JP2013185112A - Method of producing polyester porous body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of easily producing a polyester porous body with homogeneous pore size without using a large quantity of organic solvents.SOLUTION: In a method of producing a polyester porous body, a polyester comprising a monomer component, which is any one of a combination of a polycarboxylic acid compound and a polyhydric alcohol compound, a combination of a polycarboxylic acid compound and/or a polyhydric alcohol compound and a hydroxycarboxylic acid compound, and a hydroxycarboxylic acid compound alone, is brought into contact with a basic aqueous medium including at least an anionic surfactants and salts.

Description

  The present invention relates to a method for producing a porous polyester body that can be suitably used for applications such as heat insulating materials, various separation membranes, optical films, and capacitor insulating materials.

  Polyesters are excellent in mechanical properties, electrical insulation, chemical stability, and the like, and are used in a wide range of fields in the form of fibers, films, molded articles, and the like. In recent years, production of a porous polyester body has been studied as one measure for further functionalization of polyester.

  For example, there is a method for producing a polyester porous membrane by mixing and dispersing an alcohol in a polyester solution to produce a cast membrane and then extracting the alcohol with a polyester poor solvent (for example, Patent Document 1). . However, since a large amount of organic solvent is used, the environmental load may increase, which is not preferable.

  As a method for producing a polyester porous body that does not use an organic solvent, a cyclic amide compound that is highly compatible with polyester and water-soluble is melt-mixed with the polyester, and then the cyclic amide compound is eluted with water to obtain a polyester. There is a method for producing a porous body (for example, Patent Document 2). However, since an additive compatible with the polyester is used, the additive tends to remain in the polyester, and the physical properties of the polyester may be impaired. Moreover, since it has the melt | dissolution process in the polyester of an additive and the extraction process, the process was complicated and the more simple manufacturing method was calculated | required.

  Moreover, the manufacturing method of the polyester resin molding which has an unevenness | corrugation in the surface layer by hydrolyzing using alkaline aqueous solution or enzyme aqueous solution is proposed (for example, patent document 3).

  According to this method, although it is possible to easily produce a porous body, since the pore size distribution of the surface layer is broad, anisotropy is likely to occur in the mechanical strength, such as a heat insulating material or an insulating material. When used for various purposes, there was room for improvement.

JP 2001-064433 A JP 2003-313415 A JP 2003-277534 A

  An object of the present invention is to solve the above-described problems, and to provide a method for producing a porous polyester body that is simple and does not use a large amount of organic solvent during production, and has a uniform pore diameter.

  As a result of intensive studies, the present inventors contacted a polyester composed of a specific monomer species with a basic aqueous medium containing at least an anionic surfactant and a salt, thereby producing a large amount of organic solvent at the time of production. It was found that a polyester porous body that is simple and has a uniform pore diameter can be produced without using the above, and reached the present invention.

  That is, the configuration of the present invention is as follows.

  The present invention is a combination of a polycarboxylic acid compound and a polyhydric alcohol compound, or a polycarboxylic acid compound and / or a combination of a polyhydric alcohol compound and a hydroxycarboxylic acid compound, or a hydroxycarboxylic acid compound alone. The present invention relates to a method for producing a porous polyester body comprising contacting a polyester composed of a monomer component with a basic aqueous medium containing at least an anionic surfactant and salts.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method of the polyester porous body which is simple and does not use a large amount of organic solvent at the time of manufacture, and the pore diameter is uniform.

It is a figure which shows the hole form which observed the film | membrane obtained in Example 1 by SEM. It is a figure which shows the hole form which observed the film | membrane obtained in the comparative example 1 with SEM.

  Hereinafter, the manufacturing method of the polyester porous body by this invention is demonstrated in detail, giving preferred embodiment.

  The present invention is a combination of a polycarboxylic acid compound and a polyhydric alcohol compound, or a polycarboxylic acid compound and / or a combination of a polyhydric alcohol compound and a hydroxycarboxylic acid compound, or a hydroxycarboxylic acid compound alone. The polyester comprising the monomer component is brought into contact with a basic aqueous medium containing at least an anionic surfactant and salts.

