WO1989008679A1 - Procede de production de membranes polymeres poreuses et de membranes polymeres composites - Google Patents

Procede de production de membranes polymeres poreuses et de membranes polymeres composites Download PDF

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Publication number
WO1989008679A1
WO1989008679A1 PCT/JP1989/000239 JP8900239W WO8908679A1 WO 1989008679 A1 WO1989008679 A1 WO 1989008679A1 JP 8900239 W JP8900239 W JP 8900239W WO 8908679 A1 WO8908679 A1 WO 8908679A1
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Prior art keywords
liquid crystal
polymer
membrane
film
composite
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PCT/JP1989/000239
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English (en)
Japanese (ja)
Inventor
Takeo Furukawa
Yukio Inaba
Original Assignee
Rikagaku Kenkyusho
Kyowa Hakko Kogyo Co., Ltd.
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Application filed by Rikagaku Kenkyusho, Kyowa Hakko Kogyo Co., Ltd. filed Critical Rikagaku Kenkyusho
Publication of WO1989008679A1 publication Critical patent/WO1989008679A1/fr
Priority to US07/769,169 priority Critical patent/US5238636A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition

Definitions

  • the present invention relates to a method for producing a porous polymer membrane and a polymer composite membrane.
  • liquid crystals are used in various fields, and the characteristics of liquid crystals are that their molecular arrangement changes easily due to optical anisotropy and external fields such as electric and magnetic fields. Especially in ferroelectric liquid crystals, mutual polarization and electric field
  • the torque generated by the action is the driving force, and this driving force is very large and is attracting attention as a material for high-speed display elements.
  • some dyes have excellent optical characteristics such as electro-optical effects due to ordinary electric and photoelectric fields, and non-linear optical effects.
  • Low-molecular-weight liquid crystals and dyes with these functions have various molecular design possibilities and various optical properties 5, but they have fluidity and have problems in fixing the structure.
  • the following two methods can be mentioned as a method for obtaining a conventionally known composite film of a liquid crystal display and a polymer.
  • a method of forming a cast film from a mixed solution of a liquid crystal and a polymer by a solvent evaporation method that is, a polymer such as polychloride bur or polymer and N— (4-d. Toxibenzylidene) 1 4'—Butylanilin, butyl — 4— (4-etoxyphenoxycarbonate)
  • a liquid crystal such as funylcarbonate is dissolved in a common solvent, and the mixed solution is used as a seal.
  • Water surface development method that is, a method in which a liquid crystal and polymer mixed solution is dropped onto the water surface via a tank wall, and dozens of composite ultrathin films obtained by self-diffusion are laminated to form a film.
  • the dispersion diameter of the functional low molecules is not uniform, or the dispersion is not uniform. Therefore, the electrical and optical characteristics were not always satisfactory.
  • the inventor of the present invention dissolved a 65/35 mol% copolymer of vinylidene fluoride and trifluorinated polymer in a mixed solvent of tetrahydrofuran and benzene, and utilized the difference in boiling point.
  • a composite film in which a porous V DF / Tr FE film is made in advance and then filled with liquid crystal and its manufacturing method are described in the "Proceedings of the Polymer Society (Volume 36, No. 8, No. 2 3 8)" published by the Society of Polymer Science. 3 ⁇ 2 3 8 5). ”(Published October 5, 1987) t
  • a porous membrane is obtained. It was difficult.
  • An object of the present invention is to provide a novel method for producing a porous polymer membrane.
  • the present invention further provides a method for producing a composite film capable of uniformly dispersing functional low molecules such as liquid crystal (and ⁇ or dye) in a polymer and uniformly dispersing functional low molecules.
  • the purpose is to do.
  • Another object of the present invention is to provide a method for producing a composite membrane capable of adjusting the diameter of a functional small molecule in a polymer, and a fixing membrane obtained by this method.
