JP2003113307A - Polyphenylene sulfide resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition suitable as a molding material having excellent mechanical characteristics and properties of reduced flashes. SOLUTION: This polyphenylene sulfide resin composition has the structure controlled to a two-phase continuous structure having 0.01-1 μm structural period or a dispersed structure having 0.01-1 μm center distance of dispersed particles. A method for producing the polyphenylene sulfide resin composition comprises carrying out phase separation of a polyphenylene sulfide resin composition composed of at least two or more components of resins and containing one or more kinds of polyphenylene sulfide resins by spinodal decomposition. Furthermore, the method for producing the polyphenylene sulfide resin composition comprises forming the two-phase continuous structure having 0.001-0.1 μm structural period in the initial period of the spinodal decomposition and then further developing the resultant structure into the two-phase continuous structure having 0.01-1 μm structural period or the dispersed structure having 0.01-1 μm interparticle distance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition which can be effectively used as a structural material by utilizing excellent mechanical properties and as a functional material by utilizing excellent regularity. The present invention also relates to a method for producing a polyphenylene sulfide resin composition whose structure can be controlled from the nanometer order to the micron order.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter P
Abbreviated as PS resin. ) Has excellent heat resistance, flame retardancy, chemical resistance, dimensional stability, rigidity, and electrical insulation properties, making it suitable for engineering plastics. It is used for machine parts and automobile parts.

However, the PPS resin is known to be brittle and inferior in impact resistance and mechanical properties, and in most cases, it is used in a reinforced system to which an inorganic reinforcing agent such as glass fiber is added. Therefore, the field of use as a molding material is currently limited. Further, the PPS resin has a relatively large amount of burrs generated during molding, and its use is limited particularly in applications such as small precision parts that require low burrs.

Under these circumstances, a method of blending another thermoplastic resin is known as a method of improving the toughness of the PPS resin. JP-A-58-145757 discloses a composition comprising a PPS resin and a glycidyl-modified polyolefin resin, and JP-A-60-120753 discloses a PP.
Composition comprising S resin and rubber compound, JP-A-59-5
No. 8052 discloses a composition comprising a PPS resin and a thermoplastic polyester resin, JP-A No. 51-59952 discloses a composition comprising a PPS resin and a polycarbonate resin, and JP-A No. 53-69255 discloses a PPS. A composition comprising a resin and a polyamide resin is disclosed. However, even if any of the resins is used, the compatibility with the PPS resin is poor and the effect of improving the toughness is not sufficiently obtained by simply blending the resins.

Further, in JP-A-2000-248179, both phases are continuously connected by kneading a PPS resin and a thermoplastic resin selected from polycarbonate, polysulfone and polyetherketone under specific melt-kneading conditions. A PPS resin composition having a different structure is disclosed. However, since the biphasic continuous structure obtained by this method is of the order of a few micrometers and the regularity of the structure is low, the present situation is that sufficient effect for improving the toughness is not obtained.

Further, some studies have been made so far for the purpose of reducing the burr of the PPS resin. JP-A-6
Japanese Patent Application Laid-Open No. 4-9266 discloses a method of blending a highly crosslinked PPS resin as a property improving agent, JP-A-63-25143.
No. 0 discloses a method of adding a silane compound to a PPS resin, and JP-A-3-197562 uses a combination of a specific linear PPS resin and a crosslinked PPS resin in a base polymer, and further uses a silane coupling agent. And the like are disclosed.

However, although the conventional technique alone can reduce the burr to some extent, it still has a large amount of burr as compared with other engineering plastics such as PBT resin and polyamide, and further burr reduction is desired at present. .

On the other hand, a polymer alloy utilizing spinodal decomposition is disclosed in Japanese Patent Laid-Open No. 8-113829.
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, in the invention described in the publication, polyester resin is mainly used, and use of PPS resin is not described. Further, in the invention described in the publication, a special method of forming the structure through an extensional flow field in melt spinning has been adopted to obtain a finely dispersed structure, which has excellent mechanical properties and low burr property. There is no description of a technical idea for obtaining a structural material having

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a PPS resin composition having excellent mechanical properties and excellent low flash properties, which is useful as a molding material. In a preferred embodiment, it is an object of the present invention to provide a PPS resin composition having excellent regularity, finely controlling its structure, and further sufficiently developing a concentration difference between two phases of the structure. Is.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a PPS resin composition containing at least one PPS resin has a structural period of 0.01 to 1
Biphase continuous structure of μm, or distance between particles 0.01 to 1 μm
It was found that the PPS resin composition having a structure controlled to have a dispersed structure of m has the above-mentioned characteristics, and the present invention has been completed.