<Polyester used in the present invention>
The polyester used in the present invention is a combination of a polycarboxylic acid compound and a polyhydric alcohol compound, a polycarboxylic acid compound and / or a combination of a polyhydric alcohol compound and a hydroxycarboxylic acid compound, or a hydroxycarboxylic acid compound alone. It is obtained by polycondensing a monomer component composed of any of the above.

  The polyhydric alcohol compound is a compound containing two or more hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, bisphenol Z, alkylene oxide adducts of bisphenols, glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine, but the polyhydric alcohol compound in the present invention is limited to these compounds Is not to be done.

  The polyvalent carboxylic acid compound is a compound containing two or more carboxyl groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, itaconic acid, adipic acid, glutaric acid, β-methyladipic acid, azelaic acid, sebacic acid, suberic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid , Tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid , N-octenyl succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucoic acid , Phthalate , Isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid , Diphenylacetic acid, diphenyl-p, p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, norbornene-2,3 -Dicarboxylic acid, adamantane dicarboxylic acid, adamantane diacetic acid, trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, pyrene tetracarboxylic acid, mesaconic acid, and lower esters thereof However, the polyvalent carboxylic acid compound in the present invention is not limited to these compounds.

  The hydroxycarboxylic acid compound of the present invention is a compound having at least one hydroxyl group and carboxyl group in the same molecule, and may be saturated or unsaturated.

  Examples of the hydroxycarboxylic acid compound include aliphatic hydroxycarboxylic acids, alicyclic hydroxycarboxylic acids, aromatic hydroxycarboxylic acids and the like. Examples of the aliphatic hydroxy acids include glycolic acid, lactic acid, malic acid, citric acid, glyceric acid, castor oil fatty acid, 12-hydroxystearic acid, and ricinoleic acid. Examples of the alicyclic hydroxycarboxylic acid include hydroxycyclopropanecarboxylic acid such as 1-hydroxy-1-cyclopropanecarboxylic acid. Examples of the aromatic hydroxy acids include salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid, coumaric acid, and caffeic acid. The hydroxycarboxylic acid compounds in the present invention are those compounds. It is not limited to.

  The polyvalent carboxylic acid compound and the polyhydric alcohol compound may be used alone or in combination of two or more, respectively, in order to produce a kind of polyester resin. You may use each. Moreover, when using a hydroxycarboxylic acid compound independently, it may use individually by 1 type, may use 2 or more types, and may use a polyhydric carboxylic acid compound and a polyhydric alcohol compound together.

  The polyester may be crystalline or amorphous.

  The molecular weight of the polyester is preferably a polystyrene-equivalent weight average molecular weight of 3,000 to 500,000, more preferably 10,000 to 300,000, from the viewpoint of uniformity of pore diameter.

  In addition, the form of the polyester that can be used in the present invention may be, for example, a film shape, a fiber shape, or a particle shape, and is not particularly limited as long as it is a known molded product.

  The film thickness in the case of using as a film | membrane can be suitably selected according to a use, and is not specifically limited. The polyester film production method includes, for example, a solution film forming method such as a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a die coating method, and a melting method. A known method such as a film forming method can be used and is not particularly limited. When used as a film, the film may be processed as it is formed on the substrate.

  In addition, the thickness of the fiber when used as a fiber can be appropriately selected depending on the application, and is not particularly limited. However, in the application of giving a clear porous structure without breaking the fiber, 0 is used. It is preferable to have a thickness of 0.03 μm or more. As a method for producing the polyester fiber, a known method such as a melt spinning method or an electrostatic spinning method can be used, and it is not particularly limited.

