JP2014226842A - Method for producing resin molding having co-continuous structure, and method for producing porous resin molding having co-continuous structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin molding having a co-continuous structure, which can be realized simply and easily in polymer-alloy systems including an immiscible system.SOLUTION: The method for producing the resin molding having the co-continuous structure comprises a step of heat-treating the resin molding (c), that has a sea-island structure the sea component of which comprises a thermoplastic resin (a) and the island component of which comprises another thermoplastic resin (b) and that has 0.2 or lower standard deviation of the number-average diameter of the island components, at the temperature which is higher than the temperature of the higher one of the melting point of the thermoplastic resin (a) and that of the thermoplastic resin (b) by 0.1-500°C and at which the thermoplastic resin (a) and the thermoplastic resin (b) are not dissolved with each other.

Description

  The present invention relates to a method for producing a molded body comprising a resin molded body having a co-continuous structure and a method for producing a porous resin molded body.

  Technologies based on various functions of polymer materials form an indispensable foundation in all industrial fields, from electronics and information industries to automobiles, aircraft, electronics devices, and medical devices. In recent years, market needs have become diversified and sophisticated, and performances that cannot be easily obtained with a single resin have been demanded. Development of new materials by so-called polymer alloying technology, which combines the properties of resins, draws out the advantages of each resin as raw material, and compensates for the disadvantages, and develops superior properties compared to a single resin Is being actively conducted.

  The physical properties of the polymer alloy are greatly affected by the phase separation structure of each resin to be mixed. Among them, a polymer alloy having a structure in which a plurality of resin components form a continuous phase with each other, that is, a so-called co-continuous structure has excellent mechanical strength because stress is dispersed by a three-dimensional network structure. In addition, when a substance-permeable polymer is included as a component, a polymer alloy having excellent substance permeability can be obtained because the continuous phase becomes a permeation path. Furthermore, by removing one phase of the co-continuous structure with a solvent, etc., it is possible to easily form a network structure consisting of the other phase, so it can be used as a separation membrane or filter that matches their size. Has been proposed (for example, Patent Document 1).

  As a method for producing a polymer alloy having a bicontinuous structure, a method using spinodal decomposition is disclosed (for example, Patent Documents 2 to 5). In this method, once the mixed system is uniformly mixed, the temperature is rapidly changed to a temperature in an unstable region, thereby rapidly causing spinodal decomposition type phase separation to form a co-continuous structure. Although this method can obtain a uniform and fine co-continuous structure, this method cannot be applied unless it is a combination of resins capable of achieving a compatible state. In general, since most of the resin combinations are incompatible, the range of application of this technology is extremely narrow. Polymers containing heat-resistant resins, such as polyphenylene sulfide, polyetheretherketone, and liquid crystal polymers, that are expected to expand applications and increase demand due to the recent development of electrical and electronic equipment and higher performance of automobiles. With regard to alloys, there are currently few combinations that can be in a compatible state. In addition, regarding the formation of the co-continuous structure by spinodal decomposition, there is a difficulty in that a large pore diameter cannot be obtained when one phase is removed as described above.

  As for the production of a co-continuous structure using an incompatible polymer alloy, a method using an inversion region of a sea-island structure is known (for example, Non-Patent Document 1). In general, it is well known that a high-order structure of an incompatible polymer alloy forms a sea-island structure by one polymer being a continuous phase and the other being a disperse phase. Phase transition occurs under conditions such that the composition between the polymers to be mixed and the melt viscosity ratio are substantially proportional, and a co-continuous structure appears near the conditions under which this phase transition occurs. However, the co-continuous structure produced by this method is thermally unstable and the size of the continuous phase is uniquely determined by the composition between the polymers to be mixed and the melt viscosity ratio. It is difficult to control freely. Although a structure control method by addition of a filler is also disclosed (Patent Document 6), there is a concern that the added filler may affect the physical properties of the polymer alloy, and the resin combination and the filler addition ratio are excessive. It is difficult to say that this is a general-purpose method because it needs to be studied and kneading by high shear is essential. In addition, in this method, since the shear is applied when the co-continuous structure is formed, it is a big problem that the co-continuous structure is oriented.

  Thus, the present condition is that the method of obtaining the resin molding which has a co-continuous structure simply in the polymer alloy type | system | group containing an incompatible type | system | group has not been found.

JP 2000-1612 A Japanese Patent Laid-Open No. 3-20333 JP 2010-195964 A JP 2003-286414 A Japanese Patent Application Laid-Open No. 8-113828 JP 2009-29114 A

"Polymer Alloy First Edition" edited by Polymer Society, p. 30

  An object of the present invention is to provide a method for producing a resin molded body having a co-continuous structure, which can be easily realized in a polymer alloy system including an incompatible system.

  In response to the above problems, the present invention is as follows. That is, the method for producing a resin molded body having a co-continuous structure of the present invention has a sea-island structure in which the thermoplastic resin (a) constitutes a sea component and the thermoplastic resin (b) constitutes an island component. The resin molded body (c) having a relative standard deviation of the number average diameter of 0.2 or less is 0.1 to higher than the higher one of the melting point of the thermoplastic resin (a) and the melting point of the thermoplastic resin (b). This is a method for producing a resin molded body having a co-continuous structure, which includes a step of performing a heat treatment at a temperature that is 500 ° C. higher and at which the thermoplastic resin (a) and the thermoplastic resin (b) are not compatible.