  • the problems of the prior art as described above are the porous polymer membrane obtained by evaporating the solvent from the polymer solution containing water and alcohol, and the function of the pores of the porous polymer membrane. It is solved by a composite membrane obtained by filling a small molecule.
  • the diameter of the pores of the porous polymer membrane can be adjusted by adjusting the humidity in a humid environment or the amount of water in the polymer solution. be. Therefore, if electrodes are provided on the composite film obtained by filling the pores of the porous polymer film produced in this way with functional low molecules such as liquid crystals and dyes, electrical and optical It is possible to obtain a fixed film with excellent properties.
  • the three molecules of etyl alcohol and water form a cyclic claster due to the hydrogen bond between the etyl alcohol, and three of these clasters are associated with each other, and one of them is present.
  • Hydronium It forms an inclusion compound that incorporates on, and is hydrogen-bonded to this inclusion compound or molecule. Therefore, the polymer is dissolved in a good solvent. ⁇ ⁇ The alcohol water in the solution in which a certain amount of alcohol water is dispersed in the solution becomes uniform spherical particles due to the interfacial tension as the solvent evaporates, and after the solvent evaporates, the porous structure becomes It is formed.
  • the polymer composite membrane is prepared by adjusting the humidity in a humid environment or in a solution in which a certain amount of alcohol water is dispersed in a solution in which the polymer is dissolved in a good solvent. It was found that the mystery of the pores of the porous polymer can be adjusted by adjusting the permanent amount of alcohol water. That is, the pore diameter increases and the number of holes increases as the humidity in a humid environment or the amount of alcohol water increases, and conversely, the pore diameter decreases and the number of holes decreases as the humidity or the amount of water in the alcohol water decreases. It is.
  • the porous membrane having a very small diameter is particularly susceptible to the influence of the amount of water in the air, it is preferable to prepare the porous membrane in a container controlled to a constant temperature and humidity.
  • Fig. 1 shows the composite membrane obtained in Example 2 and the vinylidene fluorinated copolymer as a starting material and the fluoroetylene copolymer. This is a graph showing the temperature dispersion of the linear permittivity of DOBAMBC.
  • ⁇ is a composite membrane
  • ⁇ is a fluorinated vinylidorifluoloethylene co-child combination
  • ⁇ is DOBAMBC.
  • FIG. 2 shows the composite membrane obtained in Example 2 and the vinylidene fluoride trifluoloethylene copolymer as a starting material
  • DOBAMBC ⁇ This is a graph showing the temperature dispersion of the third-order nonlinear permittivity.
  • FIG. 3 is a graph showing the linear dielectric constant of the composite film obtained in Example 3 and the composite film obtained by a conventional method.
  • the number a is the composite membrane of the present invention, and b is the composite membrane obtained by a conventional method.
  • Fig. 4 is a graph showing the relationship between the pore size and the relaxation frequency f m related to the liquid crystal display Z L I — 3 4 8 9 Z polymer composite film.
  • Fig. 5 is a graph showing the frequency spectrum of the linear permittivity of the liquid crystal display Z L I — 3 4 8 9 Z porous porous composite film.
  • Figure 6 is a graph showing the frequency spectrum of the linear permittivity of the liquid crystal display Z L I -3 4 8 9.
  • Fig. 7 is a graph showing the relationship of relaxation frequencies f m related to various porous polymer composite films of liquid crystal display Z L I -3 4 8 9 Z.
  • Fig. 8 is a graph showing the DE hysterism curve of the liquid crystal display Z L I — 3 4 8 9 Z porous porous composite membrane.
  • Fig. 9 is a graph showing the DE hysterism curve of the liquid crystal display Z L I — 3 4 8 9 Z polycarbonate composite film formed by the conventional method.
  • Fig. 10 shows an example of measuring the switching characteristics when the pore size of the liquid crystal Z L I — 3 4 8 9 Z porous porous composite film is 12 m.
  • Figure 11 shows the LCD ZLI -3 4 8 9 and the LCD ZLI -3 4 8 9 It is a graph which showed the relationship between s and the applied electric field in the switching characteristic time of the Z porous pocarbonate composite film.