  Moreover, the diameter of the particle | grains when using as particle | grains can be suitably selected according to a use, Although it does not specifically limit, It is preferable that an average diameter is 0.03 micrometer or more. If it is 0.03 micrometer or more, since a clear porous structure can be provided, it is preferable. In addition, as a method for producing particles, for example, a phase inversion emulsification method, a reprecipitation method, an emulsion polymerization method, an emulsion aggregation method, a wet method such as a spray dry method, or a dry method such as a pulverization method can be used. In particular, a known method can be used without being limited thereto.

<Anionic surfactant used in the present invention>
The anionic surfactant used in the present invention may be a surfactant having an anionic property in a basic aqueous medium, and some amphoteric surfactants are also included.

  Examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfones such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphate esters such as ruphosphate; Dialkylsulfosuccinates such as sodium dioctylsulfosuccinate; Sulfosuccinates such as disodium lauryl sulfosuccinate, Lauryldimethylamine oxide, Myristyldimethylamine oxide, Stearyldimethylamine oxide, Dihydroxyethyllaurylamine Oxide, polyoxyethylene coconut oil alkyldimethylamine oxide. One of these surfactants may be used alone, or two or more thereof may be used in combination.

  Moreover, a nonionic surfactant can also be used together as needed.

  Examples of the nonionic surfactant that can be used include, but are not limited to, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylamine. Things can be used.

  The concentration of the anionic surfactant in the basic aqueous medium is preferably such that the concentration in the basic aqueous medium is equal to or higher than the critical micelle concentration, and the anionic surfactant can be used up to the saturation solubility.

  In addition, the mixing ratio in the case of using a nonionic surfactant is not particularly limited as long as the anionic surfactant is within the above concentration range, but from the viewpoint of uniformity of pore diameter, the mixing ratio in the basic aqueous medium Preferably it is 5 mass% or more with respect to the total mass of surfactant, More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more.

<Salts used in the present invention>
The salts used in the present invention are water-soluble inorganic salts or water-soluble organic salts other than surfactants.

  Examples of the salts used in the present invention include water-soluble inorganic salts and water-soluble organic salts, with water-soluble inorganic salts being preferred.

  Examples of water-soluble inorganic salts include salts of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid, and examples of water-soluble organic salts include salts of organic acids such as citric acid, malic acid, succinic acid, and lactic acid. Examples of the cation forming the salt include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, aluminum, and ammonium. Among these, sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, sodium carbonate, and aluminum chloride are particularly preferably used.

  These salts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of salt added depends on the type of salt used, but from the viewpoint of uniformity of pore size, the concentration in the basic medium is preferably 0.01% by mass or more, more preferably 0.10% by mass or more. . Moreover, although it is possible to add and use it to the density | concentration more than saturation solubility, from a viewpoint of detergency, less than saturation solubility is preferable.

<Basic aqueous medium used in the present invention>
In the present invention, the polyester is brought into contact with a basic aqueous medium and hydrolyzed so as to make it porous. A basic aqueous medium refers to an aqueous medium containing a basic compound.

  As a basic compound, any of an inorganic basic compound and an organic basic compound may be sufficient. Examples of the inorganic basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, weak acid salts such as carbonates and acetates thereof, partially neutralized salts, and ammonia. Examples of the organic basic compound include alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine, and alkanolamines such as diethanolamine. These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  On the other hand, the aqueous medium has water as a main component, and from the viewpoint of reducing environmental burden, the water content is preferably 50% by mass or more, more preferably 80% by mass or more, and 100% by mass in the aqueous medium. % Is more preferable.

  In the present invention, the polyester can be made porous using only water without substantially using an organic solvent. Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, from the viewpoint of preventing deterioration of mechanical properties due to mixing into polyester, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol that do not dissolve the resin are preferable.

  The addition amount of the basic compound in the basic aqueous medium depends on the type of the basic compound used, but from the viewpoint of processing efficiency, the pH of the aqueous medium is 9 or more, preferably 10 or more, more preferably 11 or more. It is preferable to select and add as appropriate.