  According to the present invention, in a polymer alloy system including an incompatible system, a resin molded body having a co-continuous structure and a porous resin molded body having continuous pores can be obtained by a simple method.

[Sea-island structure]
In the method for producing a resin molded body having a co-continuous structure of the present invention, the thermoplastic resin (a) has a sea-island structure in which the sea component and the thermoplastic resin (b) constitutes an island component, and the number of the island components A resin molded body (c) having a relative standard deviation of an average diameter of 0.2 or less is used. There is a standard deviation as an index representing the dispersion of the particle size of the island component, that is, the thermoplastic resin (b) in the resin molded body (c), but this value cannot be simply compared when the average particle size is different. Therefore, when comparing the particle size variation, a value obtained by dividing the standard deviation by the number average diameter of the particles, that is, a relative standard deviation (variation coefficient) is used.

  In the present invention, the number average diameter of the thermoplastic resin (b) particles is all the particles whose structure can be completely confirmed in the observation section by observing the structure of the resin molded body with a transmission electron microscope (TEM). It is a value calculated | required as an average diameter when the diameter of a vertical direction and a horizontal direction is measured about. At that time, if the number of particles whose contours can be completely confirmed is 39 or less, the observation range is expanded and the average particle size is calculated using information of 40 or more particle sizes.

  In the present invention, the thermoplastic resin (b) dispersed in the resin molded body (c) by heat treatment is simultaneously and repeatedly connected to develop a co-continuous structure. It is essential that the relative standard deviation of the number average diameter of the island components is 0.2 or less. From the viewpoint of obtaining a highly uniform co-continuous structure, the relative standard deviation is preferably 0.17 or less, more preferably 0.15 or less.

The average particle size of the island component made of the thermoplastic resin (b) is preferably 0.2 to 300 μm and more preferably 0.2 to 30 μm or less from the viewpoint of versatility of the co-continuous structure by heat treatment. Preferably, it is 0.3-5 micrometers.
[Combination of thermoplastic resin (a) and thermoplastic resin (b)]
The weight fraction of the thermoplastic resin (a) and the thermoplastic resin (b) in the resin molded body (c) is preferably 30/70 to 70/30 because a highly uniform co-continuous structure can be obtained. 35/65 to 65/35, more preferably 40/60 to 60/40.

  In general, a polymer alloy composed of two or more components has a compatible system that is compatible in all practical ranges above the glass transition temperature and below the thermal decomposition temperature, and vice versa. There is a partially compatible system that is compatible with each other and incompatible with other regions.

  In the present invention, the basic technical idea is that the island components in the sea-island structure are connected to develop a co-continuous structure by performing heat treatment in a temperature range equal to or higher than the melting point. Therefore, it is important that the thermoplastic resin (a) and the thermoplastic resin (b) are not compatible with each other during the heat treatment, and must be a combination of an incompatible system or a partially compatible system. In general, it is known that in a combination that is not compatible, the sea-island structure is maintained even after heat treatment, or the two layers are completely separated. However, in the present invention, a co-continuous structure can be formed in a specific sea-island structure by heat treatment performed under conditions determined by a simple method described later. Further, if the combination of the thermoplastic resin (a) and the thermoplastic resin (b) is a partially compatible system, the heat treatment temperature is selected in a temperature region where the compatible state is not achieved.

Here, “incompatible” in the present invention refers to a state in which the phase mainly composed of the resin of the thermoplastic resin (b) forms a phase structure having a dispersion diameter of 0.2 μm or more. In order to confirm the incompatibility at a specific temperature, a compatibility test showing the following procedure is performed. First, the two thermoplastic resins to be mixed were kneaded in a biaxial kneader at a shear rate of 500 s ⁻¹ and a residence time of 30 seconds for applying shear at a temperature 30 ° C. higher than the melting point of the high-melting thermoplastic resin. Thereafter, the resin molded body is solidified by dropping into water at 25 ° C. within 5 seconds after discharge. Next, a small piece is cut out from the resin molded body, placed on an optical microscope with a stage that is held in advance at a temperature desired to be measured higher than the melting point, sandwiched between cover glasses, and held for 10 minutes for observation. Here, when a phase structure of 0.2 μm or more is observed, it can be confirmed that the phase structure is not compatible at that temperature.

In the present invention, the thermoplastic resin (a) and the thermoplastic resin (b) are not particularly limited except that they are incompatible or partially compatible, and various combinations can be used. Generally, in order to improve the uniformity of the phase separation structure in the resin molded body, it is preferable that the compatibility of the resin as a component is high. One of the indexes for this purpose is a solubility parameter (SP value), and this index can be referred to in the present invention. The SP value is a parameter reflecting the cohesive strength of a substance defined by (evaporation energy / molar volume) ^1/2 , and there is a high possibility that a polymer alloy having good compatibility is obtained between resins having close SP values.

The polymer alloy of the present invention must be a combination of a partially compatible system or an incompatible system. On the other hand, if the SP value is not too large, the uniformity of the final co-continuous structure tends to be higher, and the process stability in heat treatment is improved. Since the property increases, the absolute value of the difference in SP value is preferably 0.1 to 9 (J / cm ³ ) ^1/2 , and 1 to 6 (J / cm ³ ) ^1/2. Is more preferable. The SP value is known for various polymers, and is described, for example, in “Plastic Data Book”, edited by Asahi Kasei Amidus Corporation / Plastics Editorial Department, page 189. As will be described later, a combination of a certain thermoplastic resin (a) and a certain thermoplastic resin (b) can be obtained by conducting a test for confirming the above-described incompatible combination while referring to the value of the SP value difference. It can be simply evaluated whether it can be used for invention.