That is, the present invention is: (1) PP comprising at least two resin components and containing at least one PPS resin.
An S resin composition, wherein the PPS resin composition has 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) A PPS resin composition that is phase-separated by spinodal decomposition and that is composed of at least two-component resins and that contains at least one PPS resin, and has a structural period of 0.0 in the initial stage of the spinodal decomposition.
After the formation of a biphasic continuous structure of 01 to 0.1 μm, it is further developed to a biphasic continuous structure of a structural period of 0.01 to 1 μm, or a dispersed structure of an interparticle distance of 0.01 to 1 μm. A PPS resin composition, (3) the P
The PPS resin composition according to any one of (1) to (2) above, wherein the PS resin composition is produced through melt-kneading, and (4) the spinodal decomposition is under shear during melt-kneading. The PPS resin composition according to the above (3), which is compatible with each other and undergoes phase separation under non-shearing after discharge, (5) above P
A PS resin composition is obtained by inducing spinodal decomposition by chemically reacting a precursor of at least one resin component of the PPS resin composition in the presence of the remaining resin component. There is (1) above
(4) The PPS resin composition according to any one of (1) to (6), wherein the spinodal decomposition is once compatible with each other before the chemical reaction and phase-separated after the chemical reaction.
Resin composition, (7) above for injection molding (1) to
(6) The PPS resin composition according to any one of (1) to (6) above, which is for film and / or sheet extrusion molding.
(9) A method for producing a PPS resin composition, which comprises a PPS resin composition comprising at least two resin components and containing at least one PPS resin, phase-separated by spinodal decomposition. After the formation of the bicontinuous phase structure of 0.001 to 0.1 μm, the PPS is further developed to a bicontinuous phase 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. Method for producing resin composition, (1
0) Production of a PPS resin composition according to the above (9), characterized by inducing spinodal decomposition by melt-kneading a PPS resin composition comprising at least two components and containing at least one PPS resin. Method (11) compatibilizing at least two resin components under shear during melt-kneading,
(12) A method for producing a PPS resin composition according to the above (10), characterized in that the phases are separated under non-shearing after discharging.
The PPS resin according to (9) above, wherein a precursor of at least one of the resin components constituting the PPS resin composition is chemically reacted in the presence of the remaining resin component to induce spinodal decomposition. (13) The method for producing a composition, and (13) the method of (12), wherein the chemical components are once compatible with each other before the chemical reaction and phase-separated after the chemical reaction.
It is a method for producing a PS resin composition.

[0012]

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

The PPS resin used in the present invention is a polymer containing a repeating unit represented by the following structural formula,

[0014]

[Chemical 1]

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is preferable. Further, the PPS resin can comprise 30 mol% or less of its repeating unit with a repeating unit having the following structural formula.

[0016]

[Chemical 2]

The PPS resin used in the present invention is a known method, that is, a method for obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368 or JP-B-52.
It can be produced by the method described in JP-A-12240 or JP-A-61-7332 for obtaining a polymer having a relatively large molecular weight. In the present invention, the PPS resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment in an atmosphere of an inert gas such as nitrogen or under reduced pressure,
Washing with organic solvent, hot water, acid aqueous solution, acid anhydride,
It is possible to use it after various treatments such as activation with a functional group-containing compound such as amine, isocyanate, or a functional group-containing disulfide compound, and it is of course possible to carry out two or more of these treatments. is there.
Further, it is of course possible to use the PPS resin which has been subjected to these treatments in a mixture of two or more kinds. As a specific method in the case of using a mixture of two or more kinds, a PPS resin crosslinked by heating in air is used. And P without heat treatment
Examples include mixing of PS resin, mixing of PPS resin washed with an acid aqueous solution and PPS resin washed with an organic solvent, mixing of PPS resin washed with an organic solvent and PPS resin not washed with an organic solvent. it can.

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, and is usually 5 to 5.
1,000Pa ・ s (320 ℃, shear rate 1000se
c ^-1 ) is used, among which 10 to 500 Pa · s
Are preferred. In addition, it is effective to use two or more kinds of PPS resins having different melt viscosities in combination in order to obtain a more excellent burr reduction effect. For example, PPS resin having a melt viscosity of 30 Pa · s or more and 30 Pa · s A suitable method is a method of mixing and using a PPS resin having a melt viscosity of less than 1.

A specific method for crosslinking / polymerizing the PPS resin by heating is to use an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method of heating in an atmosphere at a predetermined temperature until a desired melt viscosity is obtained. The heat treatment temperature is usually 170 to 28
0 ° C. is selected, preferably 200-270 ° C.,
The time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours, but the target viscosity level can be obtained by appropriately controlling the heat treatment temperature and time. The heat treatment device may be a normal hot air dryer with a reduced pressure specification or a high sealing property, a rotary type or a heating device with a stirring blade, but a rotary type for efficient and more uniform treatment. Alternatively, it is more preferable to use a heating device equipped with a stirring blade.

A specific method for heat-treating the PPS resin in an atmosphere of an inert gas such as nitrogen or under a reduced pressure is as follows:
Heat treatment temperature 150 to 280 ° C., preferably 200 to 2
70 ° C., heating time 0.5 to 100 hours, preferably 2
A method of heat treatment for up to 50 hours can be exemplified. The apparatus for heat treatment may be a stationary heating apparatus or a heating apparatus with a rotary or stirring blade, but for efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade should be used. Is more preferable.

The following method can be exemplified as a specific method for washing the PPS resin with an organic solvent. That is,
The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin, but is, for example, a nitrogen-containing polar solvent such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl. Sulfoxide / sulfone type solvents such as sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone type solvents such as acetophenone, dimethyl ether, dipropyl ether, ether type solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen-based solvents such as trichlorethylene, ethylene dichloride, dichloroethane, tetrachloroethane, chlorobenzene, alcohol / phenolic solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol. And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, it is preferable to use N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like. Further, these organic solvents may be used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat. The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and any temperature from normal temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be. However, normally, a sufficient cleaning effect can be obtained at a cleaning temperature of room temperature to 150 ° C.

The PPS resin which has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method for treating the PPS resin with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to exert the effect of preferable chemical modification of the PPS resin by washing with hot water. The operation of hot water treatment is usually carried out by adding a predetermined amount of PPS resin to a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably such that the amount of water is large, but normally, a bath ratio of 200 g or less of PPS resin to 1 liter of water is selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid.