  The treatment temperature at the time of treatment with the basic aqueous medium may be a melting point of water, that is, a temperature range of 0 ° C. or higher under normal pressure, but from the viewpoint of improving the uniformity of the pore diameter, the glass transition of the polyester used. More than the point is preferable. When using a polyester whose glass transition point (Tg) exceeds 100 ° C. or for the purpose of increasing the processing efficiency, it can be carried out at a high temperature of 100 ° C. or higher using a pressure-resistant container.

  The treatment time for treatment with the basic aqueous medium is generally in the range of 15 minutes to 240 hours, although it depends on the pH of the basic aqueous medium and the treatment temperature.

  In addition, by appropriately selecting the treatment time, treatment temperature, and pH of the basic aqueous medium and changing the hydrolysis conditions, the polyester can be made porous on the surface layer or applied from the surface layer to the inside. is there.

  The usage-amount of a basic aqueous medium is not specifically limited, What is necessary is just the quantity which the polyester resin surface used as the object of porosity can contact a basic aqueous medium uniformly.

  Examples of the method of bringing into contact with the basic aqueous medium include a method in which a polyester molded product is immersed or dispersed in a container such as a beaker, or a flow of the basic aqueous medium in the container in a further immersed state. Thus, there are a method in which the basic aqueous medium is circulated, the basic aqueous medium is continuously or intermittently replaced, and a method in which the basic aqueous medium is flowed into the cylindrical molded product. However, it is not particularly limited to these. In the case of simply immersing in a container, convection of the basic aqueous medium may be promoted by a method of stirring the basic aqueous medium or shaking the container and / or the polyester molding itself. preferable.

  The polyester porous body produced by the method of the present invention means a polyester resin molded product in which independent holes or continuous holes are formed from the surface layer or from the surface layer to the inside. In the case of a continuous hole, it has a network structure in which holes in which voids communicate with each other are formed.

As for the hole diameter in the case of independent holes and the hole diameter in the case of continuous holes, the diameter (D _50P ) at which the cumulative number from the small hole diameter side in the cumulative number distribution is 50% is 0.03 μm or more and 1.00 μm. It is as follows. In addition, the ratio of the diameter (D _95P ) where the cumulative number from the small hole diameter side becomes 95% in the cumulative number distribution that is an index of the pore size distribution and the ratio of D _50P (D _95P / D _50P ) is 3.00 or less. It is.

  The method for measuring the pore diameter in the present invention is not particularly limited, and a known method such as a mercury intrusion method or image analysis after SEM observation can be used.

  The porosity of the polyester porous body produced by the method of the present invention is controlled by appropriately selecting the treatment time, treatment temperature, salt type and concentration, and pH of the basic aqueous medium, and changing the hydrolysis conditions. Although possible, it is more preferred to change either the treatment time or the pH of the basic aqueous medium alone. The porosity is generally in the range of 5% to 95%.

  As a method for measuring the porosity, for example, a method of calculating from the density difference between the non-porous polyester and the density of the polyester porous body can be used.

  Moreover, you may perform a well-known secondary process after giving a porous process with respect to a polyester molding. Examples thereof include, but are not limited to, resin crosslinking treatment, hydrophilization treatment, hydrophobization treatment, welding treatment, heat treatment, adhesion treatment using a grain adhesive, stretching treatment, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to these.

  In the following examples, evaluation was performed in the form of a polyester film. Further, various physical property values were evaluated according to the following methods.

<Measurement of pore size distribution>
The surface of the polyester film and the pore diameter (D _50P , D _90P ) of the cross section are observed with a scanning electron microscope (SEM), and an image processing system (LUZEX AP, manufactured by Nireco Corp.) is used from the obtained image. Calculated.