  • a container desiccator, chromatographic development tank, etc.
  • the liquid crystal molecules In the ferroelectric phase, the liquid crystal molecules have a tilt angle on the layer surface, and the tilt surface has a number between layers.
  • the spiral pitch of the liquid crystal is considered to be about several Iota, and it is considered that the spiral structure plays an important role in the fluctuation of the liquid crystal molecules that give a large moderate strength.
  • fm depends only on the pore phantom regardless of the type of polymer.
  • the relationship between the pore size and the relaxation frequency fm is shown in Fig. 4.
  • the liquid crystal molecules are not the movement of 5 liquid crystals alone, but the size of the main because they are a collective mode due to the torsional movement between the layers of the spectral C phase. It is considered to be affected.
  • the ferroelectric liquid crystal (ZLI — 3 4 8 9) has a nearly linear relationship in their logarithmic relationship and follows the law of 0 ⁇ , but in the composite electric field, the electric field is low.
  • r s corresponds to the dielectric relaxation time
  • the switching curve is equal to the dielectric relaxation time in the time region, and as the electric field increases, s decreases with the electric field according to the law.
  • the pore size becomes smaller in the dynamics of the liquid crystal display, the spiral structure of the Sc * phase cannot be taken, and the low frequency mode is suppressed and IS is considered. Therefore, the response speed becomes faster.
  • any polymer can be used as long as it can form a liquid crystal (and Z or dye) Z polymer fixing film, but a typical polymer is po.
  • polarizers of each other have good compatibility and excellent film forming property, but also obtained! 0
  • Various characteristics of the fixed film that is, chemical stability, weather resistance, impact resistance (thermal, mechanical). It is desirable to use them in combination in consideration of the purpose of use. --Also, a good solvent is good for dissolving the polymer, and it depends on the polymer. For example, vinyl chloride is tetolahydroflan, cyclo, 5 hexanone, methyletilketon, dimethylformamide, etc., and vinyl acetate is chlorideform, ester, etc.
  • Lonitril is dimethylformamide, etc.
  • polyethyleneoxide is benzene, dimethylformamide, etc.
  • vinylidene fluoride, vinylidene cyanide and their copolymers are acetate, methyletylketo.
  • any liquid crystal that can form a liquid crystal Z polymer fixing film can be used.
  • Nematic liquid crystal display Nematic liquid crystal display, terephthalubis 1 Butylanilin, N— (4 — Ciano benziliden) 1 4'— n — Octyl talented xyanilin, dodecyloxyaso ‘ 4 — Echiluanilin, 4— (4'1 phenylbenzi redenamino) 1 n—butyl cinnamete, 4— (4'— decyloxybenzi redenamine) 2 — methylbutyl cinnamete, 4 — (n — hexyl oxy) phenyloxy 1 4 "1 (2 — methylbutyl) biphenyl 1
  • the dyes (including pigments) that can be used in the present invention are azo-based, anthracinone-based, tetrazine-based, and beari, which are conventionally mixed with liquid crystals and used for the light absorption anisotropy of dyes.
  • the alcohol used in the present invention lower monohydric alcohols such as metanol and etanol are preferable.
  • the amount of the alcohol added may be any amount, but it is preferably 5 to 30% with respect to the common solvent i s as long as the polymer does not precipitate.
  • the water used in the present invention is preferably pure water.
  • the amount of water added to alcohol may be any amount as long as the polymer does not precipitate, but since the pore size of the porous polymer film changes depending on the amount of water, 5— It is preferably 50%. Also
  • the boundary is returned.
  • the relative humidity of is 60 — 100%, preferably 75 — 95%, depending on the type of solvent.
  • porous polymer obtained by the present invention alcoholic water is uniformly present as fine droplets in the polymer solution until the time of formation, so that the pore diameter and distribution state of the resulting porous film are uniform. Is. Also minutes Since the phase-dispersed phase is formed by alcohol, the mechanical strength and dimensional stability are greatly improved without being hindered by film formation. These characteristics are important for using this porous fixing membrane as an industrial material.