  The difference in melting point between the thermoplastic resin (a) and the thermoplastic resin (b) is preferably 80 ° C. or lower because deterioration due to thermal decomposition or the like is suppressed during heating, more preferably 65 ° C. or lower, and 50 ° C. More preferably, it is as follows.

  Further, when at least one component of the thermoplastic resin (a) and the thermoplastic resin (b) is a crystalline resin, the structure of the molded body can be easily fixed by crystallization of the crystalline resin. Is preferably a crystalline resin.

  The crystalline resin is not particularly limited as long as the crystal melting temperature is observed with a differential scanning calorimeter (DSC). For example, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyphenylene sulfide, Examples include polyether ether ketone, fluororesin, liquid crystal polymer, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl chloride.

  When polyphenylene sulfide (hereinafter sometimes referred to as PPS) is applied to the present invention as one of the crystalline resins, a polymer containing 70 mol% or more of p-phenylene sulfide as a repeating unit is used. The molded product after heat treatment is excellent in heat resistance and chemical resistance, and is preferable from the viewpoint of being able to be used in a wide range of applications as a molded product having a bicontinuous structure of the present invention.

  PPS is a known method, for example, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight. The obtained PPS is washed with an acid aqueous solution (acid washing), treated with an organic solvent or hot water, washed with water containing an alkaline earth metal salt, acid anhydride, amine, isocyanate, functional group-containing disulfide compound, etc. Various treatments such as activation with functional group-containing compounds, cross-linking / high molecular weight by heating in air, use after applying heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, and these treatments Can be used after being repeated several times or by combining different processes.

  The viscosity of the raw material PPS is not particularly limited as long as it can be used as a molding material, but the melt flow rate (hereinafter referred to as MFR) is 50 to 180 g / 10 minutes, particularly 50 to 150 g / 10 minutes. Are preferably used. Here, the MFR of PPS is spilled resin amount per 10 minutes (g) measured under the conditions of 316 ° C., orifice diameter 2.095 mm, orifice length 8.00 mm, and load 5 kg in accordance with ASTM D1238-86. It is represented by When manufacturing a sea-island-structured resin molded product (c) containing PPS as a sea component by melt-kneading with another thermoplastic resin, if the MFR of PPS is 50 g / 10 min or more, PPS will be finely dispersed. It is preferable because a fine cocontinuous structure obtained by heat treatment can be obtained, and the control range of the size of the cocontinuous structure is widened. When the MFR is 180 g / 10 min or less, the shape of the finely dispersed PPS particles becomes close to a true sphere, and the uniformity of the co-continuous structure obtained by heat treatment is further preferable.

  When polyethylene terephthalate (hereinafter sometimes referred to as “PET”), which is one of the crystalline resins, is applied to the present invention, even homo-PET having no copolymerization component is copolymerized PET. May be.

  As long as the effect of the present invention is not impaired, any component may be copolymerized with PET, and the amount of copolymerization is not particularly limited, but when the thermoplastic resin (b) is polyphenylene sulfide. The thermoplastic resin (a) is polyethylene terephthalate copolymerized with 0.01 to 20 mol% of dimethyl sodium 5-sulfoisophthalate (hereinafter sometimes referred to as SSIA), and the period of the co-continuous structure is This is a preferred embodiment that tends to be uniform. When the SSIA copolymerization ratio is 0.01 mol% or more, a highly uniform co-continuous structure can be obtained. When the SSIA copolymerization ratio is 20 mol% or less, the SSIA copolymer PET has sufficient heat resistance, and the melting point of PPS. When melt-kneading with PPS at the above temperature, mixing of bubbles due to generation of pyrolysis gas can be suppressed. That is, when the SSIA copolymerization ratio is 0.01 to 20 mol%, both the heat resistance of the SSIA copolymer PET and the high uniformity of the co-continuous structure obtained after the heat treatment can be achieved. The SSIA copolymerization ratio is preferably 5 to 15 mol%, and particularly preferably 8 to 12.5 mol%, since a co-continuous structure with higher uniformity can be obtained.

  The combination with a small SP value difference is a reference in selecting the thermoplastic resin (a) and the thermoplastic resin (b) of the present invention, but this is not necessarily a combination that is excellent in the ease and uniformity of formation of a bicontinuous structure. It cannot be said. For example, when SSIA, which is a hydrophilic component, is copolymerized with PET, the SP value difference with PPS is larger than PET without the copolymer component, but the homogeneity of the resulting co-continuous structure is that the copolymer component is PET with SSIA copolymerized is higher than PET without it. As described above, the homogeneity of the co-continuous compound obtained from the SP value alone is difficult to predict completely, but can be confirmed by a preliminary experiment for obtaining a guideline for the heat treatment time described later. The combination of PPS and SSIA copolymerized PET is a particularly preferred embodiment in the present invention in terms of ease of formation of a co-continuous structure and uniformity of structure in addition to excellent heat and chemical resistance. .

  When the thermoplastic resin (b) is polyphenylene sulfide, the co-continuous structure can be obtained more uniformly when the thermoplastic resin (a) is SSIA copolymerized PET than when it is homo-PET without a copolymer component. The reason why the property has increased is not clear, but it is considered that SSIA may have a high affinity specifically for a part of the structure of PPS.