<Calculation method of porosity>
The porosity was calculated according to the following formula by measuring the thickness and mass of a 10 mm × 10 mm polyester porous membrane. S is the area of the porous film, d is the film thickness, w is the mass of the porous film, and D is the density of the polyester.
Porosity (%) = (D / w) × (S × d) × 100

<Measurement of glass transition point of resin>
The glass transition point (Tg) of the polyester resin can be measured using a differential scanning calorimeter (DSC) measuring device. In DSC measurement, from the measurement principle, it is preferable to measure with a differential scanning calorimeter of high accuracy internal heat type input compensation type. The measurement method is performed according to ASTM D3418-82. Specifically, 10 mg of a sample was heated to 140 ° C. at 10 ° C./min, cooled to 25 ° C. at 100 ° C./min, and then measured again when the temperature was raised to 140 ° C. at 10 ° C./min. Calculate the glass transition point from the resulting DSC curve. The central value of the intersection of the baseline before and after the endotherm and the tangent to the endothermic curve was defined as the glass transition point (° C.).

<Resin production example 1>
Three mouthpieces of 50 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 28 parts by mass of terephthalic acid, 20 parts by mass of isophthalic acid, and 0.03 parts by mass of dibutyltin oxide The flask was charged and stirred at 230 ° C. for 24 hours under a nitrogen stream, and then stirred for 4 hours while reducing the pressure at 3 mmHg to obtain polyester resin 1 having a glass transition point of 68 ° C.

<Resin production example 2>
A three-necked flask was charged with 100 parts by mass of terephthalic acid, 64 parts by mass of ethylene glycol, and 0.03 parts by mass of dibutyltin oxide, stirred at 230 ° C. for 24 hours in a nitrogen stream, and reduced in pressure at 3 mmHg. The polyester resin 2 whose glass transition point is 71 degreeC was obtained by stirring for time.

<Resin production example 3>
100 parts by mass of terephthalic acid, 80 parts by mass of ethylene glycol, 64 parts by mass of lactic acid and 0.03 parts by mass of dibutyltin oxide were charged into a three-necked flask and stirred at 230 ° C. for 24 hours in a nitrogen stream. A polyester resin 3 having a glass transition point of 61 ° C. was obtained by stirring for 4 hours while reducing the pressure.

<Example of production of polyester film 1>
To 20 parts by mass of the polyester resin 1, 80 parts by mass of chloroform was added and dissolved by stirring at 55 ° C. for 2 hours to obtain a polyester solution. This solution was spin-coated on a 10 mm × 10 mm stainless steel substrate, dried under reduced pressure at room temperature for 3 hours, and further heat-treated at 80 ° C. for 24 hours in a vacuum oven to obtain a polyester film 1 on the stainless steel substrate. . The film thickness was 75 μm.

<Example of production of polyester film 2>
A polyester film 2 was obtained from the polyester resin 2 by the same preparation method as that for the polyester film 1. The film thickness was 69 μm.

<Example of production of polyester film 3>
A polyester film 3 was obtained from the polyester resin 3 by the same preparation method as that for the polyester film 1. The film thickness was 70 μm.

<Example of production of polyester film 4>
A polyester film 4 was obtained from polylactic acid (RVODE 101 (Ogami Pharmaceutical Co., Ltd., glass transition point 60 ° C.)) by the same preparation method as for the polyester film 1. The film thickness was 57 μm.

<Example 1>
1.54 parts by mass of Neogen RK (produced by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass) and 0.62 parts by mass of sodium chloride (salts) which are anionic surfactants, 5.0 × 10 ⁻² mol / It was dissolved in 100.00 parts by mass of 1 KOH (basic compound) aqueous solution. The pH of the solution was 12.6. This solution was put into a 200 ml beaker, and the polyester film 1 was dipped in the solution together with the stainless steel substrate, and then treated at 95 ° C. for 2.0 hours under stirring at 100 r / min with a chi-type stirrer. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained film by SEM (FIG. 1) and as a result of image analysis, it was found that D _50P = 0.21 μm, D _95P = 0.37 μm, and D _95P / D _50P = 1.76. A polyester porous membrane having a pore size was obtained. The porosity was 65%.

<Example 2>
A polyester porous membrane was obtained by the same method as in Example 1 except that the treatment temperature was 80 ° C. and the treatment time was 8.0 hours.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 1.78 at D _50P = 0.27 μm, D _95P = 0.48 μm was obtained. . The porosity was 48%.

