JP2003286414A - Polymer alloy and its preparation process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer alloy which comprises at least two resins, is useful for a structural material by taking advantages of its excellent mechanical properties and for a functional material by taking advantages of its excellent regularity, has a finely controllable structure, and has a sufficiently developed concentration-difference between two phases in its structure. <P>SOLUTION: This polymer alloy is obtained by the phase separation by a spinodal decomposition and comprises at least two resins. In the early stage of the spinodal decomposition, after forming a two-phase continual structure having a structure interval of 0.001-0.1 μm, another two-phase continual structure having a structure interval of 0.01-1 μm or a dispersion structure having a distance between particles of 0.01-1 μm is furthermore developed. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can be effectively used as a structural material by taking advantage of excellent mechanical properties and as a functional material by taking advantage of excellent regularity, and can control the structure from nanometer order to micron order. Regarding polymer alloys.

[0002]

2. Description of the Related Art Polymer alloys obtained by once compatibilizing two or more kinds of resins in a one-phase state and then phase-separating them are known to consist of nucleation and growth and those of spinodal decomposition. ing.

Japanese Unexamined Patent Publication (Kokai) No. 3-20333 describes a method for producing a polymer alloy having a biphasic continuous structure by spinodal decomposition after compatibilizing two kinds of resins for the purpose of improving impact resistance. The above publication teaches that the toughness can be improved when the dispersed phase is smaller than 1 μm, but the publication does not disclose the dispersed diameter of the polymer alloy described in the publication at all. According to the studies by the present inventors, it was difficult to control the dispersion diameter to be small by the method described in the publication. Therefore, there has been a demand for a method of finely controlling the structure in order to improve the impact strength.

Further, Japanese Patent Laid-Open No. 8-113829 discloses that
A fiber obtained by melt-spinning a partially compatible polymer blend that is compatible with each other in a specific temperature range in a compatible state is then subjected to spinodal decomposition or nucleation and growth by heat treatment, etc. Polymer blend fibers having a dispersed structure of ˜0.4 μm are described. However, this method has reached a fine dispersion structure by adopting a special method of forming the structure through an extensional flow field in melt spinning, and since the shape is fixed, the usable range is There was a limitation, and a universally applicable method was desired. In the invention described in the publication, although there is an example that a fine and uniform size is obtained by initially forming a dispersed structure of 0.002 μm in the fiber cross section and growing the structure by heat treatment, Under the condition that a dispersed structure is formed, it is generally difficult to obtain a uniform dispersed state because phase decomposition occurs due to nucleation and growth.
Not suitable for structural materials with excellent mechanical properties. Up to now, a structure having excellent regularity, a fine structure, and a uniform distribution of the structure has not been known.

Further, Japanese Unexamined Patent Publication No. 9-169867 discloses that
A microporous membrane composed of a gel having a biphasic continuous structure with a periodic structure of 0.05 to 2 μm is described by spinodal decomposition between a resin and a solvent. However, this method is a method in which spinodal decomposition is carried out between a resin and a solvent, so that a gel-like porosity is finally obtained, and a biphasic continuous structure composed of two or more kinds of resins is obtained. It was impossible.

Polyester resins represented by polyethylene terephthalate and polybutylene terephthalate are excellent in mechanical properties, heat resistance, chemical resistance, weather resistance, and electrical properties, and are used in a wide range of fields such as automobiles and electric / electronic parts. ing.

Since the polyester resin has excellent heat resistance, it can be continuously used in a high temperature atmosphere. However, when the polyester resin is exposed to high temperature and high humidity for a long time, the polyester resin has a drawback that hydrolysis and thermal deterioration gradually progress and the toughness decreases.

On the other hand, since rubbery polymers are generally excellent in impact resistance and hydrolysis resistance, it is considered to be effective to use them in combination with polyester, and many studies have been conducted. There is. Among them, Japanese Patent Publication 57-540
58 and JP-B-57-59261, a method of blending a modified ethylene polymer grafted with an unsaturated carboxylic acid and its derivative into a polyester resin, and JP-B-7-62105 discloses a polyester resin, ethylene / α. A method of melt-mixing an olefin copolymer, maleic acid or its anhydride, and a radical generator is disclosed. However, although the impact resistance is improved to some extent by these methods, the effect of preventing reduction in strength and toughness after the high temperature and high humidity treatment is insufficient, and a method for finer structure control has been desired.

[0009]

DISCLOSURE OF THE INVENTION In providing a structural material having excellent mechanical properties and a functional material having excellent regularity, the present invention has excellent regularity and a fine structure. It is an object of the present invention to provide a polymer alloy which is controllable and whose structure is uniformly dispersed and which is composed of at least two-component resin.

[0010]

Means for Solving the Problems The inventors of the present invention have made extensive studies to provide a structural material having excellent mechanical properties and a functional material having excellent regularity. , A specific structural period is formed in the initial process, and then the structural period is 0.01 by heat treatment.
The inventors have found that the structure is controlled to have a biphasic continuous structure of ˜1 μm or a dispersed structure with a center distance of dispersed particles of 0.01 to 1 μm, and have completed the present invention.

That is, the present invention is (1) a polymer alloy comprising at least two resin components which are phase-separated by spinodal decomposition, and both phases having a structural period of 0.001 to 0.1 μm are formed in the initial stage of the spinodal decomposition. After forming a continuous structure, the structure period is further 0.01 to 1 μm.
(2) At least one component of the polymer component, which is a polymer alloy having a biphasic continuous structure, or a dispersed structure having an interparticle distance of 0.01 to 1 μm. Is a crystalline resin, the polymer alloy according to (1) above, (3) the polymer resin according to (2) above, characterized in that the crystalline resin is a polyester resin, and (4) the polymer alloy is at least The polymer alloy according to the above (3), which comprises one type of rubbery polymer, (5) a polymer alloy containing a polybutylene terephthalate resin and a polycarbonate resin, wherein the polymer alloy has a structural period of 0.01. A polymer alloy having a biphasic continuous structure of ˜1 μm, (6) the polymer alloy is produced by melt-kneading. The above (1)-
(5) The polymer alloy according to any one of (1), (7) the spinodal decomposition is compatible under shear during melt kneading,
The polymer alloy according to (6) above, which undergoes phase separation under non-shearing after discharge, and (8) the polymer alloy is at least one of resin components constituting the polymer alloy.
The polymer alloy according to any one of (1) to (5) above, wherein the precursor of the component is chemically reacted in the presence of the remaining resin component to induce spinodal decomposition. ) The polymer alloy according to the above (8), wherein the spinodal decomposition is one that is compatible before the chemical reaction and phase-separates after the chemical reaction. (10) The polymer alloy according to any one of (1) to (9), which is for injection molding. (11) The polymer alloy according to any one of (1) to (9) above, which is for film and / or sheet extrusion molding. (12) A method for producing a polymer alloy in which at least two resin components are phase-separated by spinodal decomposition, wherein a biphasic continuous structure having a structural period of 0.001 to 0.1 μm is formed in the initial stage of spinodal decomposition, and then a structure is further formed. Bi-phase continuous structure with a period of 0.01 to 1 μm,
Alternatively, a method for producing a polymer alloy is characterized by developing a dispersed structure having an interparticle distance of 0.01 to 1 μm.
(13) A method for producing a polymer alloy according to the above (12), which comprises inducing spinodal decomposition by melt-kneading at least two resin components, (14) at least two components under shear during melt-kneading. Compatible with resin,
(3) The method for producing a polymer alloy according to (13) above, which comprises phase separation under non-shearing after discharge, and (15) at least one precursor of the resin components constituting the polymer alloy, and the remaining resin. A method for producing a polymer alloy according to the above (12), characterized by inducing spinodal decomposition by causing a chemical reaction in the presence of components.
And (16) The method for producing a polymer alloy according to the above (15), wherein the chemical alloys are once compatible with each other before the chemical reaction and phase-separated after the chemical reaction.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The polymer alloy of the present invention, which comprises at least two resin components, has a biphasic continuous structure having a specific structural period or a dispersed structure having a specific interparticle distance.

The polymer alloy having such a structure has a structural period of 0.001 to 0.001 in the initial process of phase separation by specific spinodal decomposition, specifically, spinodal decomposition.
It can be obtained by forming a 0.1 μm biphasic continuous structure and then further developing it to a biphasic continuous structure having a structural period of 0.01 to 1 μm or a dispersed structure having an interparticle distance of 0.01 to 1 μm.

In general, a polymer alloy composed of a two-component resin is compatible with these compositions in a practically compatible range from the glass transition temperature to the thermal decomposition temperature, and vice versa. There are incompatible systems that are incompatible with each other, and partial compatible systems that are compatible with each other in one region and become phase-separated in another region. Some are phase-separated by decomposition, and some are phase-separated by nucleation and growth.

In the case of a polymer alloy composed of three or more components, a system in which all of the three or more components are compatible, a system in which all of the three or more components are incompatible, and a compatible phase of two or more components. And a system in which the remaining one or more phases are incompatible, a system in which the two components are partially compatible systems, and a system in which the remaining components are distributed into a partially compatible system composed of these two components. In the present invention, a polymer alloy composed of three or more components is a system in which two components are a partial compatible system and the remaining components are distributed in a partial compatible system composed of these two components. In this case, the structure of the polymer alloy is 2 Since a partial compatible system structure composed of components can be substituted, a polymer alloy composed of two component resins will be described below as a representative.