  • the film thus prepared was impregnated with a liquid crystal display Z L I — 3 4 8 9 (manufactured by Melk) in a vacuum dryer at 80 ° C and filled to obtain a composite film.
  • Z L I — 3 4 8 9 oozes out on the film surface.
  • the liquid crystal display ZLI — 3 4 8 9 is a continuous phase domain formed by the continuous pores formed by the fluoroethylene filament ethylene and the methyl matrix metallate. This is because it is squeezed out, which is in good agreement with the result of the SEM image. This phenomenon is observed above the transition point of the liquid crystal display Z L I — 3 4 8 9 from the colletic phase to the isotropic phase at 87 ° C.
  • pancreas was cast in a flat tone and heat-treated for 8 hours in a chromato developing tank whose relative humidity was adjusted to 80%, and alcohol and water were removed to obtain a porous pancreas. ..
  • the membrane obtained from the SEM image of this membrane was found to be a porous polymer with pores 4-5 ⁇ .
  • FIG. 1 is a graph showing the temperature dispersion of the composite membrane of the present invention obtained in Example 2 and the vinylidene fluoride trifluorethylene co-is polymer and D0BAMBC having a dielectric constant ⁇ , as a starting material. Is. Fig.
  • Example 2 is a graph showing the temperature dispersion of the composite membrane of the present invention obtained in Example 2, the vinylidene fluoride copolymer as a starting material, and the nonlinear dielectric constant ⁇ 3 of D0BAMBC. be. ( ⁇ corresponds to the composite membrane, ⁇ corresponds to vinylidene fluoride 0 trifluoloethylene copolymer, and ⁇ corresponds to D0BAMBC).
  • the dielectric properties of the composite membrane independently reflect the properties of both phases, ⁇ ,, e 3 at each phase transition point. Jump is also found in the composite five membranes.
  • the peak of the liquid crystal polymer composite film 1 is at the transition point (76 .C) from the crystal phase of D0BAMBC to the SmC * phase.
  • the peak of (2) is at the curry point 95 of the vinylidene fluoride copolymer, and the increase of the dielectric constant near (3) is the phase transition from the SmA phase of D0BAMBC to the isotropic (1). It corresponds to 17 ° C).
  • the dielectric constant of the composite film is higher than that of D0BAMBC, a vinylidene fluoride-polyethylene copolymer, and it is noteworthy that a synergistic composite is realized in this system. NS. again,
  • the jump of ⁇ at the transition point of D0BAMBC is also larger in the composite film than in D0BAMBC, which means that the polarization reversal of the liquid crystal can be controlled more easily.
  • D0BAMBC a vinylidene fluoride copolymer using a tetrahydrofuran as a common solvent
  • a cast film formed by a conventional method have a D0BAMBC switch on one side of the film.
  • a non-uniform film was formed by forming a vinylidene fluoride copolymer lithium copolymer layer on one side. The permittivity of this non-uniform composite film lies between the permittivity of both phases, and it can be seen that a very common-sense composite occurs.
  • the film thus obtained was dipped in 2.5 parts of liquid crystal ZLI 1 3 4 8 9 in a vacuum dryer at 90 ° C to obtain a composite film, and an electrode was attached to the test piece. Then, the temperature dependence of the dielectric constant was measured. For comparison About 7.5 parts of Niliden trifluoletyrene copolymer and 2.5 parts of liquid crystal ZLI 1 3 4 8 9 2 parts Common solvent Tetra hydrofuran 100 parts dissolved and cast film formed by a conventional method Also conducted a similar experiment. The temperature dispersion of the linear permittivity ei is shown in Fig. 3 (a corresponds to a double-layered film using a porous polymer film prepared by the method of the present invention, and b corresponds to a composite film obtained by a conventional method).