<Example 3>
Anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass) 1.54 parts by mass, sodium chloride 0.62 parts by mass 5.0 × 10 ⁻² mol / l KOH aqueous solution 100.00 parts by mass Dissolved in the part. The polyester film 1 was immersed in this solution together with the stainless steel substrate, and treated at 120 ° C. for 0.5 hour under stirring at 100 r / min using a pressure-resistant stirrer TEM-V1000N (made by pressure-resistant glass industry). After cooling to 95 ° C., the treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 1.53 with D _50P = 0.19 μm and D _95P = 0.29 μm was obtained. . The porosity was 55%.

<Example 4>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the treatment temperature was changed to 70 ° C. and the treatment time was changed to 24.0 hours.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 1.93 with D _50P = 0.28 μm and D _95P = 0.54 μm was obtained. . The porosity was 45%.

<Example 5>
A polyester porous membrane was obtained by the same method as in Example 1 except that the treatment temperature was 50 ° C. and the treatment time was changed to 72.0 hours.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 2.16 with D _50P = 0.32 µm and D _95P = 0.69 µm was obtained. . The porosity was 44%.

<Example 6>
A polyester porous membrane was obtained by the same method as in Example 1 except that the treatment temperature was 30 ° C. and the treatment time was changed to 120.0 hours.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 2.12 with D _50P = 0.33 µm and D _95P = 0.70 µm was obtained. . The porosity was 40%.

<Example 7>
1.54 parts by mass of an anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass) and 0.62 parts by mass of sodium chloride were 2.6 × 10 ⁻¹ mol / l. Dissolved in 100.00 parts by mass of diethylaminoethanol aqueous solution. The pH of the solution was 11.3. This solution was put into a 200 ml beaker, and the polyester film 1 was immersed in the solution together with the stainless steel substrate, and then treated with a chi-type stirrer at 95 ° C. for 1.5 hours under 100 r / min stirring. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.63 with D _50P = 0.27 μm and D _95P = 0.44 μm was obtained. . The porosity was 51%.

<Example 8>
A polyester porous film was obtained in the same manner as in Example 1 except that the polyester film 1 was changed to the polyester film 2.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.67 with D _50P = 0.24 μm and D _95P = 0.40 μm was obtained. . The porosity was 48%.

<Example 9>
A polyester porous film was obtained in the same manner as in Example 1 except that the polyester film 1 was changed to the polyester film 3.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.64 with D _50P = 0.28 μm and D _95P = 0.46 μm was obtained. . The porosity was 46%.

<Example 10>
A polyester porous film was obtained in the same manner as in Example 1 except that the polyester film 1 was changed to the polyester film 4.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.76 with D _50P = 0.22 μm and D _95P = 0.38 μm was obtained. . The porosity was 49%.

<Example 11>
Amphoteric surfactant Amorgen AOL (produced by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 32% by mass) 3.13 parts by mass and sodium chloride 0.62 parts by mass were added to a KOH aqueous solution 100 of 5.0 × 10 ⁻² mol / l. Dissolved in 0.000 part by mass. This solution was put into a 200 ml beaker, and the polyester film 1 was immersed in the solution together with the stainless steel substrate, and then treated with a chi-type stirrer at 95 ° C. for 2 hours under 100 r / min stirring. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a porous polyester membrane having a uniform pore diameter of D _95P / D _50P = 1.56 at D _50P = 0.25 μm and D _95P = 0.39 μm was obtained. . The porosity was 45%.

<Example 12>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the salts were changed to lithium chloride.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.74 at D _50P = 0.23 μm, D _95P = 0.40 μm was obtained. . The porosity was 49%.

<Example 13>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the salts were changed to potassium chloride.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.72 at D _50P = 0.25 μm, D _95P = 0.43 μm was obtained. . The porosity was 47%.