The phase separation by spinodal decomposition refers to the phase separation that occurs in an unstable state inside the spinodal curve in the phase diagram for different two resin compositions and temperature, and the phase separation by nucleation and growth. , Refers to phase separation that occurs in a metastable state inside the binodal curve and outside the spinodal curve in the phase diagram.

The spinodal curve means the composition and
When two different resins are mixed with respect to temperature,
In the two phases that are incompatible with the free energy when dissolved
Concentration of difference (ΔGmix) from total free energy
Partially differentiated twice by (φ) (∂ ²ΔGmix / ∂φ²)But
It is a curve that becomes 0, and within the spinodal curve
On the side, ∂²ΔGmix / ∂φ²<0 is an unstable state,
∂ on the outside²ΔGmix / ∂φ²> 0.

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

Here, the case of being compatible in the present invention means that
It means a state of being uniformly mixed at the molecular level, and specifically refers to a case where no phase mainly composed of two different resin components forms a phase structure of 0.001 μm or more. The term “incompatible” refers to the case where the components are not in a compatible state, that is, the phases in which two different resin components are main components form a phase structure of 0.001 μm or more. . Whether or not they are compatible is determined by, for example, Polyme
r Alloys and Blends, Leszek A Utracki, hanser Publ
It can be determined by an electron microscope, a differential scanning calorimeter (DSC), or various other methods as described in ishers, Munich Viema New York, P64.

According to the detailed theory, in the spinodal decomposition, when the temperature of the mixed system which has been uniformly dissolved at the temperature of the compatible region is rapidly increased to the temperature of the unstable region, the system rapidly moves toward the coexisting composition. Phase separation begins. At that time, the concentration is monochromaticized to a constant wavelength, and both separated phases are continuously formed at a structural period (Λm) to form a continuous two-phase structure. 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 structural period constant is called the initial process of spinodal decomposition.

Further, the structural period (Λm) in the initial process of the above spinodal decomposition is thermodynamically related by 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 means that both components of the resin to be mixed are continuous. A structure that forms a phase and is three-dimensionally intertwined with each other. A schematic diagram of this biphasic continuous structure is, for example, “Polymer Alloy Basics and Applications (2nd Edition)” (10.
Chapter 1) ”(Polymer Society of Japan: Tokyo Kagaku Dojin).

In spinodal decomposition, after undergoing such an initial process, a middle stage process in which an increase in wavelength and a difference in concentration simultaneously occur, and a latter stage in which a wavelength increase occurs in a self-similar manner after the concentration difference reaches a coexisting composition. The process progresses until it finally separates into two macroscopic phases. However, in the present invention, the structure is formed at the stage when the desired structural period before finally separating into two macroscopic phases is reached. Just fix it. Further, in the process of increasing the wavelength from the middle stage process to the latter stage process, the continuity of one phase may be interrupted due to the influence of the composition and the interfacial tension, and the above two-phase continuous structure may change to a dispersed structure.
In this case, the structure may be fixed when the desired interparticle distance is reached.

The term "dispersion structure" as used in the present invention means that a matrix having one resin component as a main component is interspersed with particles having the other resin component as a main component. Refers to the structure.

In the present invention, the structural period of the initial process of spinodal decomposition is controlled in the range of 0.001 to 0.1 μm, so that even if the wavelength and the concentration difference increase after the above-mentioned intermediate process, the structural period of 0 The structure can be controlled to have a biphasic continuous structure in the range of 0.01 to 1 μm or a dispersed structure in which the distance between particles is 0.01 to 1 μm. In order to obtain better mechanical properties, the structure period is 0.01 to
It is preferable to control to a biphasic continuous structure in the range of 0.5 μm or a dispersed structure in which the interparticle distance is 0.01 to 0.5 μm, and further, the structural period is 0.01 to 0.3 μm.
Biphase continuous structure in the range of, or interparticle distance 0.01 to
It is more preferable to control the dispersion structure in the range of 0.3 μm.

On the other hand, in the nucleation and growth which are the phase separation in the above metastable region, a dispersed structure which is a sea-island structure is formed from the initial stage, and it grows. It is difficult to form a biphasic continuous structure having an average structural period of 0.01 to 1 μm or a dispersed structure having an interparticle distance of 0.01 to 1 μm.

Further, in order to confirm the biphasic continuous structure or dispersion structure due to these spinodal decomposition, it is important to confirm a regular periodic structure. This is, for example, by optical microscope observation and transmission electron microscope observation,
In addition to confirmation that a biphasic continuous structure is formed, it is necessary to confirm that a scattering maximum appears in scattering measurement performed using a light scattering device or a small-angle X-ray scattering device. In addition,
Since the light scattering device and the small-angle X-ray scattering device have different optimum measurement regions, they are appropriately selected and used according to the size of the structural period. The existence of the scattering maximum in this scattering measurement is proof that it has a regular phase-separated structure with a certain period, and its period Λm corresponds to the structural period in the case of a two-phase continuous structure, and the interparticle distance in the case of a dispersed structure. Correspond. The values are the wavelength λ of scattered light inside the scatterer and the scattering angle θ that gives the maximum scattering.
It can be calculated by the following formula Λm = (λ / 2) / sin (θm / 2) using m.

In order to realize the spinodal decomposition,
It is necessary to make the resin composed of two or more components compatible with each other, and then to make the resin unstable inside the spinodal curve.

First, as a method for achieving a compatible state with a resin composed of two or more components, after dissolving in a common solvent, spray-drying, freeze-drying from this solution, coagulation in a non-solvent substance, film formation by solvent evaporation, etc. And a melt-kneading method in which a partially compatible system is melt-kneaded under compatible conditions. Of these, compatibilization by melt-kneading, which is a dry process that does not use a solvent, is preferably used in practice.

A usual extruder is used for compatibilization by melt-kneading, but it is preferable to use a twin-screw extruder. In addition, depending on the combination of resins, it may be possible to perform compatibilization in the plasticizing step of the injection molding machine. The temperature for compatibilization needs to be a condition under which the partially compatible resin is compatible.

Next, when the polymer alloy made compatible by melt-kneading is made into an unstable state inside the spinodal curve, the temperature and other conditions for making the unstable state in spinodal decomposition differ depending on the combination of resins. Although it cannot be generally stated, it can be set by conducting a simple preliminary experiment based on the phase diagram. In the present invention, as described above, after controlling the structural period of the initial process to a specific range, it is possible to further develop the structure 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 of controlling the specific structural period defined in the present invention in this initial process,
It is preferable to perform the heat treatment at a temperature not lower than the lowest glass transition temperature of the individual resin components constituting the polymer alloy and at a temperature at which the above-mentioned thermodynamically defined structural period is reduced. Here, the glass transition temperature can be obtained from a point of inflection that occurs when the temperature is raised from room temperature at a heating rate of 20 ° C./min with a differential scanning calorimeter (DSC).

The method of developing the structure from this initial process is not particularly limited, but a method of heat treatment at the lowest temperature or higher of the glass transition temperatures of the individual resin components constituting the polymer alloy is usually preferably used. Furthermore, when the polymer alloy has a single glass transition temperature in the compatibilized state, or when the phase decomposition is progressing, the glass transition temperature in the polymer alloy is the glass transition of each resin component constituting the polymer alloy. When the temperature is between the temperatures, it is more preferable to perform the heat treatment at the lowest temperature or higher among the glass transition temperatures in the polymer alloy. Further, when a crystalline resin is used as an individual resin component constituting the polymer alloy, it is preferable that the heat treatment temperature is equal to or higher than the crystal melting temperature of the crystalline resin because the structure development by the heat treatment can be effectively obtained. It is preferable to set the heat treatment temperature within the crystal melting temperature of the crystalline resin ± 20 ° C in order to facilitate the control of the above-mentioned structural development, and more preferably within the crystal melting temperature ± 10 ° C. 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., and more preferably within the crystal melting temperature ± 10 ° C., based on the highest temperature among the crystal melting temperatures of the crystalline resin. preferable. However, when the film and / or sheet to be described later is subjected to heat treatment at the time of stretching, the heat treatment temperature is preferably equal to or lower than the temperature rising crystallization temperature of the crystalline resin. Here, the crystal melting temperature of the crystalline resin means that the temperature is from room temperature to 20 with a differential scanning calorimeter (DSC).
It can be determined from the peak temperature of the melting curve that occurs when the temperature is raised at a heating rate of ° C / min, and the temperature rise of the crystallization resin is the temperature obtained by quenching a sample melted at the crystal melting temperature or higher. Differential scanning calorimeter (DS)
In C), it can be determined from the peak temperature of the crystallization curve generated when the temperature is raised from room temperature at a rate of 20 ° C./min.

