B) hollow filler used in the present invention is not particularly limited, but the method of blending into the molten resin using a side feeder or the like minimizes the crushing of the hollow microspheres. This is a preferable method.

  The blending amount of the (B) hollow filler used in the present invention is 0.1 to 50 parts by weight and 1 to 30 parts by weight with respect to (A) 100 parts by weight of the at least two-component thermoplastic resin composition. It is preferably 3 to 20 parts by weight.

  (A) When the amount is less than 0.1 part by weight with respect to 100 parts by weight of at least the two-component thermoplastic resin composition, the degree of influence on the density of the thermoplastic resin composition is low, and hollow glass spheres are used for weight reduction. Meaning may fade. If it exceeds 30 parts by weight, the volume of the hollow glass sphere occupying the entire volume of the thermoplastic resin composition becomes excessive, and the kneadability and moldability are significantly reduced, and the hollow glass sphere and the reinforcing fiber may be damaged. is there.

  In the present invention, in order to impart other properties such as mechanical strength of the resin composition, fillers other than (C) the hollow filler can be blended.

  (C) As a kind of filler other than the hollow filler, any filler such as fibrous, needle-like, plate-like, and granular can be used. Specifically, glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers Fibrous fillers such as alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, etc., acicular fillers such as wollastonite, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker Examples thereof include plate-like fillers such as talc, mica, glass flake, synthetic hydrotalcite, graphite, kaolin, and clay, and granular fillers such as molybdenum disulfide, montmorillonite, titanium oxide, and barium sulfate.

  When talc is used as a filler other than the hollow filler (C) of the present invention, the bulk density of talc is preferably 0.1 to 2.0, more preferably 0.3 to 1.5, and 0.5 to Most preferably, it is 1.0. When the bulk specific gravity is 0.1 or more, the rigidity, impact resistance and thermal stability of the resin composition tend to be further improved. When the bulk specific gravity is 2.0 or less, the appearance of the molded product of the resin composition And impact resistance tends to be further improved.

Here, the bulk density is a value obtained by the following method.
(1) Place talc on a sieve with an opening of 1.4 mm, and pass the sieve while sweeping lightly with a brush.
(2) The talc passed through the sieve is put into a receiver attached to the bulk density measuring device specified in JISK5101 until it reaches a heap.
(3) The top pile of talc is scraped off with a spatula from the inlet of the receiver, the weight of the talc in the receiver is measured, and the bulk density is calculated by the following equation.
Bulk density = weight of talc in the receiver (g) / capacity of receiver (ml).

  As a method of increasing the bulk density using raw material talc, any conventionally known granulation method can be used, and there are a case where a binder is not used and a method where a binder is used.

  As an example of a method not using a binder, there is usually a method of deaeration compression. A typical example of such a method is a method of performing roller compression with a briquetting machine or the like while degassing.

  As an example of a method using a binder, there is a method in which a liquid in which a resin or the like serving as a binder is dissolved or dispersed and talc are uniformly mixed with a mixer such as a super mixer and granulated through a granulator. Further, it is preferable to dry the talc and remove components such as water from the talc.

  The talc can be surface-treated in advance. Examples of surface treatment include chemical treatment with various treatment agents such as silane coupling agents, higher fatty acids, fatty acid metal salts, and polyalkylene glycols, as well as physical surfaces such as mechanofusion methods and high-speed air-flow impact methods. Processing is also possible. Specific examples of suitable talc include HT-7000 manufactured by Harima Kasei Co., Ltd., and B-10 and R-10 manufactured by Matsumura Sangyo Co., Ltd.

  When carbon fiber is used as a filler other than the hollow filler (C) of the present invention, there is no particular limitation, and it is produced using various known carbon fibers such as polyacrylonitrile, pitch, rayon, lignin, hydrocarbon gas and the like. Carbon fiber or graphite fiber, or a fiber obtained by coating these fibers with metal may be used. The carbon fibers are usually in the form of chopped strands, roving strands, milled fibers, etc., and have a diameter of 15 μm or less, preferably 5 to 10 μm.

  The carbon fiber used in the present invention is preferably a chopped strand, and the number of filaments of the carbon fiber strand which is a precursor of the chopped carbon fiber is preferably 1,000 to 150,000. If the number of filaments is less than 1,000, the production cost increases, and if it exceeds 150,000, the production cost increases and the stability in the production process may be greatly impaired.