That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of the acid, and it is also possible to appropriately stir or heat as necessary. The acid used is P
There is no particular limitation as long as it has no action of degrading PS resin, for example, formic acid, acetic acid, propionic acid, aliphatic saturated monocarboxylic acid such as butyric acid, chloro-substituted aliphatic saturated carboxylic acid such as dichloroacetic acid, Acrylic acid, aliphatic unsaturated monocarboxylic acid such as crotonic acid, benzoic acid, aromatic carboxylic acid such as salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, dicarboxylic acid such as fumaric acid, sulfuric acid, phosphoric acid, Examples thereof include inorganic acidic compounds such as hydrochloric acid, carbonic acid, and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the preferred chemical modification effect of the PPS resin by acid treatment is not impaired.

The PPS resin composition of the present invention is a polymer alloy of PPS resin and other resins, and as the resin other than the PPS resin, the spinodal decomposable resin described later is preferable, for example, polyester, polyamide, polyphenylene. Oxide, polysulfone, tetrafluoropolyethylene, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketone, epoxy resin, phenolic resin,
Polyethylene, polystyrene, polypropylene, ABS
Examples thereof include resins, polyamide elastomers, polyester elastomers, polyalkylene oxides, resins such as olefinic copolymers containing a carboxyl group, and the like.

The composition of the resin component constituting the PPS resin composition of the present invention is not particularly limited, but the PPS resin is usually 50 to 50% by weight with respect to 100% by weight of the total of the resin components constituting the PPS resin composition. The range of 97% by weight is preferably used, and the range of 50 to 95% by weight is more preferable, and the range of 50 to 75% by weight is particularly preferable because a biphasic continuous structure is relatively easily obtained.

The PPS resin composition of the present invention must have a biphasic continuous structure with a structural period of 0.01 to 1 μm or a dispersed structure with an interparticle distance of 0.01 to 1 μm. In order to obtain such a structure, PPS resin and PP
It is preferable that the resin other than the S resin is once phase-dissolved and the structure is formed by spinodal decomposition described later. Furthermore, in order to realize this structure formation, PPS resin and P
The resin other than the PS resin is preferably a partial compatibility system described later, a shear field-dependent phase dissolution / phase decomposition system, or a reaction-induced phase decomposition system.

In general, a polymer alloy composed of a two-component resin is compatible with these compositions in a practical compatible range above the glass transition temperature and below 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.In addition, in this partially compatible system, spinodal decomposition occurs depending on the conditions of the phase-separated state. In some cases, phase separation occurs due to 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 diagrams for different two-component resin compositions and temperature, and the phase separation by nucleation and growth. , Refers to the phase separation that occurs in the 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 the composition and the temperature.

Here, the case of compatibility in the present invention means:
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 once been homogeneously 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) The biphasic 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)”.
(Chapter 10.1) "(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, but in order to obtain the structure defined by the present invention, the desired structural period before finally separating into this two macroscopic phases The structure may be fixed at the stage when is reached.

In the process of increasing the wavelength from the middle stage process to the latter stage process, depending on the influence of composition and interfacial tension,
In some cases, the continuity of one phase is interrupted and the above-mentioned biphasic continuous structure is changed to a dispersed structure. In this case, the structure may be fixed when the desired interparticle distance is reached.

The term "dispersed structure" as used in the present invention means a so-called sea-island in which a matrix containing one resin component as the main component is interspersed with particles containing the other resin component as the main component. Refers to the structure.

The PPS resin composition of the present invention must be structurally controlled to have 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. However, by controlling the structural period of the initial process of spinodal decomposition within the range of 0.001 to 0.1 μm, the structural period of 0.01 to The structure can be controlled to have a biphasic continuous structure in the range of 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, after structural evolution, the structural period 0.01
It is preferable to control the biphasic continuous structure in the range of 0.5 to 0.5 μm or the dispersed structure in which the interparticle distance is in the range of 0.01 to 0.5 μm, and 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. The effect of the present invention can be obtained by controlling the range of such a structural period and the range of the distance between particles, but by further developing the concentration difference sufficiently, a structure having more excellent mechanical characteristics and low burr effect can be obtained. You can get it.

On the other hand, in the nucleation and growth, which are the phase separation in the 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 by 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 using m. Λ m = (λ / 2) / sin (θ m / 2) In order to realize the above spinodal decomposition, it is necessary to make the PPS resin and other resins compatible with each other and then make the inside of the spinodal curve unstable. is necessary.

First, as a method for realizing a compatible state with a resin composed of two or more components, after dissolving in a common solvent, spray drying, freeze drying, coagulation in a non-solvent substance, film formation by solvent evaporation, etc. from this solution 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 resin composition which has been made compatible by the melt-kneading is made into an unstable state inside the spinodal curve, the temperature and other conditions for making the unstable state during spinodal decomposition are as follows. It can be set by conducting a simple preliminary experiment based on the phase diagram, though it cannot be said to be unequivocally different. 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 in the initial process, but the temperature is not lower than the lowest glass transition temperature among the glass transition temperatures of the individual resin components constituting the PPS resin composition and the above-mentioned. Heat treatment is preferably used at a temperature that reduces the thermodynamically defined structural period. 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).