Further, as a method for immobilizing the structural product by spinodal decomposition, the structural immobilization of one or both components of the phase-separated phase in a short time such as rapid cooling, or when one is a thermosetting component Structural fixation using the fact that the phase of the curable component cannot move freely due to reaction,
Furthermore, when one is a crystalline resin, structural fixation utilizing the fact that the crystalline resin phase cannot move freely due to crystallization can be mentioned. Among them, when a crystalline resin is used, structural fixation by crystallization is preferable. Used.

Regarding the resin used in the present invention,
There is no particular limitation as long as at least two components that are phase-separated by spinodal decomposition are used in combination, but such a two-component system is generally selected so that the difference in the solubility parameter of the resins constituting the two components becomes small. Alternatively, it is realized by using one of the resins having a low molecular weight.

The combination of at least two components which are phase-separated by spinodal decomposition includes, for example, a combination of partially compatible systems.

The partially compatible system has a low temperature compatible type phase diagram that facilitates compatibility on the low temperature side with the same composition, or a high temperature compatible type phase diagram that facilitates compatibility on the high temperature side. It has been known. The lowest branching temperature of compatible and incompatible in this low temperature compatible phase diagram is the lower critical commutation temperature.
(lower critical solution temperature LCS for short
T), which is the highest branching temperature of compatible and noncompatible phases in the high temperature compatible phase diagram.
It is called abbreviated as UCST).

In the case of a low temperature compatibility type phase diagram, two or more resins which have been made compatible with each other by using the partial compatibility system can be used by adjusting the temperature to a temperature above LCST and a temperature inside the spinodal curve to obtain a high temperature phase. In the case of a solution phase diagram, spinodal decomposition can be carried out at a temperature below UCST and a temperature inside the spinodal curve.

Examples of the combination 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 polymethylmethacrylate, chlorinated polybutadiene and chlorinated polyethylene, polyphenylene ether and orthochlorostyrene-parachlorostyrene copolymer, polyphenylene ether and orthofluorostyrene-parafluorostyrene copolymer and the like. Further, as a combination of the resins having the above-mentioned low temperature compatible phase diagram, polyvinyl chloride and poly (n-alkyl methacrylate), polyvinyl chloride and poly (n-alkyl acrylate), polyvinyl phenol and poly (n-alkyl methacrylate), Polydimethylsiloxane and polystyrene, polyvinylidene fluoride and polymethylmethacrylate,
Polyvinylidene fluoride and polyvinyl acetate, polyvinylidene fluoride and polymethyl acrylate, polyvinylidene fluoride and polyethyl acrylate, polyvinyl acetate and methyl polyacrylate, polystyrene and polyvinyl methyl ether, polymethyl methacrylate and styrene-acrylonitrile Polymer, polymethylmethacrylate and vinylphenol-styrene copolymer, polyvinylacetate and vinylidene fluoride-hexafluoroacetone copolymer, tetramethylpolycarbonate and styrene-methylmethacrylate copolymer, tetramethylpolycarbonate and styrene- Acrylonitrile copolymer, polyvinylphenol and ethylene-methylmethacrylate copolymer, polyvinylphenol and ethylene-vinylacetate copolymer, poly-ε-caprolactone and styrene Down - acrylonitrile copolymers, polyisoprene and butadiene - vinyl ethylene copolymer,
Styrene-acrylonitrile copolymer and styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer and styrene-N-phenylmaleimide, ethylene-
Examples thereof include vinyl acetate copolymer and vinylidene fluoride-hexafluoroacetone copolymer.

In addition to the spinodal decomposition by this partially compatible system, inducing spinodal decomposition by melt-kneading also in a non-compatible system, for example, once compatibilized under shear during melt-kneading and again under non-shear Phase separation by spinodal decomposition is also possible by so-called shear field-dependent phase dissolution / phase decomposition, which leads to a stable state and phase decomposition.In this case as well, the decomposition proceeds in the spinodal decomposition mode in the same manner as in the case of the partial compatible system It has a continuous biphasic structure.
Furthermore, this shear field-dependent phase dissolution / phase decomposition is the same as the method by the temperature change of the partial compatible system where the spinodal curve does not change because the spinodal curve changes due to the shear field and the unstable state region expands. Even in the range of temperature change, the substantial degree of supercooling (| Ts-T |) increases,
As a result, it becomes easier to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, and thus it is more preferably used.

For compatibilizing under shear during such melt-kneading, an ordinary extruder is used, but it is preferable to use a twin-screw extruder. In addition, depending on the combination of resins, it may be possible to perform compatibilization 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 structurally developing from the initial process, and other conditions differ depending on the combination of resins and cannot be generally stated, but various shearing conditions The conditions can be set by performing a simple preliminary experiment based on the phase diagram below. Further, as a method for surely realizing the compatibilization in the plasticizing step of the injection molding machine, it is melt-kneaded and compatibilized with a twin-screw extruder in advance, and after discharge, it is rapidly cooled in ice water or the like to fix the structure in the compatibilized state. A preferable example is a method of injection molding using the above materials.

The combination of the above-mentioned shear-field-dependent phase-dissolving / phase-decomposing resins is a combination that is compatible even under incompatibility and undergoes spinodal decomposition under non-shear, such as polycarbonate. And styrene-acrylonitrile copolymer, polycarbonate and polybutylene terephthalate, polystyrene and polyvinyl methyl ether, polystyrene and polyisoprene, polystyrene and polyphenylmethyl siloxane, ethylene / vinyl acetate copolymer and chlorinated polyethylene, polybutyl acrylate and chlorine Polyethylene, poly (methyl methacrylate) and styrene / acrylonitrile copolymer, polypropylene and high density polyethylene, polypropylene and ethylene / α
-Olefin copolymer, polypropylene and ethylene-polypropylene copolymer, polypropylene and styrene-butadiene copolymer, hydrogenated product of polypropylene and styrene-butadiene copolymer, polycarbonate and styrene
Butadiene copolymers, hydrogenated products of polycarbonate and styrene-butadiene copolymers, polybutylene terephthalate and styrene-butadiene copolymers, hydrogenated products of polybutylene terephthalate and styrene-butadiene copolymers, and the like. Polycarbonate and styrene
Acrylonitrile copolymer, polycarbonate and polybutylene terephthalate, polypropylene and high-density polyethylene, polypropylene and ethylene / α-olefin copolymer, and polypropylene and ethylene / polypropylene copolymer are preferred because they have excellent mechanical properties. In particular, a polymer alloy containing a polybutylene terephthalate resin and a polycarbonate resin, and the polymer alloy having a biphasic continuous structure with a structural period of 0.01 to 1 μm is preferable because it has excellent strength and toughness.

Further, even in a compatible system, phase separation by spinodal decomposition is possible also by so-called reaction-induced phase decomposition, which causes an unstable state due to a change in molecular weight accompanying a chemical reaction and the like. For example, the raw material of the resin component constituting the polymer alloy, the oligomer or the low molecular weight substance (precursor of the resin component) is a compatible system with the remaining resin component,
A precursor of at least one of the resin components constituting the polymer alloy, in the case where the above-mentioned monomer, oligomer or low molecular weight substance has a high degree of polymerization and phase separation occurs with other resin components when it is made into a resin to be alloyed. It is possible to induce spinodal decomposition by chemically reacting with the other resin component in the coexistence. In this case as well, as in the case of the partially compatible system, the decomposition proceeds in the spinodal decomposition mode and has a regular biphasic continuous structure.
Furthermore, in this reaction-induced phase decomposition, the spinodal curve changes due to the molecular weight change, and the unstable state region expands, so compared with the method by the temperature change of the partial compatible system in which the spinodal curve does not change, the same temperature change width Also, since the substantial degree of supercooling (| Ts-T |) becomes large, and as a result, it becomes easy to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, it is more preferably used. In this case, the glass transition temperature and the crystal melting temperature in the case of a crystalline resin change due to the change in the molecular weight due to polymerization or crosslinking, and the change from phase dissolution to phase decomposition due to the change in the molecular weight is different depending on the system. The temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for structural evolution from the initial process, and other conditions cannot be said unequivocally, but the phase diagram in combination with various molecular weights Based on the above, the conditions can be set by performing a simple preliminary experiment.

The above-mentioned reaction-induced phase decomposition resin combination is such that the precursor and the remaining resin components are once in a compatible state before the chemical reaction, and the precursor is made into a resin by the chemical reaction to effect spinodal decomposition. Is a combination of resins that induces, and the chemical reaction is not particularly limited as long as it causes an increase in molecular weight, such as polycondensation, radical polymerization, cationic polymerization, anionic polymerization, and ionic copolymerization. In addition to polymerization reactions such as addition polymerization, polyaddition, addition condensation and ring-opening polymerization, crosslinking reaction and coupling reaction can be mentioned as preferable examples. Usually, the reaction-induced phase decomposition occurs by carrying out such a chemical reaction in the presence of the remaining resin which alloys. As a specific example of the reaction-induced phase decomposition, for example, a resin such as a polyether sulfone or a 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. And a method of causing phase decomposition by curing an epoxy resin, or a thermosetting polyallyl ether oligomer, polyethersulfone, polysulfone, polyetherimide, polyarylate, polyamideimide, polyetheretherketone, polyetherketone, polyether Ketone A method of compatibilizing one or more thermoplastic resins selected from ketone and polymerizing a thermosetting polyallyl ether oligomer to cause phase decomposition, acrylic rubber is once phase-dissolved in polyester resin, and then a cross-linking agent is added. Add the ac Method to cause phase decomposition with increasing molecular weight by cross-linking rubber, once the polyester oligomer and rubbery polymer are phase-dissolved, and then a chain extender is added to cause phase decomposition with increasing molecular weight by cross-linking the polyester oligomer Methods and the like.