  • the peak in the region of 120 to 60: is the ferroelectric phase of the liquid crystal display ZLI -3 4 8 9, and the peak near ⁇ 0 is the fluorinated trifluoretylene copolymer curry.
  • Each corresponds to one point. Difference between these two types «As can be seen from 0, the composite film in which the porous film is filled with liquid crystal has a larger jump in the dielectric constant in the strongly induced phase of the liquid crystal than that obtained by the conventional method. It can be seen that the polarization reversal of the liquid crystal can be controlled more easily.
  • Example 4 the composite film in which the porous film is filled with liquid crystal has a larger jump in the dielectric constant in the strongly induced phase of the liquid crystal than that obtained by the conventional method. It can be seen that the polarization reversal of the liquid crystal can be controlled more easily.
  • Example 3 instead of the liquid crystal ZLI— 3 4 8 9, o — nitro is alinin 0.5 g 3 ⁇ 4 ethyl alcohol 0.5 and a mixture of ZLI— 3 4 8 9 with 2.5 g The same treatment as in Example 3 was carried out except for the use of, and a composite film was obtained by using a liquid crystal Z dye mixture as a fine spherical dispersion in the polymer.
  • This film was impregnated with 2.5 parts of liquid crystal ZLI -3 4 8 9 in a vacuum dryer at 90 ° C, filled, and an electrode was attached to obtain a liquid crystal fixing film, which was used as a specimen.
  • the frequency spectrum of the linear dielectric constant of the composite film and liquid crystal obtained as described above is shown in Fig. 5 and Fig. 6.
  • the volume fraction of the liquid 5 crystals related to the composite film is about 20 to 25% in each data. Since the permittivity relaxation strength ⁇ ⁇ is the value obtained by subtracting the instantaneous permittivity ⁇ ⁇ from the equilibrium permittivity ⁇ (0) at which the real part ⁇ 'of the permittivity is in the equilibrium state, the characteristic curve of ⁇ 'in Fig. 5 As the pore size becomes smaller (from 12 zm to 0.1 m), the decrease in ⁇ can be read.
  • the hole diameter' is 1 2 «m to 0.1; from the peak position of um relaxation, the frequency on the horizontal axis' (logistic scale) 80 Hz, It can be read that 300 Hz and 100 Hz. 300 Hz are each read, and it can be seen that the relaxation frequency has largely shifted to the high frequency side.
  • the multi-is porous polymer film according to the present invention has a pore size of 1 2 ⁇ ⁇ ⁇ at 80 Hz, 5 ⁇ m at 300 Hz, and 1 ⁇ m at 1 ⁇ m, while the liquid crystal alone is at about 60 Hz.
  • the liquid crystal display alone is about 2.6 5 ms, but when the pore size is 1 2 ⁇ m, it is 1.98 ms, and when it is 5 / m, it is 5 30 is, 1 At m, it becomes 1 5 9, and at 0.1 ⁇ m, it becomes 5 3, and it becomes faster as the hole diameter 0 becomes smaller.
  • a film was formed by evaporating the solvent in the tank. Then, it was treated in a vacuum dry heat sterilizer at 100 for 8 hours to obtain a cast film.
  • the obtained membrane is a porous membrane with pores of about 12 ⁇ m from the SEM image, and the pores of each form a continuous phase connected by a thin channel.
  • This film was impregnated with liquid crystal Z L I-3 4 8 9 in a vacuum drier at 80 to obtain a composite film, and an electrode was attached to make a specimen. For comparison, 7.5 parts of polycarbonate and 2.5 parts of liquid crystal ZLI-3 4 8 9 were dissolved in 1 part of ⁇ 100 as a common solvent.
  • Fig. 8 shows the system in which the porous film according to the present invention is filled with liquid crystal display
  • Fig. 9 shows the DE hysteric curve of the system in which the cast film is formed by a conventional method. From Fig. 8, it can be seen that in a system in which a porous film is filled with liquid crystal, the liquid crystal Z L I -3 4 8 9 performs ferroelectric polarization inversion i.