Homo PET or copolymerized PET applied to the present invention can be obtained by a known method. The PET or SSIA copolymerized PET of the present invention has sufficient heat resistance when 75 mol% or more of all repeating units are composed of ethylene terephthalate units, from the viewpoint of suppressing thermal decomposition during melt-kneading with PPS. preferable. Moreover, there is no problem even if other components are contained. For example, as an acid component other than terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p- An aromatic, aliphatic or alicyclic carboxylic acid such as oxybenzoic acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid may be copolymerized, and as a glycol component other than ethylene glycol, Alicyclic, aliphatic or aromatic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S may be copolymerized.
[Resin molding (c)]
The resin molded body (c) does not include an intermediate with melt remolding. That is, in the practice of the present invention, the shape of the molded body is substantially maintained even when heat treatment at a melting point or higher is performed, and the resin is heat-treated to such an extent that it exhibits fluidity to substantially have another shape. Items to be molded (for example, chips used for melt molding) are not included. The shape of the resin molded body (c) is not particularly limited, but for example, fibers, films, sheets, plates, disks, blocks, balls, lenses, rods, strands, tubes, cords, chips, and the like are preferable.
〔Heat treatment〕
In the present invention, the heat treatment of the molded body composed of the sea-island-structured resin molded body (c) is performed by the thermoplastic resin (a) and the thermoplastic resin (b) having the higher melting point (hereinafter simply referred to as “high”). The temperature is 0.1 to 500 ° C. higher than the melting point of the “melting point thermoplastic resin”, and the thermoplastic resin (a) and the thermoplastic resin (b) are not compatible with each other. By setting the temperature to 0.1 ° C. or more higher than the melting point of the high melting point thermoplastic resin, both the thermoplastic resin (a) and the thermoplastic resin (b) are melted to form the co-continuous structure of the present invention. Can do. The heat treatment temperature is preferably 0.5 ° C. or more, more preferably 1 ° C. or more higher than the melting point of the high-melting thermoplastic resin, in that the formation speed of the co-continuous structure can be increased. Moreover, deterioration by the thermal decomposition etc. of a thermoplastic resin (a) and a thermoplastic resin (b) can be suppressed by setting it as 500 degrees C or less higher than the melting point of a high melting point thermoplastic resin. The heat treatment temperature is preferably 80 ° C. or less, more preferably 10 ° C. or less, higher than the melting point of the high-melting thermoplastic resin in terms of ease of structure control.

  The heat treatment temperature is not the set value of the heating equipment but the resin surface temperature, which can be obtained by actual measurement. For example, when the molded body is heated by bringing it into contact with a solid, such as heating the support, the surface temperature is measured with a contact thermometer to determine the heat treatment temperature. When the molded body is heated in contact with a heat medium, such as when introduced into a high-temperature gas or high-temperature liquid, the temperature varies depending on the desired heat treatment temperature and the thermometer used. The heat treatment temperature is determined by measuring the temperature of the heat medium.

The heat treatment time can be appropriately selected depending on the thermoplastic resin to be selected, but it is preferable to predict the standard in advance by conducting a simple preliminary experiment. This time is important in that it determines whether a co-continuous structure can be formed, whether it stays in the sea-island state, or is completely separated into two layers. First, a small piece of a resin molded body having a sea-island structure equivalent to the resin molded body (c) forming the molded body to be heat treated is prepared. The small piece is sandwiched between cover glasses, and placed on an optical microscope with a heating stage previously held at the predetermined heat treatment temperature, and observation is performed while measuring time. At that time, island components of the sea-island structure are connected after a certain period of time, and a co-continuous structure is observed. When the smallest island component within the field of view is the time to start bonded to another island component and t _1, it is preferable to determine the heat treatment time t ₂ in the present invention the time t1 as a guide. The heat treatment time t ₂ is preferably t ₁ to t ₁ × 20, depending on the heating method, the size of the molded body, the efficiency of the heat treatment equipment, and the like. bicontinuous structure throughout the molded body sufficiently islands connected by the t ₂ and t ₁ or more is uniformly formed. The t ₂ With t ₁ × 20 or less, it is possible to suppress thermal degradation of the thermoplastic resin (a) or the thermoplastic resin (b). T ₂ from the viewpoint of suppressing coarse island of by division of coarse and ligated island structure of the bicontinuous structure, more preferably to t ₁ ~t ₁ × 10, and t ₁ ~t ₁ × 5 it is more preferable, and particularly preferably _{t 1} × _{1.1~t 1} × 2.

  Although there is no restriction | limiting in particular in the heating method in the heat processing of this invention, It is preferable to superheat in the state in which shearing is not provided to a resin molding (c) substantially. The state where substantially no shear is applied refers to a state in which the size of the molded body does not change by 5% or more before and after heat treatment and during heat treatment. It is preferable that a co-continuous structure is formed in a state where no shear is substantially imparted, because a co-continuous structure with almost no orientation is obtained.

  It is a preferred embodiment that at least a part of the resin molded body (c) is in contact with the support during the heat treatment. The support referred to in the present invention is a member for maintaining the overall shape of the resin molded body (c) in the heat treatment step. The support is preferably made of a material that retains its shape at the heat treatment temperature. Examples of suitable materials include metals (steel, copper, nickel, aluminum, silver, gold, etc.) and other inorganic substances (silica, alumina). , Carbon, glass, etc.), high heat resistant resin (polyimide, etc.) and the like. When using a support made of a material having high thermal conductivity such as metal, the temperature of the molded body can be quickly raised to a desired temperature, and accordingly, the time required for heat treatment can be shortened. Particularly preferred. The support may have a release layer made of a release agent such as silicon resin, wax, fluororesin, or polyimide on the contact surface with the molded body. Although there is no restriction | limiting in particular regarding the size and shape of a support body, From the viewpoint of releasability with a molded object and the viewpoint of the smoothness of a molded object surface, it is preferable that the contact surface with a molded object has few unevenness | corrugations.