When at least one of the resin components constituting the polymer alloy is a crystalline resin, at least one component is crystallized because the crystallization of the crystalline resin phase facilitates fixing the structure of the polymer alloy. It is preferably a resin.

The crystalline resin referred to in the present invention is not particularly limited as long as it is a resin whose crystal melting temperature is observed by a differential scanning calorimeter (DSC). For example, polyester resin, polyethylene, Polyolefin such as polypropylene, polyvinyl alcohol, polyvinyl chloride, etc.
Examples thereof include vinyl.

As the above-mentioned polyester resin, a polymer or copolymer obtained by a condensation reaction containing a dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative) as main components, or these A mixture may be mentioned.

As the above-mentioned dicarboxylic acid, terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecanedioic acid, alicyclic compounds such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Examples include dicarboxylic acids and their ester-forming derivatives. The diol component is an aliphatic glycol 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. , Cyclohexanedimethanol, cyclohexanediol and the like, or long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like, and ester-forming derivatives thereof and the like.

Preferred examples of these polymers or copolymers are polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxyl). Rate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / 5-sodium sulfoisophthalate),
Examples thereof include polybutylene (terephthalate / 5-sodium sulfoisophthalate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, and the like. Polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / Decanedicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / adipate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, etc. are particularly preferable,
Most preferred is polybutylene terephthalate.

Further, these polyester resins have an intrinsic viscosity of 0.36 to 1.60 dl / g, especially 0.52 to 1.35 when measured at 25 ° C. in an o-chlorophenol solution.
Those in the range of dl / g are preferable from the viewpoint of mechanical properties and moldability.

Further, the polymer alloy of the present invention preferably contains at least one rubber-like polymer in order to improve its impact strength and its resistance to hydrolysis under wet heat.

Examples of the rubbery polymer include polybutadiene, polyisoprene, random copolymers of styrene-butadiene and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene. Diene rubbers such as copolymers, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins, ethylene- Methacrylate, copolymers with ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylic ester-butadiene copolymers, acrylic rubber such as butyl acrylate-butadiene copolymer, ethylene such as ethylene-vinyl acetate And fatty acid Copolymers of Le, ethylene - propylene - ethylidene norbornene copolymer, ethylene -
Examples thereof include ethylene-propylene non-conjugated diene terpolymer such as propylene-hexadiene copolymer, butylene-isoprene copolymer, and chlorinated polyethylene.

Acrylic rubber, which has been mentioned as an example of the above-mentioned reaction-induced phase decomposition method, is once phase-dissolved in a polyester resin, and then a crosslinking agent is added to cause phase decomposition with an increase in the molecular weight by crosslinking the acrylic rubber. The acrylic rubber used in the method is preferably an olefin / acrylic acid ester copolymer rubber, and examples of this include at least one α-olefin and at least one C1 to
The thing manufactured by polymerizing C18 alkyl (meth) acrylate (acrylate or methacrylate) is mentioned.
Further, in order to crosslink the acrylic rubber, it is effective to copolymerize a small amount of a functional group-containing unsaturated monomer capable of imparting a crosslinking site to the acrylic rubber. Such a functional group-containing unsaturated monomer contains an acid group, a hydroxyl group, an epoxy group, an isocyanate group, an amine group, an oxazoline group, a diene group, or another functional group reactive with a crosslinking agent. When such a functional group-containing unsaturated monomer is not copolymerized, the crosslinking site can be generated by, for example, partial hydrolysis of the ester group of the rubber. Suitable α-olefins for the polymerization of such a copolymer rubber include ethylene, propylene, butene-1,
Included are isobutylene, pentene, heptene, octene, and the like and mixtures thereof, with C1-C4 alpha-olefins being preferred and ethylene being most preferred. Suitable alkyl (meth) acrylates for copolymerization with α-olefins are methyl acrylate, ethyl acrylate, t-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid. Included are methyl, n-butyl methacrylate, and the like and mixtures thereof. C1-C12 alkyl (meth) acrylates are often preferred, and C1-C4 alkyl (meth) acrylates.
Most often acrylate is most preferred. Among them, a terpolymer of ethylene, a C1-C4 alkyl acrylate and a functional group-containing unsaturated monomer whose functional group is an acid group is preferable, and a specific composition of such a terpolymer is at least about ethylene. 30 mol%, methyl acrylate about 10 ~
69.5 mol%, and monoethyl maleate about 0.5-10
Those containing mol% are preferable examples. It is preferred that the acrylic rubber be essentially amorphous and have a glass transition temperature below room temperature, that is, below about 23 ° C.

The crosslinking agent used to crosslink the acrylic rubber is a polyfunctional compound selected to crosslink the rubber by covalently bonding with the reactive functional groups of the acrylic rubber,
That is, it means at least a bifunctional compound. When the rubber has carboxy functional groups derived from, for example, acrylic acid or maleic acid units, covalent crosslinkers include hydroxyl, amine, isocyanato, epoxy or other acid reactive functional groups. The use of compounds having is suitable. Effective cross-linking agents include diols such as bisphenol A, polyols such as pentaerythritol, amines such as methylene dianiline and diphenyl guanidine, toluene diisocyanate, polyester having isocyanate as an end group. There may be mentioned isocyanates such as oligomers and epoxides such as diglycidyl ether of bisphenol A. Generally, the amount of the cross-linking agent used depends on the molecular weights of the acrylic rubber and the cross-linking agent, but is usually not more than about 15% by weight of the acrylic rubber.

The method of adding the above-mentioned crosslinking agent is not particularly limited, but in order to obtain the effect of the present invention, a method of adding it to the alloy once made compatible and crosslinking it by causing a crosslinking reaction is mentioned as a preferable method. To be For example, a method of melt-kneading in an extruder such as a single-screw or twin-screw extruder after adding a cross-linking agent to the alloy once made compatible,
Examples include a method in which a resin forming an alloy is first added from a main feeder of an extruder such as a shaft extruder, melt-kneaded, and then the cross-linking agent is additionally added from an intermediate portion of the extruder. When the cross-linking reaction of the cross-linking agent is slow and the time required for compatibilizing the alloy component is shorter than the time required for cross-linking, the resin constituting the alloy and the cross-linking agent are blended at the same time, and a single-screw or twin-screw extruder is used. It is also possible to melt-knead at the same time with an extruder such as.

The polyester oligomer to be used when the polyester oligomer and the rubbery polymer are once phase-dissolved, and then a chain extender is added to extend the chain of the polyester oligomer.
Those having an intrinsic viscosity in the range of 0.1 to 0.35 dl / g, particularly 0.2 to 0.3 dl / g, are preferably used. The chain extender used for such chain extension is
There is no particular limitation as long as it has a bifunctional or higher functional group, for example, an isocyanate compound,
Examples include oxazoline compounds, phenyl carbonate-based or phenyl ester-based compounds, lactam compounds, epoxy compounds, aromatic tetracarboxylic acid anhydrides, and the like. Preferred are isocyanate compounds, oxazoline compounds and phenyl carbonate compounds. These may be used alone or in combination of two or more as needed.

Examples of the isocyanate compound used in the chain extender include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 2, Examples thereof include 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and norbornene diisocyanate, but are not limited thereto. Further, as the isocyanate compound, a dimerized and carbodiimidated compound may be used. Further, two or more of these may be used in combination. Preferred examples include 4,4′-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

The oxazoline compound used as the chain extender is a compound having two or more oxazoline rings in one molecule, such as 2,2-bis (2-oxazoline),
1,3-bis (4,5-dihydro-2-oxazoyl)
Benzene, 1,4-bis (4,5-dihydro-2-oxazoyl) benzene, 2,2-bis (4-methyl-2-oxazoline), 2,2-bis (4,4-dimethyl-2-oxazoline) ), 2,2-bis (4-ethyl-2-oxazoline), 2,2-bis (4,4-diethyl-2-oxazoline), 2,2-bis (4-propyl-2-oxazoline),
2,2-bis (4-butyl-2-oxazoline), 2,2-
Bis (4-hexyl-2-oxazoline), 2,2-bis (4-phenyl-2-oxazoline), 2,2-bis (4-
Cyclohexyl-2-oxazoline), 2,2-bis (4-
Benzyl-2-oxazoline), 2,2-ethylenebis (2-oxazoline), 2,2-tetramethylenebis (2
-Oxazoline), 2,2-hexamethylenebis (2-oxazoline), 2,2-octamethylenebis (2-oxazoline), 2,2-ethylenebis (4-ethyl-2-oxazoline), 2,2- Tetraethylene bis (4-ethyl-2-
Examples thereof include bisoxazoline compounds such as oxazoline) and 2,2-cyclohexylenebis (4-ethyl-2-oxazoline), and preferably 2,2-bis (2-oxazoline).