  The carbon fibers used in the present invention can be suitably used that are bundled with various sizing agents. Sizing agents include epoxy resin, urethane-modified epoxy resin, epoxy-modified urethane resin, phenol resin, polyamide resin, polycarbonate resin, polyimide resin, polyetherimide resin, bismaleimide resin, polysulfone resin, polyethersulfone resin, polyvinylpyrrolidone resin And at least one resin component selected from the group consisting of a polyacrylic resin and a polyurethane resin. In the present invention, among these resin components, those containing an epoxy resin and a polyurethane resin are preferably used from the viewpoint of compatibility with the thermoplastic resin.

  When glass fiber is used as a filler other than the hollow filler (C) of the present invention, there is no particular limitation, but chopped strand type or roving type glass fiber can be used, and silanes such as aminosilane compounds and epoxysilane compounds. Glass fibers treated with a sizing agent containing a coupling agent and / or one or more epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, and novolak epoxy compounds are preferably used, and silane coupling agents and The sizing agent may be used by being mixed with the emulsion liquid. The fiber diameter is 1 to 30 μm, preferably 5 to 15 μm. In addition, although the fiber cross section is circular, a fiber reinforcing material having an arbitrary cross section such as an elliptical glass fiber, a flat glass fiber and an eyebrow-shaped glass fiber having an arbitrary aspect ratio can be used. It is characterized by improved fluidity at the time and a molded product with less warping.

  Among the fillers other than these (C) hollow fillers, in the obtained thermoplastic resin composition, when a good surface appearance, an excellent surface impact strength and a low linear expansion coefficient are required, a plate-like or granular shape Fillers are preferred, plate-like fillers are more preferred, and talc is particularly preferred. Moreover, when high rigidity and a low linear expansion coefficient are required, a fibrous filler is preferable and glass fiber is particularly preferable. Furthermore, when high rigidity, low specific gravity, and a low linear expansion coefficient are required, a fibrous filler is preferable and carbon fiber is particularly preferable.

  Fillers other than the above (C) hollow filler can also be used in combination of two or more. By using two types of talc / glass fiber and talc / carbon fiber in combination, a good surface appearance can be obtained. It becomes possible to achieve both high rigidity and high degree.

  The blending amount of the filler other than (C) the hollow filler is 0.1 to 200 parts by weight with respect to 100 parts by weight of (A) the thermoplastic resin composition of at least two components. It is preferable at the point of a physical property, It is more preferable to mix | blend in 1-150 weight part, It is further more preferable to mix | blend in 5-100 weight part.

  In the present invention, (D) an organic acid can be used for the purpose of improving the thermal stability, impact resistance and the like of the thermoplastic resin composition.

  (D) Various types of organic acids can be used, for example, fatty acids having 6 to 30 carbon atoms such as caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, arachidic acid, Examples of representative compounds include maleic anhydride and acid-modified siloxane. In particular, maleic anhydride and capric acid are preferably used.

  (D) The blending amount of the organic acid is 0.001 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition (A) of at least two components, from the viewpoint of improving thermal stability and fluidity. It is preferable that it is 0.01 to 1 part by weight. (D) If the blending amount of the organic acid is less than 0.001 part by weight, the effect of improving the melt stability is not exhibited, and if it exceeds 5 parts by weight, the fluidity and impact resistance are lowered.

  The thermoplastic resin composition of the present invention may further contain other various additives as long as the object of the present invention is not impaired. Examples of these other additives include, for example, antioxidants (phosphorus, sulfur, etc.), ultraviolet absorbers, heat stabilizers (hindered phenols, etc.), lubricants, mold release agents, antistatic agents, antiblocking agents. , Colorants including dyes and pigments, flame retardants (halogen, phosphorus, etc.), flame retardant aids (antimony compounds typified by antimony trioxide, zirconium oxide, molybdenum oxide, etc.), foaming agents, coupling agents ( Examples thereof include silane coupling agents and titanium coupling agents containing at least one epoxy group, amino group mercapto group, vinyl group, and isocyanate group, and antibacterial agents.

  These additives can be blended at an arbitrary stage for producing the thermoplastic resin composition of the present invention. For example, a method of adding at least two resins at the same time, or two components in advance. And a method of adding the resin after melt-kneading, or a method of adding the resin to one resin first and then melt-kneading, and then blending the remaining resin.