  In the case of using a support, a method of performing a heat treatment by heating the support is preferable from the viewpoint of simplicity and good process stability. As other methods, a method of introducing into a high-temperature gas or a high-temperature liquid serving as a heat medium, a method of radiant heating using a laser or infrared rays, or the like is employed regardless of whether or not the support is used. When introduced into a high-temperature gas or high-temperature liquid, it is preferable to use a fan to promote the movement of the high-temperature gas or high-temperature liquid that serves as a heat medium from the viewpoint of heating efficiency to the molded body and uniformity of the ambient temperature. . Moreover, it is preferable that a high temperature gas and a high temperature liquid are inactive with respect to the resin molding which comprises a molded object in the heat processing temperature.

  In the step of performing the heat treatment, the plurality of heating methods described above may be used in combination or may be performed stepwise. In the heating method used at the same time, the respective heat treatment temperatures may be different. However, in order to form a uniform co-continuous structure throughout the molded body, the difference in the respective heat treatment temperatures by the plurality of heating methods used at the same time is 50. It is preferably at most 0 ° C, more preferably at most 20 ° C, further preferably at most 2 ° C. As an example of simultaneous use of a plurality of heating methods, introduction into a high-temperature gas in a state where one surface of a film-shaped molded body is held by a heated support can be mentioned.

  When the resin molded body exhibiting a co-continuous structure by the heat treatment is cooled as it is, it is possible to solidify the structure with the co-continuous structure and obtain a resin molded body having the co-continuous structure. There is no restriction | limiting in the cooling method, What is necessary is just to cool by the well-known method used for the manufacturing process of a resin product. A higher cooling rate is preferable because coarsening of the co-continuous structure can be suppressed. For example, water cooling is preferable to air cooling.

When the shape of the molded body of the resin molded body (c) is a fiber and when a support is not used during the heat treatment, it is 100 s ^{−1 at a} temperature 20 ° C. higher than the melting point of the thermoplastic resin (a). The melt viscosity of the thermoplastic resin (a) is preferably 300 Pa · s or more from the viewpoint of preventing the fibers from being melted. Furthermore, from a viewpoint of heat processing process stability, it is more preferable that it is 400-1000 Pa.s or more. Here, the melting point in the present invention means a temperature at which a crystal melting peak is observed when the temperature is raised from 50 ° C. to 10 ° C./min in differential scanning calorimetry.
[Co-continuous structure]
The co-continuous structure means a structure determined as follows. First, it is important that the co-continuous structure in the present invention has a regular phase separation structure having a certain period, and specifically, it can be confirmed that the scattering spectrum obtained by the light scattering measurement has a maximum value. In addition to this, in the structure observation with a transmission electron microscope (TEM), the network structure in which the two-component resins enter each other and are both continuous phases is clearly different from the particulate dispersion structure. Observed as the main structure. It can be determined that a co-continuous structure is formed based on the confirmation methods of both light scattering measurement and TEM observation.

  In the light scattering measurement, the presence of the scattering maximum is a proof of a regular phase separation structure having a certain period, and the period Λm corresponds to the structure period of the bicontinuous structure. The value can be calculated by the equation Λm = (λ / 2) / sin (θm / 2) using the wavelength λ of the scattered light in the scatterer and the scattering angle θm that gives the scattering maximum. The structural period of the co-continuous structure obtained using this is preferably 0.2 to 300 μm, more preferably 0.2 to 30 μm or less, from the viewpoint of versatility of the co-continuous structure. More preferably, it is 3-5 micrometers.

  If the uniformity of the co-continuous structure is low and there is a rough part in the structure, the original polymer alloy characteristics may not be obtained. The structural period in the co-continuous structure of the alloy is preferably uniform.

  The uniformity of the co-continuous structure in the resin molded body (c) after the heat treatment in the present invention can be evaluated by light scattering measurement. In addition to the structural period in the bicontinuous structure, the light scattering measurement provides information on its distribution. Specifically, the peak position of the scattering maximum in the spectrum obtained by measurement, that is, the scattering angle θm corresponds to the structural period in the co-continuous structure, and the way the peak spreads corresponds to the uniformity of the structure. In the present invention, as an index of uniformity, in light scattering measurement, attention was paid to the scattering maximum peak half width of the spectrum in which the scattering intensity is plotted against the wave number of the scattered light. However, since the half width of the peak tends to increase as the peak maximum wave number increases, the value of (A) / (B) calculated from the half width of the peak (A) and the peak maximum wave number (B) is It was used as an index of structural uniformity. In order to express physical properties such as excellent mechanical properties, it is preferable that the structural uniformity is high, and the value of (A) / (B) is preferably 1.6 or less, and 1.3 or less. More preferably, it is 1.0 or less. Moreover, since the polymer alloy is preferably as uniform as possible, the lower limit of (A) / (B) is not particularly limited.