Examples of the phenyl carbonate compound or phenyl ester compound used for the chain extender include diphenyl carbonate, diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate,
Diphenyl 2,6-naphthalenedicarboxylate, 1,5-
Examples thereof include diphenyl naphthalenedicarboxylate, diphenyl 2,7-naphthalenedicarboxylate, and diphenyl 4,4-biphenyldicarboxylic acid, but are not limited thereto. Preferably, diphenyl carbonate, diphenyl terephthalate and diphenyl phthalate may be used alone or in admixture of two or more.

Examples of the lactam compound used as the chain extender include compounds represented by the following general formula (1), wherein Ar is an arylene group having 6 to 20 carbon atoms, specifically p-phenylene, m-phenylene, o-phenylene, 2,6-naphthylene, 1,5-naphthylene, 2,7
-Naphthylene and 4,4'-biphenylene, but not limited thereto.

[0061]

[Chemical 1]

Examples of the epoxy compound used as the chain extender include diglycidyl esters of various aromatic dicarboxylic acids such as terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and phthalic acid diglycidyl ester, and p-phenylenediglycidyl ester. Aromatic diglycidyl ethers including ethers, diglycidyl esters of various aliphatic dicarboxylic acids, diethylene glycol diglycidyl ether, and the like,
It is not limited to this.

As the aromatic tetracarboxylic acid anhydride used for the chain extender, for example, pyromellitic dianhydride,
Examples thereof include 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, but are not limited thereto.

The above-mentioned various chain extenders are usually used in an equivalent amount to 1.5 times the molar amount of the polymer in the reaction system.
The optimum amount of addition depends on the type of chain extender used, reaction temperature, and the like. If the amount added is small, the chain extension reaction may be insufficient.

The method of adding the above-mentioned chain extender is not particularly limited, but in order to obtain the effects of the present invention, a method of adding to the alloy which has been once compatibilized and causing the chain extension reaction to extend the chain is a preferred method. As. For example, a method of melt-kneading in a single-screw or twin-screw extruder or the like after adding a chain extender to the alloy once made compatible, or alloying from a main feeder of an extruder such as a single-screw or twin-screw extruder Examples of the method include a method in which the resin or oligomer constituting the above is first added, melt-kneaded, and then the chain extender is additionally added from the intermediate part of the extruder. When the reaction of the chain extender is slow and the time for compatibilizing the alloy component is shorter than the time required for chain extension, the resin or oligomer forming the alloy and the chain extender are blended at the same time, and the uniaxial or It is also possible to simultaneously melt-knead with an extruder such as a twin-screw extruder.

Further, it is possible to add a third component, which is a copolymer such as a block copolymer, a graft copolymer or a random copolymer, containing the component constituting the polymer alloy, to the polymer alloy comprising the two-component resin constituting the present invention. It is preferably used because it lowers the free energy of the interface between the phases decomposed and facilitates the control of the structural period in the biphasic continuous structure and the distance between dispersed particles in the dispersed structure. In this case, usually, the third component such as the copolymer is distributed to each phase of the polymer alloy composed of the two-component resin excluding the third component, and therefore can be handled like the polymer alloy composed of the two-component resin.

The composition of the resin component constituting the polymer alloy of the present invention is not particularly limited, but in the case of two components, it is usually 95% by weight / 5% by weight to 5% by weight / 95% by weight.
Is preferably used, and further 90% by weight / 10
The range of 10% by weight to 90% by weight is more preferable, and the range of 75% by weight / 25% by weight to 25% by weight / 75% by weight is particularly preferable because it is relatively easy to obtain a two-phase continuous structure. To be

The polymer alloy of the present invention may further contain various other additives as long as the object of the present invention is not impaired. As these other additives, for example, talc, kaolin, mica, clay, bentonite, sericite, basic magnesium carbonate, aluminum hydroxide, glass flakes, glass fiber, carbon fiber, asbestos fiber, rock wool, calcium carbonate, Quartz sand,
Wallacenite, barium sulfate, glass beads, titanium oxide and other reinforcing materials, non-plate fillers, or antioxidants (phosphorus, sulfur, etc.), UV absorbers, heat stabilizers (hindered phenol, etc.), Lubricants, mold release agents, antistatic agents, antiblocking agents, colorants including dyes and pigments, flame retardants (halogen-based, phosphorus-based, etc.), flame retardant aids (antimony compounds typified by antimony trioxide, zirconium oxide) , Molybdenum oxide), a foaming agent, a coupling agent (a silane coupling agent or a titanium coupling agent containing at least one of an epoxy group, an amino group, a mercapto group, a vinyl group, and an isocyanate group), an antibacterial agent, and the like.

These additives can be added at any stage of producing the polymer alloy of the present invention,
For example, a method of simultaneously adding at least two-component resin, a method of adding after melt-kneading the two-component resin in advance, a method of adding to one resin first and melt-kneading, and then mixing the remaining resin And the like.

The method for molding the polymer alloy obtained from the present invention can be any method, and the molding 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 phase-dissolved in the plasticizing step at the time of injection, and after injection, spinodal decomposition is performed and the inside of the mold is decomposed. It is preferable that the heat treatment and the structure fixing can be performed at the same time, and in the case of film and / or sheet extrusion molding, they are phase-dissolved during extrusion, spinodal decomposed after discharge and heat treated during film and / or sheet stretching, and then wound up. It is preferable because the structure can be fixed during the previous natural cooling. Of course, it is also possible to heat treat the above-mentioned molded article separately to form a structure. As the method for producing such a film and / or sheet, a method of melt-extruding from a T-die using a single-screw or twin-screw extruder, cooling and solidifying with a cast drum to form a sheet, a melt-extruded sheet between two rolls There is a polishing method and a calendering method for molding with, but the method is not particularly limited here. Also when casting on 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 of using an air knife, a method of using a pressing drum facing the cast drum, or the like can be used. Further, it is more preferable to use pellets that have been preliminarily compatibilized using a twin-screw extruder and frozen in their structure before being fed to the extruder for film and / or sheet formation. Further, the method of stretching to form a film is
There is no particular limitation, sequential biaxial stretching or simultaneous biaxial stretching may be used, and the stretching ratio is usually between 2 and 8 and the stretching speed is 5
It is often used between 00 and 5000% / min. Further, as the heat treatment temperature during stretching, a method of heat treatment at the lowest temperature or higher of the glass transition temperatures of the individual resin components constituting the polymer alloy is usually preferably used, but the polymer alloy has a single glass transition temperature in a compatibilized state. When the temperature is high or the glass transition temperature in the polymer alloy in the state where phase decomposition is progressing is between the glass transition temperatures of the individual resin components constituting the polymer alloy, It is more preferable to perform the heat treatment at the lowest temperature or higher of the glass transition temperatures. When a crystalline resin is used as an individual resin component that constitutes the polymer alloy, setting the heat treatment temperature to be equal to or lower than the temperature rising crystallization temperature of the crystalline resin makes it difficult to prevent stretching due to crystallization of the crystalline resin. From the viewpoint of

The polymer alloy of the present invention generally has various uses depending on the characteristics of its constituent components.
Among them, as one resin, a structural material having high impact resistance using a resin having excellent impact resistance, or a heat-resistant resin material having high heat resistance using a resin having excellent heat resistance as one resin, or It can be suitably used for a functional resin material in which a magnetic material, a catalyst, or the like is carried on a resin and a functional component is finely dispersed. Further, the structural control of the present invention can be preferably used for a transparent resin material that utilizes the fact that the wavelength can be controlled to a wavelength of visible light or less.

The structural material having improved impact resistance can be suitably used for, for example, automobile parts and electric parts.

Examples of automobile parts are an alternator terminal, an alternator connector, an IC regulator, a potentiometer base for light deer,
Air intake nozzle snorkel, intake manifold, air flow meter, air pump, fuel pump, engine cooling water joint, thermostat housing, carburetor 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,
Accelerometer, distributor cap, coil base, ABS actuator 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 cover, brake booster parts, various cases, various tubes for fuel / exhaust system / intake system, various tanks, fuel / exhaust Various hoses for various systems and intake systems, various clips,
Various valves such as exhaust gas valves, various pipes, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, brake pad wear sensors,
Throttle position sensor, crankshaft position sensor, air conditioner thermostat base, air conditioner panel switch board, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, step motor rotor,
Brake piston, solenoid bobbin, engine oil filter, ignition device case, torque control lever, starter switch, starter relay, safety belt parts, register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, dusty Viewer, sun visor bracket, various motor housings, roof rails, fenders, garnish, bumpers, door mirror stays, horn terminals,
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,
Examples include various connectors such as PCB connectors, door grommet connectors, fuse connectors, and the like.