There are no particular restrictions on the method of developing the structure from this initial stage, but the method of heat treatment at the lowest temperature or higher of the glass transition temperatures of the individual resin components constituting the PPS resin composition is usually preferably used. To be
Further, 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 due to the heat treatment can be effectively obtained, and the heat treatment temperature is the crystal melting temperature ± 20 ° C.
It is preferable that the temperature is within the range in order to facilitate the control of the above-mentioned structure development, and it is more preferable that the temperature is within the crystal melting temperature ± 10 ° C. When two or more crystalline resins including PPS resin are used as the resin component, the heat treatment temperature is within the crystal melting temperature ± 20 ° C. based on the highest temperature among the crystal melting temperatures of the crystalline resin. It is more preferable that the temperature is within ± 10 ° C. of the crystal melting temperature. Here, the crystal melting temperature of the crystalline resin is from room temperature to 2 by 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 0 ° C./min.

As a method of immobilizing the structural product by spinodal decomposition, one or both components of the phase-separated phase are structurally immobilized in a short time by rapid cooling, or when one is a component which is thermally cured, it is thermally cured. Structural fixation utilizing the fact that the phase of the sexual component cannot move freely due to the reaction, and when one of them is a crystalline resin, structural fixation utilizing the fact that the crystalline resin phase cannot move freely due to crystallization Among them, when at least one of them is a crystalline resin such as a PPS resin composition, structural fixing by crystallization is preferably used.

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, nylon 6 and nylon. Aromatic polyamides such as 66, aromatic polyamides such as nylon 6T and nylon 6I, aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and their copolymers, and poly- aliphatic polyester such as ε-caprolactam, polyethylene, polypropylene, polyvinyl alcohol,
Examples thereof include polyolefin vinyl such as polyvinyl chloride and polyether such as polyoxymethylene.

In the present invention, the PPS resin and the other resins are phase-separated by the above spinodal decomposition to obtain the PPS resin composition of the present invention. As described above, the PPS resin and the partial compatible system and the shear field dependent type are used. It is preferable to combine a resin that is a system capable of phase dissolution / phase decomposition or a system capable of reaction-induced phase decomposition.

Generally, a partially compatible system has a low temperature compatible type phase diagram in which the same composition easily becomes compatible at a low temperature side, and a high temperature compatible type phase diagram easily becomes compatible at a high temperature side. Things are known. The lowest branching temperature of compatible and incompatible in this low temperature compatible phase diagram is the lower critical solution temperature (abbreviated as L
CST), which is the highest branching temperature of compatible and noncompatible phases in the high temperature compatible phase diagram.
Critical solution temperature is abbreviated as UCST).

In the case of a low temperature compatibility type phase diagram, two or more resins which have become 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.

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 way as in the case of partial compatible systems 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. A usual extruder is used for compatibilizing under shearing during the melt-kneading, but a twin-screw extruder is preferably used. In addition, depending on the combination of resins, it may be possible to perform compatibilization in the plasticizing step of the injection molding machine. In this case, 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. The conditions can be set by carrying out a simple preliminary experiment based on the phase diagram under the shearing conditions. Further, as a method for surely realizing the compatibilization in the plasticizing step of the injection molding machine, it is melt-kneaded and compatibilized in advance with a twin-screw extruder, 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.

As a combination of the above-mentioned shear field-dependent phase-dissolving and phase-decomposing resins, a mixture of PPS resin and nylon 4,6 may be mentioned.

Further, even in a compatible system, phase separation by spinodal decomposition is possible also by so-called reaction-induced phase decomposition in which an unstable state occurs due to a change in molecular weight accompanying a chemical reaction or the like. For example, the precursor of the resin component that is finally contained, such as the raw material of the resin component that constitutes the polymer alloy, the oligomer or the low molecular weight substance, is a compatible system with the remaining resin component, and When a resin to be polymerized and alloyed causes phase separation with other resin components, at least one precursor of the resin components constituting the polymer alloy is added in the presence of the remaining resin components. , It is possible to induce spinodal decomposition by causing a chemical reaction. 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 or the crystal melting temperature in the case of a crystalline resin changes with the change in the molecular weight due to polymerization or crosslinking, and further, the change from the phase dissolution to the phase decomposition due to the change in the molecular weight is different depending on the system. The temperature for solubilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for structurally developing from the initial process, and other conditions cannot be said unequivocally, but in the phase diagram in combination with various molecular weights. Based on this, the conditions can be set by performing a simple preliminary experiment.

Further, in the combination of the above reaction-induced phase decomposition resins, the precursor and the rest of the 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. Examples of such a material include PPS resin and polyphenylene oxide resin mixed system, PPS resin and thermosetting polyallyl ether oligomer system, and the like. As such a manufacturing method,
For example, a method of polymerizing the alloy once phase-melted again at the time of melt kneading in an extruder such as a single-screw or twin-screw extruder, or an extruder such as a single-screw or twin-screw extruder having a long residence time is used. Then, there is a method in which the components are once phase-dissolved in one extrusion and then polymerized to cause phase decomposition.

Further, addition of a third component, which is a copolymer such as a block copolymer, a graft copolymer or a random copolymer, containing a component constituting a polymer alloy, to the PPS resin composition constituting the present invention,
It is preferably used in order to reduce the free energy of the interface between the phases that have been phase-decomposed and to facilitate 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.

In the PPS resin composition of the present invention, the combined use of an alkoxysilane compound is effective for obtaining excellent mechanical strength. Examples of the alkoxysilane compound include an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. Specific examples thereof include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ
An ureido group-containing alkoxysilane compound such as-(2-ureidoethyl) aminopropyltrimethoxysilane,
γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanato Propylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Amino group-containing alkoxysilane compound such as γ-aminopropyltrimethoxysilane, hydroxyl group-containing alkoxy such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane Is like orchid compounds, among others .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropyl triethoxy silane,
Epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-
Ureido group-containing alkoxysilane compounds such as ureidopropyltrimethoxysisilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane Etc. are preferred. Particularly preferred are epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. .