  In the present invention, the half width of the peak means that the peak apex is a point A, a straight line parallel to the vertical axis of the graph is drawn from the point A, and the intersection of the straight line and the spectrum base line is a point B. This is the width of the peak at the midpoint (point C) of the line segment connecting the points B. In addition, the width | variety of the peak said here is a width | variety on the straight line which is parallel to a base line and passes along the point C. FIG.

  In the present invention, when performing light scattering measurement or TEM observation of a polymer alloy, the sample needs to be a thin film. Thinning at the time of light scattering measurement can be performed by section cutting with a microtome or the like, or by heating press. In the case of a heating press, if too much heat is applied or the pressing time is long, the structure may be coarsened depending on the sample. Therefore, it is necessary to carefully determine the pressing conditions. In the case of a crystalline resin, since the alloy structure may change due to crystallization, it is necessary to rapidly cool after heat pressing to fix the structure.

  In TEM observation, ultra-thin sectioning is performed using an ultramicrotome, and the center of the material is adjusted to 5 ± 0.5 (nm / pixel), with a resolution of 700,000 pixels or more. And observe.

In the case of light scattering measurement or TEM observation, when the contained resin is small and measurement and observation are difficult, it is also effective to treat with a staining reagent such as iodine, RuO ₄ , OsO _{4 as} necessary.
〔Additive〕
As long as the effect of the present invention is not impaired, the resin molded body (c) is a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, talc, kaolin, an organic phosphorus compound, poly Crystal nucleating agents such as ether ether ketone, polyolefin-based compounds, silicone-based compounds, long-chain aliphatic ester-based compounds, long-chain aliphatic amide-based compounds, release agents such as inorganic particles and fillers, anticorrosives, anti-coloring agents, Conventional additives such as antioxidants, heat stabilizers, lubricants, UV inhibitors, colorants, flame retardants, foaming agents, matting agents, plasticizers, dyes, pigments and crystal nucleating agents can be included.

These additives can be blended in the resin molded body (c) of the present invention at an arbitrary stage, and are contained in either the thermoplastic resin (a) or the thermoplastic resin (b). May be included in both.
[Method for producing porous resin molding having continuous pores]
Another aspect of the present invention is a porous material having continuous pores obtained by removing the thermoplastic resin (a) or the thermoplastic resin (b) from the resin molded body having a co-continuous structure obtained in the present invention. It is a manufacturing method of a conductive resin molding.

  The method for removing the thermoplastic resin (a) or the thermoplastic resin (b) from the molded article having a co-continuous structure obtained in the present invention is not particularly limited, but the thermoplastic resin to be removed (hereinafter referred to as a removal component and Or the other thermoplastic resin (hereinafter sometimes referred to as a matrix component) is dissolved and removed with a solvent that does not dissolve, or only the removed component is an acidic aqueous solution or alkaline solution. A method of chemically decomposing and removing with an aqueous solution is preferably used.

  When the removal component is a polyester component, the swelling of the matrix component by the solvent can be suppressed, the extraction time of the polyester component can be greatly reduced, and the solvent remains in the matrix component and is released during use. Therefore, a method of chemically decomposing and removing with an acidic aqueous solution or an alkaline aqueous solution is a preferred embodiment. In particular, decomposition and removal with an alkaline aqueous solution is a more preferable embodiment because the efficiency of hydrolysis is high and the removal operation can be performed in a shorter time.

  The alkaline substance constituting the alkaline aqueous solution is not particularly limited, but it is preferable to use an alkali metal hydroxide or an alkaline earth metal hydroxide, which is advantageous in terms of cost, availability, and hydrolysis rate. From the balance, it is preferable to use sodium hydroxide or potassium hydroxide, and sodium hydroxide is preferable because it is easily available and has a good balance of cost.

  The concentration of the alkaline aqueous solution is not particularly limited, but a higher concentration is preferable because the time required for decomposition and removal can be reduced. A lower concentration is preferable because damage to the manufacturing apparatus and costs required for safety measures can be reduced. From these points, the concentration of the aqueous solution is preferably in the range of 0.10 to 10 N.

  The temperature of the alkaline aqueous solution is preferably 60 to 130 ° C. from the viewpoint of the hydrolysis rate of the polyester component. The viewpoint of suppressing the evaporation of water from the aqueous solution and maintaining the hydrolysis rate while keeping the concentration constant and achieving a stable treatment. Therefore, the temperature is more preferably 60 to 90 ° C.

In the case of decomposing and removing with an alkaline aqueous solution, it is preferable from the viewpoint of the removal efficiency of the polyester component to stir the solution in the solution bath.
[Use]
According to the method of selecting the combination of the resin molded body (a) and the resin molded body (b), the molded body comprising the resin molded body having a co-continuous structure obtained according to the present invention can have impact resistance, heat resistance, and chemical resistance. , Stress crack properties, moldability, economy, transparency, friction resistance, wear resistance, dimensional stability, gas barrier properties, antistatic properties, etc. can be imparted. Useful for electronic parts, audio equipment parts, household, office electrical product parts, machine-related parts, optical equipment, precision machine-related parts, automobile / vehicle-related parts, and other various applications. For example, when used as film or sheet, magnetic recording Media film, photographic film, capacitor film, electrical insulation film, packaging film, automotive interior ceiling, door trim, instrument panel pad material, bumper Useful for side frame cushioning materials, sound absorbing pads such as the back of bonnets, seating materials, pillars, fuel tanks, brake hoses, nozzles for window washer fluid, air conditioner refrigerant tubes and their peripheral parts. Rubber cords such as tire cords, conveyor belts, hoses, ropes, cables, speaker cones, tension members, screen anchors, sealant reinforcements, battery separators, campus, base fabrics, fishing nets, non-woven fabrics, safety wear, bulletproof vests, space suits It is useful in a wide range of fields such as undersea work clothes.