As examples of electric parts, connectors,
Coil, various sensors, LED lamp, socket, resistor, relay case, small switch, coil bobbin, condenser, variable capacitor case, optical pickup, oscillator,
Various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts , Generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts,
Switch, circuit breaker, knife switch, other pole rod, electric parts cabinet, VTR parts, TV parts, iron,
Hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disk (registered trademark) / compact disk / DVD, lighting parts, refrigerator parts, air conditioner parts, typewriter parts,
Word processor parts, office computer related parts, telephone related parts, mobile phone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriter related parts, microscopes, binoculars, cameras, watches, etc. Optical equipment / precision machinery related parts.

[0075]

EXAMPLES The effects of the present invention will be further described below with reference to examples. Examples 1 to 5 A twin-screw extruder (PCM-3 manufactured by Ikegai Kogyo Co., Ltd.) was used, in which a raw material having the composition shown in Table 1 was set at an extrusion temperature of 250 ° C.
0) and discharged from the die, the gut was immediately cooled in ice water to fix the structure. All of the guts were transparent, and the guts were stained with a polycarbonate by an iodine staining method, and a sample obtained by cutting out an ultrathin section was observed with a transmission electron microscope at a magnification of 100,000 times. In all of the samples, it was confirmed that no structure having a size of 0.001 μm or more was observed and they were compatibilized.
This indicates that the system compatibilizes under shear in an extruder at an extrusion temperature of 250 ° C. Also 1 from the gut
The glass transition temperature of the sample cut out at 0 mg was measured by DSC.
Table 1 shows the results of measurement at a heating rate of 20 ° C./min.

The present system is a system having an LCST type phase diagram, in which the compatible region is expanded under the shear of the extruder.

Further, it was rapidly cooled in the ice water, and a 100 μm-thick section was cut out from the gut with the fixed structure.
C. and Example 5 were heat-treated at 230.degree. C., respectively, and the structure formation process during this heat-treatment was traced using small-angle X-ray scattering. In all the samples, a peak appeared after 1 minute from the start of the heat treatment, and it was observed that the peak increased in intensity without changing the peak position. In this small angle X-ray scattering, the process of increasing the intensity without changing the peak position corresponds to the initial process of spinodal decomposition. Table 1 shows the structural period (Λm) calculated from the peak position (θm) by the following formula. Λm = (λ / 2) / sin (θm / 2) As for the section of the initial process during the small-angle X-ray scattering measurement, a part of it was immediately quenched in ice water to fix the structure, and then the polycarbonate was stained by iodine staining. After staining, the ultrathin sections were cut out and observed with a transmission electron microscope at a magnification of 100,000 times. As a result, a biphasic continuous structure was observed in all the samples.

FIG. 1 shows a transmission electron micrograph of the structure obtained in the initial process of spinodal decomposition in Example 2.
In the photograph, the black part is the phase containing polycarbonate as the main component, and the white part is the phase containing polybutylene terephthalate as the main component.

The small-angle X-ray scattering measurement was carried out, and after the structure was formed in the initial process, the section was further heat-treated at each temperature described above for a total of 10 minutes,
The structure was formed to obtain the polymer alloy structure of the present invention. Also for this sample, the small angle X
Table 1 shows the results of observing the structure period from the line scattering and the structure state from the transmission electron micrograph. The interparticle distance in the case of having a dispersed structure is also calculated by the same method as the structural period in the two-phase continuous structure.

FIG. 2 shows a transmission electron micrograph of the structure obtained by developing the biphasic continuous phase in the initial stage of the spinodal decomposition of Example 2 and then developing it. In the photograph, the black part is the phase containing polycarbonate as the main component, and the white part is the phase containing polybutylene terephthalate as the main component.

After discharging from the die, a sheet (thickness 0.2 mm) was prepared by heat-pressing at the same temperature and time as the heat-treatment by using a gut having a structure fixed by rapid cooling in ice water. . Furthermore, from the sheet, thickness 1
Table 1 shows the results of observing the structure period or interparticle distance from small-angle X-ray scattering and observing the structure condition from transmission electron micrographs, as in the case of the sample cut out from the above-mentioned gut. Described. From this result, it is understood that the structure is formed similarly to the sample cut out from the gut by the heat treatment in the hot press. Next, from the sheet, length × width × thickness = 50 m
A sample of m × 10 mm × 0.2 mm was cut out, a tensile strength measured at a chuck distance of 20 mm, a tensile speed of 10 mm / min, a tensile elongation, and a test piece was taken with a punching press, and a tensile impact test was performed according to ASTM D1822. Is shown in Table 1.

Further, after discharging from the die, gut in a state in which the structure was fixed by quenching in ice water and fixing the structure was supplied to a strand cutter to produce pellets. Next, using the pellets, the extrusion temperature was set again to 250 ° C., and the pellets were fed to a single-screw extruder (φ40 mm) having a T die at the tip adjusted to a residence time of 10 minutes to form a sheet.
In the sheeting, the resin discharged from the die of the T die was cast on a hard chrome mirror surface cast drum whose temperature was adjusted to 50 ° C under the T die, and after passing through the second drum whose temperature was adjusted to 50 ° C. , So that the winding speed is constant,
After passing between the rolls set to 5 m / min, a sheet was obtained by winding with a winding roll. The thickness of the obtained sheet was 0.1 mm. The obtained sheet was transparent, but a sample obtained by cutting an ultrathin section after staining the polycarbonate by the iodine staining method was observed under a transmission electron microscope at a magnification of 100,000 times. It was confirmed that the sample of 1) also had a biphasic continuous structure. Further, the glass transition temperature and the temperature rising crystallization temperature of the sample cut out by 10 mg from the obtained sheet were measured by DSC at a temperature rising rate of 20 ° C./min, and the results are shown in Table 1. From the DSC measurement results, the obtained sheet has two glass transition temperatures, which again suggests that phase separation is progressing during the melting time in the extruder. Next, in order to confirm this, another sample was cut out from the obtained sheet and the structure formation process during heat treatment at 250 ° C. was traced by using small-angle X-ray scattering. The peak is
During the subsequent 1 minute, it was observed that the intensity was increased without changing the peak position. The process of increasing the intensity without changing the peak position in this small-angle X-ray scattering corresponds to the structural development in the initial process of spinodal decomposition. Table 1
In the same manner as above, the value obtained by calculating the structural period in this initial process is described. From the above, it is considered that the spinodal decomposition proceeded again during the melting time in the extruder, and the sheet obtained as a result had a biphasic continuous structure.

Next, a 100 mm square sample was cut out from the above-obtained sheet, and four sides were fixed with clips, and 90
After preheating at 60 ° C for 60 seconds, in an oven controlled at 90 ° C,
At a stretching rate of 2000% / min and a stretching ratio of 3 times, four side clips were stretched so as to be simultaneously biaxially stretched. Also for the sample after stretching, the results of observing the structural period from the small-angle X-ray scattering and the structural state from the transmission electron microscope photograph are shown in Table 1 in the same manner as above. In the sample after this stretching,
The structural period is increased as compared with that before stretching, and it is considered that the structure was developed during the heat treatment during stretching. Further, from the sheet obtained after stretching, length x width x thickness = 50 mm
Table 1 shows the results obtained by cutting out a sample of × 10 mm × 0.03 mm and measuring the tensile strength and the tensile elongation measured at a chuck distance of 20 mm and a tensile speed of 10 mm / min.

The following resins were used. PC-1: Aromatic polycarbonate (Mitsubishi Engineering Plastics Co., Ltd. "Iupilon" S2000,
Glass transition temperature 151 ° C.) PBT-1: polybutylene terephthalate (Toray Industries, Inc.)
"Trecon" 1100S, glass transition temperature 32 ° C, crystal melting temperature 220 ° C).

Comparative Example 1 Melt kneading was carried out in the same manner as in Example 2 except that the extrusion temperature was set to 280 ° C., and the mixture was rapidly cooled in ice water immediately after being discharged from the die.
Although a gut having a fixed structure was obtained, this gut is turbid, and after staining the gut with a polycarbonate by an iodine staining method, a sample obtained by cutting out an ultrathin section,
When observed with a transmission electron microscope at a magnification of 1000 times, a non-uniform dispersed structure of 0.5 μm or more was observed. From this, it can be seen that this system is not compatibilized under shear in an extruder at an extrusion temperature of 280 ° C. Also in this system, the results of measuring the mechanical properties and observing the state of the structure are shown in Table 1 in the same manner as in Example 2.

Comparative Example 2 The same as Example 2 except that the heat treatment was carried out at 220 ° C. for 10 minutes, and the results of measuring the mechanical properties of the sample and observing the structural period and the state of the structure were shown. It is described in Table 1. However, the structural period of this sample was measured by a small-angle light scattering device. As in this example,
When the heat treatment temperature is low and the structural period in the initial process does not become sufficiently small, it is difficult to control the structural period within the range of the present invention if structural development is performed to make the concentration difference between both components sufficient. Become. Further, as in this example, when the structural period deviates from the range of the present invention, only poor mechanical properties were obtained.

Comparative Example 3 The same as the sample of Example 4 except that it was quenched after the initial structure was formed and no heat treatment was performed, and the results of measuring the mechanical properties of the sample, the structural period and the state of the structure The results of observation are shown in Table 1.

In the initial stage of the spinodal decomposition of the present invention,
It can be seen that a sample in which a biphasic continuous structure having a specific structural period is formed and the structure is further developed has excellent strength / toughness.