The alkoxysilane compound having at least one functional group selected from the group consisting of epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group and ureido group is used for obtaining more excellent mechanical strength. The amount of addition is 100 parts by weight of PPS resin,
The range of 0.05 to 5 parts by weight is selected, and the range of 0.2 to 3 parts by weight is more preferably selected. When the amount is too small, the effect of improving the mechanical strength by the addition of the alkoxysilane compound is not sufficiently exhibited, and when the amount is too large, not only the above improving effect reaches saturation but also the gas generation amount of the composition tends to increase.

In the present invention, a filler may be used, if necessary, in order to improve strength, dimensional stability and the like. The shape of the filler may be fibrous or non-fibrous, and a fibrous filler and a non-fibrous filler may be used in combination. Such fillers include glass fibers, glass milled fibers, carbon fibers, potassium titanate whiskers, zinc oxide whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, stone fibers, and metals. Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, using these fibrous and / or non-fibrous fillers after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, It is preferable in the sense of obtaining better mechanical strength.

In order to improve strength and dimensional stability,
When such a filler is used, its compounding amount is not particularly limited, but is usually 30 to 40 relative to 100 parts by weight of the PPS resin.
0 parts by weight is compounded.

In the PPS resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer type compounds, thioether type compounds, ester type compounds and organic phosphorus compounds, talc, kaolin and organic compounds are used as long as the effects of the present invention are not impaired. Phosphorus compounds, crystal nucleating agents such as polyetheretherketone, polyolefin-based compounds, silicone-based compounds, long-chain aliphatic ester-based compounds, long-chain aliphatic amide-based compounds, release agents, anticorrosives, anti-coloring agents, Conventional additives such as antioxidants, heat stabilizers, lubricants such as lithium stearate and aluminum stearate, UV inhibitors, colorants, flame retardants, foaming agents and the like can be added.

These additives can be added at any stage of producing the PPS resin composition of the present invention. For example, a method of adding them at the same time when at least two components of the resin are added, or by previously adding A method of adding the two-component resin after melt-kneading, or a method of first adding to one resin and melt-kneading and then blending the rest of the resins may be mentioned.

The PPS resin composition obtained from the present invention can be molded by 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.
It is preferable because heat treatment and structure fixing can be performed at the same time in the mold, and in the case of film and / or sheet extrusion molding, it is possible to perform heat treatment during film and / or sheet stretching and then structure fixing during subsequent natural cooling before winding. Is preferred. Of course, it is also possible to heat treat the above-mentioned molded article separately to form a structure.

The PPS resin composition of the present invention can be usefully used as a structural material having improved impact resistance when one of the resins has excellent impact resistance. It can be suitably used for electric parts and the like.

The molded product of the PPS resin composition of the present invention includes connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, and oscillators. , Various terminal boards, transformers, plugs,
Printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base,
Power module, semiconductor, liquid crystal, FDD carriage,
Suitable for electronic parts such as FDD chassis, motor brush holder, parabolic antenna, computer related parts, etc., generator, motor, transformer,
Current transformer, voltage regulator, rectifier, inverter, relay,
Electrical equipment parts such as power contacts, switches, circuit breakers, knife switches, other pole rods, electric parts cabinets, etc.
VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio / laser disk (registered trademark) / compact disks, audio / video equipment parts such as DVDs, lighting parts, refrigerator parts, air conditioners Household and office electrical product parts represented by parts, typewriter parts, word processor parts, etc .;
Machine-related parts such as office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters and typewriters: typical microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery related parts; alternator terminal, alternator connector, IC regulator, potentiometer base for light deer,
Various valves such as exhaust gas valves, fuel-related, exhaust system, intake system various pipes, air intake nozzle snorkel,
Intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad Wear sensor, air conditioner thermostat base, heating warm air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, detributor, starter switch, starter relay, transmission wire harness, window washer. Nozzle, air conditioner panel switch substrate, fuel related electromagnetic valve coil Fuse connector, horn terminal, insulating plates for electric equipment, step motor rotor,
It can be applied to various applications such as lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, parts for automobiles and vehicles such as ignition device cases.

When a resin having excellent low burr property is used as one of the resins, it is preferable to use it for injection molding by taking advantage of its good burr characteristics. It is preferable to use an electronic component that can be used, and it is particularly preferable to use a connector.

[0068]

EXAMPLES The effects of the present invention will be further described below with reference to examples.

Reference Example (Polymerization of PPS Resin) (PPS-
1) In an autoclave equipped with a stirrer, 6.004 kg (25 mol) of sodium sulfide nonahydrate and N-methyl-2-
4.5 kg of pyrrolidone (hereinafter abbreviated as NMP) was charged,
Gradually raise the temperature to 205 ° C while flowing nitrogen, and then add water 3.6.
Distilled 1 liter. Next, after cooling the reaction vessel to 180 ° C., 3.719 kg (25.
(3 mol) and 3 kg of NMP were added, and the mixture was sealed under nitrogen, heated to 270 ° C., and reacted at 274 ° C. for 1 hour.
After cooling, the reaction product was washed twice with warm water, and then this slurry was placed in an autoclave equipped with a stirrer and 3 kg of deionized water was added.
Then, the temperature was raised to 190 ° C., and after reaching 190 ° C., the mixture was cooled to room temperature, filtered, and washed with hot water several times. After filtering this, PPS resin was dried under reduced pressure at 80 ° C. for 24 hours.
2.48 kg was obtained. This PPS resin is linear,
Melt viscosity 15 Pa · s (320 ° C, shear rate 1000 sec
^-1 ), the glass transition temperature was 89 ° C, and the crystal melting temperature was 280 ° C.