In addition, the porous body obtained by removing one component from the molded body made of the resin molded body having a co-continuous structure obtained by the present invention has a heat insulating material depending on the characteristics and pore diameter of the resin forming the matrix component. It is used in a wide range of fields as lightweight structural materials, buffer materials, adsorbent materials, sound absorbing materials, catalyst carriers, separation membranes, permeable membranes, battery separators, hemodialysis membranes, and the like.

  EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. Note that the compatibility test, the particle size and relative standard deviation of the island component of the sea-island structure, the structural period of the co-continuous structure, and the uniformity evaluation were measured by the above-described method and apparatus. In addition, as a preliminary examination for obtaining a compatibility test and a guide for heat treatment time, observation with an optical microscope with a heating stage using a heating stage THMS600 manufactured by Linkham and an optical microscope BX51 manufactured by Olympus was performed.

Example 1
A PET polymerized according to a conventional method and dried at 120 ° C. for 12 hours in a vacuum, and copolymerized with 10 mol% of SSIA after drying at 120 ° C. for 12 hours in a vacuum was used at a weight ratio of 50 A compatibility test was conducted at 285 ° C. with respect to the mixture mixed at / 50, and it was found that the mixture was not compatible. Subsequently, a dry blend of PPS and SSIA copolymerized PET at 50/50 was added to a twin-screw kneader (Technobel “KZW-15TWIN-30MG”, screw diameter 15 mm, L / D = 30, Including a ding disk) and melt-kneaded under the conditions of a temperature of 320 ° C. and a screw rotation speed of 200 rpm. Then, after forming into a sheet shape with a base having a width of 600 mm and a lip gap of 0.6 mm, a polymer alloy film (I) was obtained by casting with a metal drum controlled to a temperature of 20 ° C. One piece was cut out from it, cut into ultrathin sections using an ultramicrotome, and TEM observation was performed. As a result, it was confirmed that a sea-island structure was formed, and the average particle size of the island component and its relative standard deviation were obtained. Was measured.

  Next, a 1 cm square film was cut out from the polymer alloy film (I), and was observed using an optical microscope with a heating stage set at 285 ° C. in order to obtain a measure of the heat treatment time when the heat treatment temperature was 285 ° C. However, a behavior was observed in which the smallest particles in the visual field started to join after 8 seconds. (Indicated in Table 1 as “Guideline for heat treatment time”.) Based on this, the heat treatment time was set to 10 seconds and the polymer alloy film (I) was indirectly heated to a 285 ° C. heating roll for 10 seconds. . Subsequently, TEM observation and light scattering measurement were performed, and it was confirmed that a co-continuous structure was formed. (In Table 1, in the structure observation by TEM, the case where a network structure in which two component resins enter each other and both phases are continuous phases is observed as the main structure is indicated by ○, sea-island structure or uniform structure. The case where it was clear that a co-continuous structure was not formed, such as forming, was marked with x.) In the light scattering measurement, a scattering maximum peak was observed and calculated from its half-value width (A) and peak maximum wave number (B). The value of (A) / (B) to be performed was obtained.

(Examples 2 to 6)
A film having a co-continuous structure was obtained under the same conditions as in Example 1 except that the heat treatment temperature was changed.

(Examples 7 and 8)
A film having a co-continuous structure was obtained under the same conditions as in Example 1 except that the mixing ratio of PPS and SSIA copolymerized PET was changed.

(Examples 9 and 10)
A film having a co-continuous structure was obtained under the same conditions as in Example 1 except that the SSIA copolymerization ratio of the SSIA copolymer PET was changed.

(Example 11)
The same PPS and SSIA copolymerized PET as in Example 1 was dried and then supplied to a spinning machine to which a biaxial kneading extruder was connected. The spinning temperature was 320 ° C., and the molten polymer was filtered in a spinning pack through a metal filter having 5 μ pores, and then passed through a spinneret having a hole diameter of 0.30 mm and a hole depth / hole diameter ratio of 4 ejection holes of 50 holes. The spinning and discharging amount was adjusted to the spinning conditions so that the wound yarn was 220 dtex. Pass the chimney with the ambient temperature of 10cm below the base surface set to 220 ° C (chimney passing time: 1 second), immediately cool the yarn with cold air of 25 ° C, and then rotate at a speed of 600m / min It took up with a 20 degreeC take-up roll.

  Thereafter, a fiber having a co-continuous structure was obtained in the same procedure as in Example 1. The heat treatment was performed by bringing the fibers into contact with a heating roll in the same manner as in Example 1 while unwinding the fibers.