  The thermoplastic resin composition obtained from the present invention can be molded by any method, and the molded shape can be any shape. Examples of the molding method include injection molding, extrusion molding, inflation molding, blow molding and the like. Among them, injection molding is dissolved in the plasticizing process at the time of injection, and after injection, the spinodal is disassembled and the mold is formed. In the case of film and / or sheet extrusion molding, it is preferable to dissolve at the time of extrusion, to dissolve the spinodal after discharge, and to heat-treat at the time of stretching the film and / or sheet, and then to wind It is preferable because the structure can be fixed during the previous natural cooling. Of course, it is possible to heat-treat the molded product separately to form a structure. In addition, as a method for producing such a film and / or sheet, a method of melt extrusion from a T die using a single-screw or twin-screw extruder, cooling and solidifying with a cast drum, and forming a sheet between two rolls There are polishing methods, calendering methods, and the like, which are not particularly limited here. In addition, when casting the cast drum, in order to bring the molten resin into close contact with the cast drum, a method of applying an electrostatic force, a method using an air knife, a method using a pressing drum facing the cast drum, or the like can be used. Furthermore, it is more preferable to use pellets that have been previously compatibilized using a twin-screw extruder and frozen in their structure before being supplied to the extruder for film and / or sheeting. The method of stretching to form a film is not particularly limited, and may be sequential biaxial stretching or simultaneous biaxial stretching. Usually, the stretching ratio is 2 to 8 times, and the stretching speed is 500 to 5000% / min. Many are used. Furthermore, the heat treatment temperature at the time of stretching is usually preferably a method in which the heat treatment is performed at the lowest temperature or higher among the glass transition temperatures of the individual resin components constituting the thermoplastic resin composition, but the thermoplastic resin composition is in a compatible state. When the glass transition temperature in the thermoplastic resin composition has a single glass transition temperature or in the state where phase decomposition is proceeding, the glass transition temperatures of the individual resin components constituting the thermoplastic resin composition When it is in between, it is more preferable to heat-treat at the lowest temperature or higher among the glass transition temperatures in the thermoplastic resin composition. In addition, when a crystalline resin is used as the individual resin component constituting the thermoplastic resin composition, setting the heat treatment temperature to be equal to or lower than the temperature rising crystallization temperature of the crystalline resin may hinder stretching due to crystallization of the crystalline resin. From the viewpoint of making it difficult to receive.

  The thermoplastic resin composition in the present invention generally has various usage methods depending on the characteristics of its constituent components, among them, as one of the resins, a structural material having improved impact resistance using a resin having excellent impact resistance, A heat-resistant resin material with improved heat resistance using a resin with excellent heat resistance as one resin, or a functional resin material in which a functional substance is finely dispersed by loading a magnetic substance or catalyst on one resin It can be used suitably.

  Such a structural material with improved impact resistance can be suitably used for, for example, automobile parts and electric parts.

  Examples of automobile parts include alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dials, air intake nozzles snorkels, intake manifolds, air flow meters, air pumps, fuel pumps, engine coolant joints, thermostat housings, carburetors Main body, carburetor spacer, engine mount, ignition hobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, Coil base, Actuator for ABS -Case, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, timing belt Covers, brake booster parts, various cases, various tubes for fuel / exhaust / intake systems, various tanks, various hoses for fuel / exhaust / intake systems, various clips, various valves such as exhaust gas valves, various Pipe, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, brake pad wear sensor, throttle position sensor, crankshaft Transition sensor, thermostat base for air conditioner, air conditioner panel switch board, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, step motor rotor, brake piston, solenoid bobbin, engine oil Filter, igniter case, torque control lever, starter switch, starter relay, safety belt parts, register blade, washer lever, window regulator handle, knob of window regulator handle, passing light lever, distributor, sun visor bracket, various motors Housing, roof rail, fender, garnish, bumper, door Mirror stay, horn terminal, window washer nozzle, spoiler, hood louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp socket, lamp housing, lamp bezel, door handle, wire harness connector, SMJ connector, PCB connector And various connectors such as a door grommet connector and a fuse connector.

  Examples of electrical components include connectors, coils, various sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, and plugs. , Printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, generator, motor, transformer , Current transformer, voltage regulator, rectifier, inverter, relay, power contact, switch, circuit breaker, knife switch, other pole rod, electrical component cabinet, VTR component, TV component, iron, hair dryer, rice cooker component Microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs / DVDs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office computer parts, telephone equipment parts, mobile phones Related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriter-related parts, microscopes, binoculars, cameras, watches, and other optical equipment / precision machine-related parts.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

  The evaluation method of an Example and a comparative example is shown next. Unless otherwise specified, “part” indicates “part by weight” and “%” indicates “% by weight”.

(1) Falling ball impact strength The 3 mm thick square plate produced above is placed on a (vertical) 85 mm × (horizontal) 85 mm × (height) 50 mm cradle, and a 500 g hard ball from a height of 100 cm is placed in the center. It dropped and checked for cracks and cracks. After testing 10 samples prepared at −30 ° C., the height was changed and the same test was performed to obtain the height at which five or more test pieces were broken.

(2) Mold Shrinkage Ratio The dimension in the flow direction (MD direction) and the direction perpendicular to the flow (TD direction) of the molded product produced above was measured and obtained as a ratio to the original mold size. Moreover, the state of curvature was also observed from this test piece.