Glass transition temperature and crystal melting temperature are DSC
(PERKIN-ELMER DSC-7) was used to measure at a heating rate of 20 ° C./min.

Examples 1 to 5 A raw material having the composition shown in Table 1 was used as a twin screw extruder having an extrusion temperature of 320 ° C. (PCM-3 manufactured by Ikegai Industry Co., Ltd.).
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 dyed with nylon-4,6 by a phosphotungstic acid dyeing method, and then an ultrathin section was cut out and magnified 100,000 times with a transmission electron microscope. Observed, but 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 320 ° C.

Further, it was rapidly cooled in the ice water, and a 100 μm-thick section was cut out from the gut having the fixed structure. The samples of Examples 1 to 3 were 290 ° C., the sample of Example 4 was 310 ° C., and the sample of Example 5 was cut. Each sample was heat-treated at 270 ° C., and the structure formation process during this heat-treatment was traced using small-angle X-ray scattering. In each sample, a peak appeared 10 seconds 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 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 freeze the structure, and the phosphotungstic acid staining method was used. When ultra-thin sections were cut out after dyeing nylon 4 and 6, and observed under a transmission electron microscope at a magnification of 100,000 times, a biphasic continuous structure was observed in all the samples.

Further, the section for which the small-angle X-ray scattering was measured was subjected to a heat treatment at each temperature described above for a total of 60 seconds after forming a structure in the initial process,
The structure was formed to obtain the PPS resin composition of the present invention. 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 1 in the same manner as in the above initial process. 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.

Also, after discharging from the die, a gut having a structure fixed by being rapidly cooled in ice water was subjected to heat treatment at the same temperature and time as the heat treatment described above by a hot press to prepare a sheet (thickness 0.2 mm). 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 by a punching press, and a tensile impact test was performed according to ASTM D1822. The measurement results are shown in Table 1.

The following resins were used. PPS-1: PPS resin (PP polymerized in the above reference example
S resin) PA-1: Nylon 4,6 resin ("STANYL" manufactured by DSM Co., Netherlands, relative viscosity 3.0 at 96% sulfuric acid 1 g / dl, crystal melting temperature 295 ° C).

Comparative Example 1 A sample having a fixed structure was obtained by melt-kneading in the same manner as in Examples 1 to 5 except that the extrusion temperature was set to 300 ° C., and immediately after discharging from the die, the mixture was rapidly cooled in ice water. , This sample was turbid, and the sample in which nylon-4,6 was dyed by the phosphotungstic acid dyeing method,
When observed with a transmission electron microscope at a magnification of 1000 times, a non-uniform dispersed structure of 1.0 μm or more was observed. This shows that this sample was not compatibilized under shear in an extruder at an extrusion temperature of 300 ° C. This is presumably because this system has an LCST type phase diagram and is incompatible under the shearing conditions in the extruder at an extrusion temperature of 300 ° C. Also for this sample,
The results of measuring the mechanical properties and the results of observing the state of the structure are shown in Table 1 in the same manner as in No. 3.

Comparative Example 2 The same as Examples 1 to 3 except that the heat treatment was carried out at 260 ° C. for 60 seconds, and the results of measuring the mechanical properties of the sample, the structural period and the state of the structure were observed. The results are shown in Table 1. However, the structural period of this sample was measured by a small-angle light scattering device. When the heat treatment temperature is low and the structural period in the initial process does not become sufficiently small as in this example, the structural period is controlled within the range of the present invention by performing structural development to make the concentration difference between the two components sufficient. Will be difficult. Further, as in this example, when the structural period deviates from the range of the present invention, only poor mechanical properties were obtained.

[0078]

[Table 1]

From these results, it is found that in the initial stage of the spinodal decomposition of the present invention, the sample having the structure developed after forming the biphasic continuous structure having a specific structural period has excellent mechanical properties. Recognize.

Examples 6 to 8 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 320 ° C.
0) and discharged from the die, the gut was immediately cooled in ice water to fix the structure. Next, extruded pellets obtained by cutting this gut into pellets using a strand cutter were obtained. The extruded pellets were dyed with nylon-4,6 by a phosphotungstic acid dyeing method, and then ultrathin sections were cut out and observed with a transmission electron microscope at a magnification of 100,000 times. It was also confirmed that, except for the glass fiber, the structure having a size of 0.001 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 320 ° C.

Here, a part of the extruded pellets was supplied to an injection molding machine (PS20E2ASE manufactured by NISSEI PLASTIC INDUSTRIES CO., LTD.) In which the resin temperature was 320 ° C. and the mold temperature was 20 ° C., and 6
Injection molding was carried out under the conditions of 0% injection speed and 1-speed 1-pressure at an injection pressure described below with a time cycle of an injection time of 10 seconds and a holding pressure of 60 seconds to obtain a connector molded product having a shape described later ( This means that the progress of phase decomposition was stopped and the structure was frozen in the initial process of spinodal decomposition by setting the mold temperature to 20 ° C. and rapidly cooling the molded product after injection molding in the mold.) Nylon-4,6 was cut out from the surface layer of the obtained molded product and subjected to a phosphotungstic acid dyeing method.
After staining with, the sample obtained by cutting out an ultrathin section was observed under a transmission electron microscope at a magnification of 100,000 times, and as a result, a double-phase continuous structure of 0.01 μm was observed in each sample.