(Example 12)
A fiber having a co-continuous structure under the same conditions as in Example 11 except that it was not contacted with a heating roll but was subjected to heat treatment while running in a non-contact manner with a heater, and the heat treatment temperature was 600 ° C. Got.
(Comparative Example 1)
A polymer alloy film was obtained under the same conditions as in Example 1 except that PET homopolymer was used instead of SSIA copolymerized PET. As a result of TEM observation, it was confirmed that a sea-island structure was formed, but the uniformity of the average particle diameter of the island components was low, and the relative standard deviation was 0.44. After that, in order to obtain a measure of the heat treatment time, observation was performed under a heating condition of 285 ° C. using an optical microscope with a heating stage, and the islands were only united irregularly even after 10 minutes. The behavior at which a continuous structure starts to be formed could not be confirmed. Although the guideline for the heat treatment time could not be obtained, the heat treatment time was set to 10 seconds, and the heat treatment was performed under the condition that the polymer alloy film was indirectly attached to a heating roll at 285 ° C. for 10 seconds. Subsequently, when TEM observation and light scattering measurement were performed, a sea-island structure was observed in the TEM observation, and no scattering maximum peak was observed in the light scattering measurement. That is, it was confirmed that no co-continuous structure was formed.
(Comparative Example 2)
Instead of PPS, polyacetal having 95% acetal units (hereinafter sometimes referred to as POM) (melting point 165 ° C.) is used, and the content of D-form is 1.2% instead of SSIA copolymerized PET. There is a compatibility test in advance under the same conditions as in Example 1 using poly-L lactic acid (hereinafter sometimes referred to as PLA) (melting point: 172 ° C.) having a weight average molecular weight in terms of PMMA of 160,000. As a result, it was confirmed that they were compatible. A polymer alloy film was obtained under the same conditions as in Example 1, and no phase separation structure such as a sea-island structure or a co-continuous structure was observed even after 10 minutes at 177 ° C. using an optical microscope with a heating stage. . Although the standard of the heat treatment time was not obtained, the heat treatment time was set to 10 seconds, and the heat treatment was carried out under the condition that the polymer alloy film was indirectly attached to a 177 ° C. heating roll for 10 seconds. Subsequently, when TEM observation and light scattering measurement were performed, no phase separation structure was observed in the TEM observation, and no scattering maximum peak was observed in the light scattering measurement. (Comparative Example 3)
A polymer alloy film was obtained under the same conditions as in Comparative Example 2 except that the screw of the biaxial kneader was changed to one that did not include a kneading disk and was formed only by the flight part. In TEM, a non-uniform sea-island structure was observed, but when the optical microscope with a heating stage was observed at 177 ° C., the disappearance of the sea-island structure was observed. Despite being a compatible system, it is considered that a uniform compatible state was not reached when a polymer alloy film was obtained due to insufficient shearing in a twin-screw kneader or insufficient heat residence time. Although the standard of the heat treatment time was not obtained, the heat treatment time was set to 10 seconds, and the heat treatment was carried out under the condition that the polymer alloy film was indirectly attached to a 177 ° C. heating roll for 10 seconds. Subsequently, when TEM observation and light scattering measurement were performed, a sea-island structure was observed in the TEM observation, and no scattering maximum peak was observed in the light scattering measurement. That is, it was confirmed that no co-continuous structure was formed.

  Table 1 summarizes evaluation results, heat treatment conditions, and the like regarding the structures before and after the heat treatment for the above-described Examples and Comparative Examples.

Claims (10)

A resin molded body having a sea-island structure in which the thermoplastic resin (a) is a sea component and the thermoplastic resin (b) is an island component, and the relative standard deviation of the number average diameter of the island component is 0.2 or less ( c) is a temperature higher by 0.1 to 500 ° C. than the higher one of the melting point of the thermoplastic resin (a) and the melting point of the thermoplastic resin (b), and is thermoplastic with the thermoplastic resin (a). The manufacturing method of the resin molding which has a process of heat-processing at the temperature which resin (b) does not melt | dissolve, and has a co-continuous structure. The co-continuous structure according to claim 1, wherein a resin molded body having a weight fraction of 30/70 to 70/30 of the thermoplastic resin (a) and the thermoplastic resin (b) is used as the resin molded body (c). The manufacturing method of the resin molding which has this. The absolute value of the difference of the solubility parameter (SP value) between the thermoplastic resin (a) and the thermoplastic resin (b) is 0.1 to 9 (J / cm ³ ) ^1/2. The manufacturing method of the resin molding which has a co-continuous structure of description. The manufacturing method of the resin molding which has a co-continuous structure in any one of Claims 1-3 whose at least 1 component is a crystalline resin among a thermoplastic resin (a) and a thermoplastic resin (b). The manufacturing method of the resin molding which has a co-continuous structure in any one of Claims 1-4 which performs the said heat processing in the state in which shearing is not substantially given to the resin molding (c). The manufacturing method of the resin molding which has a co-continuous structure in any one of Claims 1-5 which performs the said heat processing in the state which contacted at least one part of the resin molding (c) with the support body.   As the resin molded body (c), a resin molded body having any shape selected from the group consisting of fibers, films, sheets, plates, disks, blocks, balls, lenses, rods, strands, tubes, cords, and chips is used. The manufacturing method of the resin molding which has a co-continuous structure in any one of Claims 1-6.   The thermoplastic resin (a) is polyethylene terephthalate copolymerized with 0.01 to 20 mol% of dimethyl sodium 5-sulfoisophthalate, and the thermoplastic resin (b) is polyphenylene sulfide. The manufacturing method of the resin molding which has a co-continuous structure in any one of Claims 4-7. Continuous hole which has the process of removing any one of a thermoplastic resin (a) or a thermoplastic resin (b) from the resin molding manufactured by the manufacturing method in any one of Claims 1-8. The manufacturing method of the porous resin molding which has this. In the step of removing either the thermoplastic resin (a) or the thermoplastic resin (b), only either the thermoplastic resin (a) or the thermoplastic resin (b) is chemically decomposed and removed. The manufacturing method of the porous resin molding which has the continuous hole of Claim 9 characterized by these.