<Example 14>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the salts were changed to magnesium chloride.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.64 with D _50P = 0.25 μm and D _95P = 0.41 μm was obtained. . The porosity was 50%.

<Example 15>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the salts were changed to aluminum chloride.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 1.62 with D _50P = 0.26 μm and D _95P = 0.42 μm was obtained. . The porosity was 49%.

<Example 16>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the amount of salt used was 5.00 parts by mass.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.60 at D _50P = 0.25 μm and D _95P = 0.40 μm was obtained. . The porosity was 46%.

<Example 17>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the amount of salts used was 20.00 parts by mass.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.64 with D _50P = 0.25 μm and D _95P = 0.41 μm was obtained. . The porosity was 44%.

<Example 18>
1.54 parts by mass of Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass), which is an anionic surfactant, and 0.62 parts by mass of sodium chloride, 1.0 × 10 ⁻⁵ mol / l It melt | dissolved in 100.00 mass part of KOH aqueous solution. The pH of the solution was 9.2. This solution was put into a 200 ml beaker, and the polyester film 1 was dipped in the solution together with the stainless steel substrate, and then treated at 95 ° C. for 192 hours with 100 ° C./min stirring with a chi-type stirrer. During the treatment, the pH gradually decreases with the progress of hydrolysis, so an aqueous KOH solution was appropriately added to maintain the pH. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.72 at D _50P = 0.25 μm, D _95P = 0.43 μm was obtained. . The porosity was 41%.

<Example 19>
1.54 parts by mass of an anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass) and 0.62 parts by mass of sodium chloride were added at 1.0 × 10 ⁻⁶ mol / l. It melt | dissolved in 100.00 mass parts of KOH (basic compound) aqueous solution. The pH of the solution was 8.3. This solution was put into a 200 ml beaker, and the polyester film 1 was dipped in the solution together with the stainless steel substrate, and then treated at 95 ° C. for 336 hours with a chi-type stirrer at 100 r / min. During the treatment, the pH gradually decreases with the progress of hydrolysis, so an aqueous KOH solution was appropriately added to maintain the pH. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 1.76 with D _50P = 0.25 μm and D _95P = 0.44 μm was obtained. . The porosity was 37%.

<Example 20>
A polyester porous membrane was obtained in the same manner as in Example 1 except that the treatment time was changed to 4.0 hours.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore size of D _95P / D _50P = 1.67 at D _50P = 0.27 μm, D _95P = 0.45 μm was obtained. . The porosity was 66%.

<Example 21>
A polyester porous membrane was obtained in the same manner as in Example 2 except that the treatment time was changed to 4.0 hours.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a uniform pore diameter of D _95P / D _50P = 1.77 with D _50P = 0.26 μm and D _95P = 0.46 μm was obtained. . The porosity was 29%.

<Comparative Example 1>
An aqueous KOH solution of 5.0 × 10 ⁻² mol / l was put into a 200 ml beaker and the polyester film 1 was immersed together with the stainless steel substrate, and then stirred at 100 ° C./min with a chi-type stirrer for 2 hours at 95 ° C. Processed. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained film by SEM (FIG. 2), D _50P = 0.51 μm, D _95P = 2.58 μm, and polyester having a broad pore size distribution of D _95P / D _50P = 5.06 A porous membrane was obtained. The porosity was 50%.

<Comparative example 2>
0.62 parts by mass of sodium chloride was dissolved in a 5.0 × 10 ⁻² mol / l aqueous KOH solution. Was placed in a 200 ml beaker and the polyester film 1 was immersed together with the stainless steel substrate, and then treated with a chi-type stirrer at 95 ° C. for 2 hours under 100 r / min stirring. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a porous polyester membrane having a broad pore size distribution of D _50P = 0.40 m, D _95P = 2.21 μm and D _95P / D _50P = 5.53 was obtained. It was. The porosity was 46%.