Next, a part of the above extruded pellets is separately
A connector molded article was injection-molded under the same conditions as above except that the mold temperature was set to 150 ° C., and a sample cut out from the surface layer of the resulting molded article was similarly subjected to structural analysis from small-angle X-ray scattering. Table 2 shows the results of determining the distance between particles and the results of observing the state of the structure with a transmission electron microscope. At the mold temperature of 150 ° C. in this example,
Similar to the above, it can be seen that the structure is developed after the structure was formed in the initial process of spinodal decomposition.

The burr length was measured by using two rows of 50 pin holes (pin hole spacing: 1.27 mm) in one row, and the number of pins was 6
8mm × 5mm × height 7mm, soft glue 70mm × 7
mm, a box-shaped product with a height of 9.3 mm, and a connector molded product having a shape in which ribs are provided at both ends in the longitudinal direction, first find the minimum injection pressure at which the resin is filled up to the tip,
Molding was performed at an injection pressure of the pressure +3 kgf / cm ² (gauge pressure), the burr length generated in the pin hole portion of the obtained molded piece was measured using a universal projector, and the average value was obtained. The results are shown in Table 2.

Further, a part of the above extruded pellets was separately supplied to an injection molding machine (PS20E2ASE manufactured by NISSEI PLASTIC INDUSTRIES CO., LTD.) In which the resin temperature was 320 ° C. and the mold temperature was 150 ° C., the injection speed was 60%, and the tip was Minimum pressure to fill up to +
Izod impact test piece in accordance with ASTM D256 is obtained by injection molding under a condition of one speed and one pressure with an injection pressure of 3 kgf / cm ² (gauge pressure) and a time cycle of an injection time of 10 seconds and a holding time of 60 seconds. It was The obtained molded product is AST
The results of measuring the Izod impact strength based on MD 256 are shown in Table 2.

The following resins were used. PPS-1: PPS resin (PP polymerized in the above reference example
S resin) PA-1: Nylon 4,6 resin ("STANYL" manufactured by DSM Co., Netherlands, relative viscosity 3.0 at 96% sulfuric acid 1 g / dl) GF-1: E glass R-1 having an average fiber diameter of 13 µm : Carboxylic acid amide wax (reaction product “WH2 of stearic acid, sebacic acid, and ethylenediamine”
55 ").

Comparative Example 4 A sample having a fixed structure was obtained by melt-kneading in the same manner as in Examples 6 to 8 except that the extrusion temperature was set to 300 ° C., and immediately after discharging from the die, the mixture was rapidly cooled in ice water. The sample was dyed with nylon-4,6 by the phosphotungstic acid dyeing method, and then an ultrathin section was cut out and magnified 1000 times with a transmission electron microscope and observed. A non-uniform dispersed structure having a size of 0.0 μm or more was observed. From this, this sample has an extrusion temperature of 3
It can be seen that they are not compatibilized under shear in an extruder at 00 ° C. This is because this system has an LCST phase diagram,
It is considered that it is incompatible under the shearing conditions in the extruder at an extrusion temperature of 300 ° C. Also for this sample, Table 2 shows the results of measuring the Izod impact strength and the burr length as in Examples 6 to 8 and observing the state of the structure.

[0087]

[Table 2]

From these results, in the initial stage of the spinodal decomposition of the present invention, after the formation of a biphasic continuous structure having a specific structural period, the structure developed sample has an excellent Izod impact strength and a burr length. It can be seen that the burrs are short and have excellent burr characteristics.

Example 9 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 3 was set at an extrusion temperature of 320 ° C.
0) and discharged from the die, the gut was immediately cooled in ice water to fix the structure. All of the guts are transparent, and the guts were stained with nylon 6 oligomer by the phosphotungstic acid staining method, and then ultrathin sections were cut out and observed with a transmission electron microscope at a magnification of 100,000 times. As a result, it was confirmed that the structures having a size of 0.001 μm or more were not seen and compatibilized in all the samples. From this, this system has an extrusion temperature of 32
It can be seen that they compatibilize under shear in an extruder at 0 ° C.

Further, it was rapidly cooled in the above ice water, a 100 μm-thick section was cut out from the gut with the fixed structure, and 320
Heat treatment was carried out at 0 ° C., and the structure formation process during this heat treatment was followed 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 this small-angle X-ray scattering measurement, a part of it was immediately quenched in ice water to fix the structure, and the phosphotungstic acid staining method was used. When a sample obtained by cutting an ultrathin section after staining with nylon 6 oligomer was observed under a transmission electron microscope at a magnification of 100,000 times, a continuous biphasic structure was observed.

Next, the above-mentioned gut was pelletized, the extrusion temperature was set again at 320 ° C., and the mixture was supplied to a twin-screw extruder (TEX30α manufactured by Japan Steel Works) whose screw rotation speed was adjusted so that the residence time was 5 minutes. Immediately after discharging from the die, the gut was rapidly cooled in ice water to fix the structure. This gut showed a slight decrease in transparency, and after the gut was dyed with nylon 6 oligomer by the phosphotungstic acid dyeing method,
When a sample obtained by cutting an ultrathin section was observed with a transmission electron microscope, a biphasic continuous structure was observed. From these facts, it is considered that in this system, the nylon 6 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 (320 ° 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, and the results of observing the structural period and the state of the structure are shown in Table 3.

The following resins were used. PPS-1: PPS resin (PP polymerized in the above reference example
S resin) PA-2: Nylon 6 oligomer (concentration 1 in concentrated sulfuric acid)
%, The relative viscosity measured at 25 ° C. is 1.20, and the crystal melting temperature measured by DSC is 225 ° C.).