[0089]

[Table 1]

Examples 6 to 7 A twin screw extruder (PCM-3 manufactured by Ikegai Kogyo Co., Ltd.) was used, in which a raw material having the composition shown in Table 2 was set at an extrusion temperature of 240 ° C.
0) and discharged from the die, the gut was immediately cooled in ice water to fix the structure. All of the guts were transparent, and the guts were stained with a polycarbonate by an iodine staining method, and a sample obtained by cutting out an ultrathin section was observed with a transmission electron microscope at a magnification of 100,000 times. In all of the samples, it was confirmed that no structure having a size of 0.001 μm or more was observed and they were compatibilized.
From this, it can be seen that all of the present systems are compatibilized under shear in an extruder at an extrusion temperature of 240 ° C.

The present system is a system having an LCST type phase diagram, in which the compatible region is expanded under the shear of the extruder.

Further, it was rapidly cooled in the ice water, and a 100 μm-thick section was cut out from the gut with the fixed structure, and heat-treated at 240 ° C. in Example 6 and 200 ° C. in Example 7, and the structure forming process during this heat treatment. Were tracked using small angle X-ray scattering. In all the samples, a peak appeared after 1 minute from the start of the heat treatment, and it was observed that the peak increased in intensity without changing the peak position. In this small angle X-ray scattering, the process of increasing the intensity without changing the peak position corresponds to the initial process of spinodal decomposition. Table 2 shows the structural period (Λm) calculated from the peak position (θm) by the following formula. Λm = (λ / 2) / sin (θm / 2) As for the section of the initial process during the small-angle X-ray scattering, a part of the section was immediately quenched in ice water to fix the structure, and the polycarbonate was subjected to iodine staining to After staining, a sample obtained by cutting out an ultrathin section was magnified 100,000 times with a transmission electron microscope, and a continuous structure of both phases was observed.

Further, the section for which the small angle X-ray scattering was measured was subjected to a heat treatment at 240 ° C. for a total of 10 minutes after the structure was formed in the initial process, and the structure was formed.
A polymer alloy structure of the present invention was obtained. As for the sample, the results of observing the structural period from the small-angle X-ray scattering and the structural state from the transmission electron microscope photograph are shown in Table 2 as in the above initial process.

Further, a sheet (thickness: 0.8 mm) was prepared by heat-pressing at the same temperature and time as the above-mentioned heat treatment using a gut having a structure fixed by being rapidly cooled in ice water after being discharged from the die. . Furthermore, from the sheet, thickness 1
Table 1 shows the results of observing the structure period or interparticle distance from small-angle X-ray scattering and observing the structure condition from transmission electron micrographs, as in the case of the sample cut out from the above-mentioned gut. Described. From this result, it is understood that the structure is formed similarly to the sample cut out from the gut by the heat treatment in the hot press. Next, from the sheet, length × width × thickness = 85 m
A strip-shaped sample measuring m × 20 mm × 0.8 mm was cut out, held at one end 20 mm of the test piece and fixed in a cantilever state so that the test piece was horizontal, 100, 110, 12
After standing in an oven at 0, 130, 140, 150, and 160 ° C. for 60 minutes, the vertical distance at which the tip on the side opposite to the held portion hung down by its own weight was measured. Next, the vertical hanging distance and the temperature at each temperature were plotted, the points were connected by a straight line, and the temperature intersecting the vertical vertical distance of 3 mm was defined as the heat resistant temperature. The values are shown in Table 2.

The following resins were used. PC-1: Aromatic polycarbonate (Mitsubishi Engineering Plastics Co., Ltd. "Iupilon" S2000,
Glass transition temperature 151 ° C.) AS-1: styrene-acrylonitrile copolymer (“Toyolac” 1050B manufactured by Toray Industries, Inc., glass transition temperature 1)
02 ° C).

Comparative Example 4 Melt kneading was carried out in the same manner as in Example 6 except that the extrusion temperature was set to 290 ° C., and the mixture was rapidly cooled in ice water immediately after being discharged from the die.
Although a gut having a fixed structure was obtained, this gut is turbid, and after staining the gut with a polycarbonate by an iodine staining method, a sample obtained by cutting out an ultrathin section,
When observed with a transmission electron microscope at a magnification of 1000 times, a non-uniform dispersed structure of 0.5 μm or more was observed. This indicates that the system was not compatibilized under shear in an extruder at an extrusion temperature of 290 ° C. Also in this system, the results of measuring the heat resistance and observing the state of the structure are shown in Table 2 in the same manner as in Example 6.

In the initial stage of the spinodal decomposition of the present invention,
It can be seen that a sample in which a biphasic continuous structure having a specific structural period is formed and the structure is further developed has excellent heat resistance.

[0098]

[Table 2]

Examples 8 to 12 Of the raw materials having the compositions shown in Table 3, a twin-screw extruder (PCM-30 manufactured by Ikegai Kogyo Co., Ltd.) was used in which the chain extender and the additive were not added and the extrusion temperature was set to 250 ° C. ), And the gut discharged from the die was immediately cooled in ice water to fix the structure. All of the guts are transparent, and the guts were stained with an ethylene-vinyl acetate copolymer (EVA) by an osniotic acid staining method, and then ultrathin sections were cut out with a transmission electron microscope at a magnification of 100,000 times. The observation was carried out by enlarging the sample to 0.0
It was confirmed that a structure having a size of 01 μm or more was not seen and the components were compatibilized. This indicates that the system compatibilizes under shear in an extruder at an extrusion temperature of 250 ° C.

Then the chain extenders and additives were added, and Table 3
A twin-screw extruder (PCM-30 manufactured by Ikegai Kogyo Co., Ltd.) in which a raw material having the composition described is set to an extrusion temperature of 250 ° C.
The gut after being discharged from the die was immediately cooled in ice water to fix the structure. From the gut thickness 100
A μm section was cut out, 250 ° C. for the samples of Examples 8 to 10, and 27 for the sample of Example 11.
The sample of Example 12 was heat-treated at 0 ° C. and at 230 ° C., and the structure formation process during this heat-treatment was traced using small-angle X-ray scattering. In each sample, a peak appeared 5 minutes after the start of heat treatment, and it was observed that the peak increased in intensity without changing the peak position. In this small angle X-ray scattering, the process of increasing the intensity without changing the peak position corresponds to the initial process of spinodal decomposition. Table 3 shows the peak position (θ
The structural period (Λm) calculated from the formula below is shown. Λm = (λ / 2) / sin (θm / 2) As for the section of the initial process during the measurement of small-angle X-ray scattering, a part of it was immediately quenched in ice water to freeze the structure, and the osmium acid staining method was used for EVA. After staining, the ultrathin sliced sample was observed under a transmission electron microscope at a magnification of 100,000 times. As a result, a biphasic continuous structure was observed in all the samples.

Next, the gut having the above structure fixed was pelletized, the extrusion temperature was set again to 250 ° C., and the residence time was 5
It was supplied to a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) in which the screw rotation speed was adjusted so as to be within a minute, and the gut discharged from the die was immediately cooled in ice water to fix the structure. This gut showed a slight decrease in transparency, and after the gut was stained with EVA by the osniotic acid staining method, an ultrathin section was cut out and observed with a transmission electron microscope. A biphasic continuous structure was observed in all samples. From these facts, it is considered that in this system, after the chain extender was added, the polyester oligomer was polymerized again during the melt-kneading, and the phase decomposition was caused by the increase in the molecular weight.

The above-mentioned melt-kneaded gut was made into a sheet by a heating press (250 ° C. × 3 minutes), and the obtained sheet (thickness 0.2 mm) was used to measure length × width × thickness = 50 mm ×
A 10 mm x 0.2 mm sample is cut out, a tensile strength measured at a chuck distance of 20 mm, a tensile speed of 10 mm / min, a tensile elongation, and a test piece is taken by a punching press, and a tensile impact test is performed according to ASTM D1822. The results are shown in Table 1. Further, the above-mentioned test piece was subjected to a wet heat treatment at 80 ° C. and 95% RH for 1000 hours, and then subjected to a tensile test and a tensile impact test in the same manner as the untreated test piece. The results obtained are shown in Table 3.

The following resins were used. PBT-2: Polyester oligomer (polybutylene terephthalate: one having an intrinsic viscosity of 0.28 dl / g as measured at 25 ° C. in an o-chlorophenol solution) EVA: rubbery polymer (ethylene-vinyl acetate copolymer: "Ultrasen" 760 manufactured by Tosoh Corporation; vinyl acetate content 42%) X-1: chain extender (dicyclohexylmethane diisocyanate) X-2: additive (trimethylphosphoric acid (TMPA)).

Comparative Example 5 Examples 8 to 1 except that the polymer PBT-1 was used as the polyester resin and no chain extender was added.
Melt kneading in the same manner as in 0, and the gut discharged from the die was immediately cooled in ice water to obtain a sample having a fixed structure.
This sample was turbid, and the gut was stained with EVA by the osniotic acid staining method, and then an ultrathin section was cut out. The above non-uniform dispersed structure was observed. This shows that this sample was not compatibilized under shear in an extruder at an extrusion temperature of 250 ° C. Also for this sample, the results of measuring the mechanical properties and observing the state of the structure are shown in Table 3 in the same manner as in Examples 8 to 12.