<Comparative Example 3>
1.54 parts by mass of an anionic surfactant, Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass) was dissolved in a 5.0 × 10 ⁻² mol / l aqueous KOH solution. Was placed in a 200 ml beaker and the polyester film 1 was immersed together with the stainless steel substrate, and then treated with a chi-type stirrer at 95 ° C. for 2 hours under 100 r / min stirring. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a porous polyester membrane having a broad pore size distribution of D _50P = 0.42 m, D _95P = 2.19 μm and D _95P / D _50P = 5.21 was obtained. It was. The porosity was 46%.

<Comparative example 4>
1.54 parts by mass of Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 65% by mass), which is an anionic surfactant, and 0.62 parts by mass of sodium chloride, 1.0 × 10 ⁻⁵ mol / l Dissolved in 100.00 parts by mass of hydrochloric acid. The pH of the solution was 6.1. Was placed in a 200 ml beaker, and the polyester film 1 was immersed together with the stainless steel substrate, and then treated at 95 ° C. for 336 hours with a chi-type stirrer at 100 r / min. During the treatment, the pH gradually decreases with the progress of hydrolysis, so an aqueous KOH solution was appropriately added to maintain the pH. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a broad pore size distribution of D _50P = 0.47 μm, D _95P = 3.31 μm and D _95P / D _50P = 7.04 was obtained. It was. The porosity was 36%.

<Comparative Example 5>
Cationicogen BC-50 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 50% by mass) 2.00 parts by mass and 0.62 parts by mass of sodium chloride, 5.0 × 10 ⁻² mol / 1 KOH aqueous solution was dissolved in 100.00 parts by mass. Was placed in a 200 ml beaker and the polyester film 1 was immersed together with the stainless steel substrate, and then treated with a chi-type stirrer at 95 ° C. for 2 hours under 100 r / min stirring. The treated polyester film 1 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a porous polyester membrane having a broad pore size distribution of D _50P = 0.46 μm, D _95P = 2.78 μm and D _95P / D _50P = 6.04 was obtained. It was. The porosity was 52%.

<Comparative Example 6>
A KOH aqueous solution of 5.0 × 10 ⁻² mol / l was put into a 200 ml beaker, the polyester film 2 was immersed together with the stainless steel substrate, and then stirred at 100 ° C./min. Treated for 0 hours. The treated polyester film 2 was collected together with the stainless steel substrate, cooled while being washed with 100 ml of room temperature water, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain a polyester porous film.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a broad pore size distribution of D _50P = 0.38 μm, D _95P = 2.54 μm and D _95P / D _50P = 6.68 was obtained. It was. The porosity was 48%.

<Comparative Example 7>
A polyester porous film was obtained in the same manner as in Comparative Example 6 except that the polyester film 2 was changed to the polyester film 3.

Results holes shape of the obtained film was observed by SEM, D _50P = 0.39μm, with D _95P = 2.61μm, to obtain a polyester porous membrane having a broad pore size distribution of D _95P / D _50P = 6.69 It was. The porosity was 46%.

<Comparative Example 8>
A polyester porous film was obtained in the same manner as in Comparative Example 6 except that the polyester film 2 was changed to the polyester film 4.

As a result of observing the pore morphology of the obtained membrane by SEM, a polyester porous membrane having a broad pore size distribution of D _50P = 0.37 μm, D _95P = 1.98 μm and D _95P / D _50P = 5.35 was obtained. It was. The porosity was 45%.

  For comparison, Table 1 shows the main treatment conditions of the above Examples and Comparative Examples, and Table 2 shows the pore size distribution and porosity of the obtained porous membrane.

Claims (2)

  A combination of a polycarboxylic acid compound and a polyhydric alcohol compound, a polycarboxylic acid compound and / or a combination of a polyhydric alcohol compound and a hydroxycarboxylic acid compound, or a monomer component of either a hydroxycarboxylic acid compound alone The polyester to be produced is brought into contact with a basic aqueous medium containing at least an anionic surfactant and salts.   The method for producing a porous polyester body according to claim 1, wherein the temperature of the basic aqueous medium is equal to or higher than the glass transition point of the polyester.

Images