(3) Molding appearance The surface appearance of the 3 mm thick square plate produced above is evaluated by measuring Ra (center line average roughness, μm) using a surface roughness measuring device (manufactured by ACCRTECH). It was.

(4) Density Measured according to ASTM D-792 using a tensile test piece. In addition, compared with the theoretical value calculated | required by calculation, the destruction state of the glass balloon was considered.

(5) Measurement of structural period or interparticle distance From a 3 mm thick square plate created above, a 100 μm thick section was cut out, stained with polycarbonate by iodine staining method, and then a sample obtained by cutting out an ultrathin section. Observation was performed with a microscope at a magnification of 10,000 times, and 100 locations where the structure could be observed were arbitrarily selected, and after measuring each structural period, an average value was calculated.

The compounding composition used for the Example and the comparative example below is shown.
(A) Thermoplastic resin composition A-1: aromatic polycarbonate resin; trade name “Toughlon” A1900, manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight 19,000
A-2: Polybutylene terephthalate resin; trade name “Toraycon” 1100M, manufactured by Toray Industries, Inc., melting point 225 ° C.
A-3: Styrene-acrylonitrile copolymer; trade name “Toyolac” 1050B, manufactured by Toray Industries, Inc., glass transition temperature 102 ° C.
(B) Hollow filler B-1: glass balloon; trade name “Glass Bubbles S60HS” (true specific gravity 0.60, average particle size 30 μm, pressure strength 124 MPa)
B-2: Glass balloon; trade name “Glass Bubbles iM30K” true specific gravity 0.60, average particle diameter 18 μm, pressure strength 190 MPa)
(C) Filler other than hollow filler C-1: Talc; Trade name “HT-7000”, Harima Kasei Co., Ltd. C-2: Talc; Trade name “LMS200”, Fuji Talc Kogyo C -3: glass fiber; trade name “CS3J948”, manufactured by Nitto Boseki Co., Ltd., chopped strand shape with a fiber diameter of about 10 μm C-4: carbon fiber; trade name “TS-15”, manufactured by Toray Industries, Inc. D-1 : Maleic anhydride; trade name “CRYSTAL MAN AB”, manufactured by NOF Corporation.

Examples 1-18, Comparative Example 1, Comparative Example 3, Comparative Examples 5-7
Three kneading blocks were prepared by blending raw materials other than the hollow filler (B) so as to have the composition shown in Tables 1 and 2, dry blending, and then setting the cylinder temperature to 240 ° C. and the screw speed to 250 rpm. (B) The hollow filler is fed from the side feeder to the place where the resin pressure of the die part is melted and kneaded so that the resin pressure of the die part becomes 2 to 5 MPa with a TEX30α twin screw extruder having a part (manufactured by Nippon Steel), and discharged from the die. The strands were cooled in a cooling bath and pelletized with a strand cutter. Each pellet obtained was dried by a hot air dryer at 110 ° C. for 8 hours, and then molded by the evaluation method described above and evaluated.

Comparative Example 2, Comparative Example 4, Comparative Example 6
Except for using a PCM30 extruder that does not have a kneading block part in which the raw materials are blended so as to have the compositions shown in Tables 1 and 2 and the cylinder temperature is set to 280 ° C. and the screw rotation speed is set to 100 rpm, Example 1 and Pellets were prepared by melt kneading in the same manner. The resin pressure at this time was 0.2 MPa. Each pellet obtained was evaluated in the same manner as in Example 1.

  As shown in Tables 1 and 2, the thermoplastic resin compositions of Examples 1 to 18 are lightweight and excellent in low-temperature impact resistance, surface appearance, and dimensional stability. On the other hand, it can be seen that any of the above properties is inferior in the thermoplastic resin compositions of Comparative Examples 1-8.

Claims (5)

(A) A resin composition comprising 0.1 to 50 parts by weight of a hollow filler with respect to 100 parts by weight of a thermoplastic resin composition of at least two components, and (A) at least two components A thermoplastic resin composition, wherein the thermoplastic resin composition forms a two-phase continuous structure with a structural period of less than 0.001 to 1 μm, or a dispersed structure with a distance between particles of less than 0.001 to 1 μm. (A) The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition of at least two components comprises a polybutylene terephthalate resin and a polycarbonate resin. (B) The thermoplastic resin composition according to any one of claims 1 to 2, wherein the hollow filler is a glass balloon. (B) The thermoplastic resin composition according to any one of claims 1 to 3, wherein the hollow filler has a compressive strength of 100 MPa or more. The molded article formed by shape | molding the thermoplastic resin composition of any one of Claims 1-4.