The following resins were used. PBT-1: Polyester resin (polybutylene terephthalate: "Toraycon" 1100S manufactured by Toray Industries, Inc.) EVA: Rubbery polymer (ethylene-vinyl acetate copolymer: "Ultracene" 760 manufactured by Tosoh Corporation; vinyl acetate content 42%) )

[0106]

[Table 3]

In the initial stage of the spinodal decomposition of the present invention,
It can be seen that the sample, in which the structure is developed after the formation of the biphasic continuous structure having the specific structural period, has excellent strength / toughness and further retains the characteristics even after the wet heat treatment.

Examples 13 to 15 Of the raw materials having the compositions shown in Table 4, first, the raw material was supplied to a twin-screw extruder (PCM-30 manufactured by Ikegai Industry Co., Ltd.) set to an extrusion temperature of 250 ° C. without adding a crosslinking agent. Then, the gut discharged from the die was immediately cooled in ice water to fix the structure. All of the guts are transparent, and the guts were stained with AR by an osniotic acid staining method, and then ultrathin sections were cut out and observed with a transmission electron microscope at a magnification of 100,000 times. It was confirmed that, in each of the samples, a structure having a size of 0.001 μm or more was not seen and they were compatibilized. This indicates that the system compatibilizes under shear in an extruder at an extrusion temperature of 250 ° C.

Next, a cross-linking agent was added to the pellets obtained from the gut to which the above structure was fixed so that the addition amount was as shown in Table 4, and a twin-screw extruder was also set at an extrusion temperature of 250 ° C. (Ikegai Industry Co., Ltd.). PCM-30) manufactured by the company, and the gut discharged from the die was immediately cooled in ice water to fix the structure. Further, a 100 μm-thick piece was cut out from the gut, heat-treated at 250 ° C., and the structure formation process during this heat-treatment was traced using small-angle X-ray scattering. In each sample, a peak appeared 5 minutes after the start of heat treatment, and it was observed that the peak increased in intensity without changing the peak position. In this small angle X-ray scattering, the process of increasing the intensity without changing the peak position corresponds to the initial process of spinodal decomposition. Table 4 shows the structural period (Λm) calculated from the peak position (θm) by the following formula. Λm = (λ / 2) / sin (θm / 2) As for the section of the initial process during the small-angle X-ray scattering measurement, a part of it was immediately quenched in ice water to freeze the structure, and the transmission electron microscope was used. When observed with 100,000 magnifications, a biphasic continuous structure was observed in all the samples.

Next, the gut having the above structure fixed was pelletized, the extrusion temperature was set again to 250 ° C., and the residence time was 5
It was supplied to a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) in which the screw rotation speed was adjusted so as to be within a minute, and the gut discharged from the die was immediately cooled in ice water to fix the structure. The gut showed a slight decrease in transparency, and after the gut was stained with AR by an osniotic acid staining method, a sample obtained by cutting out an ultrathin section was observed with a transmission electron microscope. A biphasic continuous structure was observed in all samples. From these things, this system, after adding the crosslinking agent,
It is considered that the phase decomposition was caused again by the increase in the molecular weight of the rubber-like polymer during the melt-kneading.

The above-mentioned melt-kneaded gut was made into a sheet by a heating press (250 ° C. × 3 minutes), and from the obtained sheet (thickness 0.2 mm), length × width × thickness = 50 mm ×
A 10 mm x 0.2 mm sample is cut out, a tensile strength measured at a chuck distance of 20 mm, a tensile speed of 10 mm / min, a tensile elongation, and a test piece is taken by a punching press, and a tensile impact test is performed according to ASTM D1822. The results are shown in Table 2. Further, the above-mentioned test piece was subjected to a wet heat treatment at 80 ° C. and 95% RH for 1000 hours, and then subjected to a tensile test and a tensile impact test in the same manner as the untreated test piece. The results obtained are shown in Table 4.

The following resins were used. PBT-3: Polyester resin (polybutylene terephthalate: one having an intrinsic viscosity of 0.53 dl / g when measured at 25 ° C. in an o-chlorophenol solution) AR-1: rubbery polymer (acrylic rubber: manufactured by DuPont) , VAMAC-123; about 73 mol% ethylene, about 26 mol% methyl acrylate and about 1 mol% carboxylic acid.
X-3: Cross-linking agent (isocyanate group-terminated polyester oligomer: "Monjour" E-50, manufactured by Mobay Co., Ltd.)
1).

Comparative Example 6 A twin-screw extruder (PCM-3 manufactured by Ikegai Industry Co., Ltd.) in which an extruding temperature of 200 ° C. was set in advance for a rubber polymer and a crosslinking agent.
0 to 13) except that the kneaded mixture was used.
A sample with a fixed structure was obtained by melt-kneading in the same manner as above and immediately cooling it in ice water immediately after discharging from the die. This sample was turbid, and the sample was stained with AR by the osninic acid staining method. When observed with a transmission electron microscope at a magnification of 1000, a non-uniform dispersed structure of 0.5 μm or more was observed. From this,
It can be seen that this sample is not compatibilized under shear in an extruder with an extrusion temperature of 280 ° C. Also for this sample, the results of measuring the mechanical properties and the results of observing the structural period and the state of the structure are shown in Table 4 as in Examples 13 to 15.
Described in.

[0114]

[Table 4]

In the initial stage of the spinodal decomposition of the present invention,
It can be seen that the sample, in which the structure is developed after the formation of the biphasic continuous structure having the specific structural period, has excellent strength / toughness and further retains the characteristics even after the wet heat treatment.

[0116]

As described above, the polymer alloy of the present invention has properties such as excellent strength and toughness and excellent heat resistance depending on the resin to be combined, and the structure can be utilized by utilizing these properties. It can be usefully used as a material. Furthermore, the polymer alloy of the present invention also has a property of excellent regularity, and by utilizing this property, it can be usefully used as a functional material.

[Brief description of drawings]

FIG. 1 shows a transmission electron micrograph of a structure obtained in an initial stage of spinodal decomposition in Example 2.

FIG. 2 shows a transmission electron micrograph of a structure obtained by developing after forming a biphasic continuous phase in the initial stage of spinodal decomposition in Example 2.

Claims (16)

[Claims] 1. A polymer alloy comprising a resin of at least two components which are phase-separated by spinodal decomposition, and after forming a biphasic continuous structure having a structural period of 0.001 to 0.1 μm in the initial process of the spinodal decomposition, Furthermore, the polymer alloy is characterized by being developed to a biphasic continuous structure having a structural period of 0.01 to 1 μm or a dispersed structure having an interparticle distance of 0.01 to 1 μm. 2. The polymer alloy according to claim 1, wherein at least one of the resin components constituting the polymer alloy is a crystalline resin. 3. The polymer alloy according to claim 2, wherein the crystalline resin is a polyester resin. 4. The polymer alloy according to claim 3, wherein the polymer alloy contains at least one rubbery polymer. 5. A polymer alloy comprising a polybutylene terephthalate resin and a polycarbonate resin, wherein the polymer alloy has a biphasic continuous structure having a structural period of 0.01 to 1 μm. 6. The polymer alloy according to claim 1, wherein the polymer alloy is manufactured by melt-kneading. 7. The polymer alloy according to claim 6, wherein the spinodal decomposition is compatible under shear during melt-kneading and phase-separates under non-shear after discharge. 8. The polymer alloy is obtained by inducing spinodal decomposition by chemically reacting a precursor of at least one of resin components constituting the polymer alloy in the presence of the remaining resin component. The polymer alloy according to any one of claims 1 to 5, which is a polymer alloy. 9. The spinodal decomposition is a process in which the spinodal decomposition is once compatible with each other before the chemical reaction and the phases are separated after the chemical reaction.
The polymer alloy described. 10. The polymer alloy according to claim 1, which is for injection molding. 11. The polymer alloy according to claim 1, which is for film and / or sheet extrusion molding. 12. A method for producing a polymer alloy in which at least two resin components are phase-separated by spinodal decomposition, wherein a biphasic continuous structure having a structural period of 0.001 to 0.1 μm is formed in the initial stage of spinodal decomposition. A method for producing a polymer alloy, which further comprises developing a biphasic continuous structure having a structural period of 0.01 to 1 μm or a dispersed structure having an interparticle distance of 0.01 to 1 μm. 13. The method for producing a polymer alloy according to claim 12, wherein the spinodal decomposition is induced by melt-kneading at least two resin components. 14. The method for producing a polymer alloy according to claim 13, wherein at least two resin components are compatible with each other under shearing during melt-kneading, and phase separation is carried out under non-shearing after discharge. 15. The spinodal decomposition is induced by chemically reacting a precursor of at least one of the resin components constituting the polymer alloy in the coexistence of the remaining resin components. Method for producing polymer alloy. 16. The method for producing a polymer alloy according to claim 15, wherein the polymer alloy is once compatible with each other before the chemical reaction and is phase-separated after the chemical reaction.