Comparative Example 5 Melt kneading was carried out in the same manner as in Example 9 except that nylon 6 having a high molecular weight was used as a resin to be added to the PPS resin, and immediately after discharge from the die, it was rapidly cooled in ice water to fix the structure. A sample was obtained, but this sample was turbid, and a sample obtained by dyeing nylon 6 by the phosphotungstic acid dyeing method was used to measure 1000 with a transmission electron microscope.
When magnified twice and observed, a non-uniform dispersed structure of 1 μm or more was observed. This shows that this sample was not compatibilized under shear in an extruder at an extrusion temperature of 320 ° C. Also in this system, 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 3 as in Example 9.

The following resins were used. PA-3: Nylon 6 (concentrated sulfuric acid, concentration 1%, 25 ° C)
Relative viscosity of 3.20 measured by DSC and crystal melting temperature of 225 ° C measured by DSC)

[0096]

[Table 3]

From these results, it is found that, in the initial stage of the spinodal decomposition of the present invention, the sample in which the structure is developed after the formation of the biphasic continuous structure having the specific structural period has excellent mechanical properties. Recognize.

[0098]

According to the present invention, it has excellent mechanical properties,
In addition, PP, which has excellent low burrs, is useful as a molding material.
An S resin composition can now be obtained. In a more preferred embodiment, a PPS resin composition having excellent regularity, finely controlling its structure, and further sufficiently developing the concentration difference between the two phases of the structure can be obtained. Further, according to the present invention, it has become possible to obtain a PPS resin composition which is useful as a structural material by utilizing its excellent mechanical properties and is also useful as an injection molding material by utilizing its excellent low burr property.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F070 AA13 AA15 AA18 AA24 AA44                       AA46 AA47 AA50 AA52 AA54                       AA55 AA58 AB08 FA03 FA17                       FB06 FC06                 4F201 AA34K BA03 BC37 BD04                       BD05 BM05 BM06 BM12 BM14                       BN15 BN44                 4J002 BB03X BB12X BC03X BD15X                       BN15X CC03X CD00X CF00X                       CG00X CH02X CH07X CH09X                       CL00X CM04X CN01W CN03X                       FA040 FD010 FD020 FD140                       FD160 FD170

Claims (13)

[Claims] 1. A polyphenylene sulfide resin composition comprising at least two component resins and containing at least one polyphenylene sulfide resin, wherein the polyphenylene sulfide resin composition has a two-phase continuous structure having a structural period of 0.01 to 1 μm, Alternatively, a polyphenylene sulfide resin composition having a dispersed structure with an interparticle distance of 0.01 to 1 μm. 2. A polyphenylene sulfide resin composition comprising at least two resin components, which are phase-separated by spinodal decomposition, and containing at least one polyphenylene sulfide resin. In the initial process of the spinodal decomposition, a structural period of 0.001 is obtained. After the formation of a biphasic continuous structure of 0.1 to 0.1 μm, a biphasic continuous structure of a structural period of 0.01 to 1 μm or a dispersed structure of an interparticle distance of 0.01 to 1 μm is further developed. A polyphenylene sulfide resin composition. 3. The polyphenylene sulfide resin composition is produced by melt-kneading.
The polyphenylene sulfide resin composition according to claim 1. 4. The polyphenylene sulfide resin composition according to claim 3, wherein the spinodal decomposition is compatible under shear during melt-kneading and phase-separates under non-shear after discharge. 5. The polyphenylene sulfide resin composition undergoes spinodal decomposition by chemically reacting a precursor of at least one of the resin components constituting the polyphenylene sulfide resin composition in the presence of the remaining resin components. Claims 1 to 1 obtained by induction.
4. The polyphenylene sulfide resin composition according to any one of 4 above. 6. The spinodal decomposition is such that the spinodal decomposition is once compatible with each other before the chemical reaction and is phase-separated after the chemical reaction.
The polyphenylene sulfide resin composition described. 7. The method according to claim 1, which is for injection molding.
The polyphenylene sulfide resin composition according to the item. 8. The polyphenylene sulfide resin composition according to claim 1, which is used for film and / or sheet extrusion molding. 9. A method for producing a polyphenylene sulfide resin composition, which comprises phase-separating a polyphenylene sulfide resin composition comprising at least two resin components and containing at least one polyphenylene sulfide resin by spinodal decomposition. In the process, after forming a biphasic continuous structure with a structural period of 0.001 to 0.1 μm, a biphasic continuous structure with a structural period of 0.01 to 1 μm,
Alternatively, a method for producing a polyphenylene sulfide resin composition is characterized in that a dispersion structure having an interparticle distance of 0.01 to 1 μm is developed. 10. The spinodal decomposition is induced by melt-kneading a polyphenylene sulfide resin composition comprising at least two resin components and containing at least one polyphenylene sulfide resin.
A method for producing the described polyphenylene sulfide resin composition. 11. The method for producing a polyphenylene sulfide resin composition according to claim 10, wherein at least two resin components are compatible with each other under shearing during melt-kneading, and phase separation is performed under non-shearing after discharging. . 12. A precursor of at least one of resin components constituting a polyphenylene sulfide resin composition,
The spinodal decomposition is induced by causing a chemical reaction in the coexistence of the remaining resin components.
A method for producing the described polyphenylene sulfide resin composition. 13. The method for producing a polyphenylene sulfide resin composition according to claim 12, wherein the polyphenylene sulfide resin composition is once compatible with each other before the chemical reaction and is phase separated after the chemical reaction.