  • Figure 10 shows an example of measuring the switching characteristics of the fixed film, which was obtained in Example 5 and has a pore size of 12 / m. This is a plot of the electrical displacement D and its derivative d ⁇ ⁇ d l o g t when a step electric field is applied with respect to l o g t. It can be seen that the switching time s becomes shorter as the electric field becomes higher, and the peak position, and therefore the inversion speed, becomes faster with the electric field.
  • Fig. 11 shows the plots of the various fixing films obtained in Examples 5 and 6 with respect to the logarithm of the applied electric field during the switching time.
  • the liquid crystal display ZLI — 3 4 8 9 a nearly straight line is obtained, and it is shown that it follows the rules.
  • the low electric field r s corresponds to the dielectric relaxation time
  • the switching curve is equal to the time domain dielectric relaxation curve, and as the electric field increases, r s decreases along with the electric field according to the power rule. You can see the situation. From these results, it can be understood that the switching time becomes faster when compounded.
  • the polymer membrane obtained by the present invention is a porous polymer membrane in which spherical pores are uniformly dispersed in an independent or partially continuous structure.
  • a composite film impregnated with a liquid crystal display and a low molecular weight substance such as z or a dye and filled with it has the property of having both the functions of a polymer and the functions of a low molecular weight in one material.
  • a small molecule and a polymer, which both have functionality it is possible to obtain performance that produces a synergistic effect of the functionality of both phases.
  • the polymer film obtained by the present invention can easily adjust the size of spherical pores, and therefore, it is possible to easily manufacture a composite film having a fast switching time.
  • the porous polymer film obtained by the present invention has electrical characteristics such as dielectric constant due to the interaction of pore shape, dispersed state, interface effect between low molecular weight substance and polymer, etc. of the porous high molecular weight film.
  • electrical characteristics such as dielectric constant due to the interaction of pore shape, dispersed state, interface effect between low molecular weight substance and polymer, etc. of the porous high molecular weight film.
  • Optical characteristics such as linear optical effect and double refraction are significantly improved. ⁇ :
  • porous polymer membrane produced by the method of the present invention is not only used for fixing functional small molecules such as liquid crystals, but can also be used for other purposes. ..

Abstract

Des membranes composites en cristaux liquides et/ou colorant et un polymère présentent différentes fonctions outre les effets électro-optiques et les effets optiques non linéaires des substances de départ, et se prêtent à de nombreuses utilisations industrielles. Les membranes composites en cristaux liquides-polymères produites par les procédés conventionnels ne présentent pas de propriétés électriques et optiques entièrement satisfaisantes à cause des diamètres des composés fonctionnels de faible poids moléculaire et à cause de leur distribution non uniforme. On décrit un procédé de production d'une membrane polymère poreuse par l'évaporation d'un solvant à partir d'une solution polymère contenant de l'eau et de l'alcool. Ce procédé permet d'obtenir une membrane polymère poreuse possédant des pores de taille uniforme distribués uniformément. Le procédé de production de la membrane composite ci-décrite consiste à remplir les pores de la membrane polymère poreuse avec des composés fonctionnels de faible poids moléculaire tels que des cristaux liquides ou un colorant afin d'obtenir une membrane composite dans laquelle le composé fonctionnel de faible poids moléculaire est distribué uniformément et présente une granulométrie uniforme. En outre, lors de la production de la membrane polymère poreuse, la taille des pores de la membrane polymère peut être régulée en faisant varier l'humidité dans un environnement très humide ou en faisant varier la teneur en eau de la solution polymère. On peut ainsi produire des membranes fixes présentant d'excellentes propriétés électriques et optiques en créant dans la membrane composite des électrodes que l'on obtient en remplissant les pores de la membrane polymère poreuse d'un composé fonctionnel de faible poids moléculaire, tel que des cristaux liquides ou un colorant.
PCT/JP1989/000239 1988-03-07 1989-03-07 Procede de production de membranes polymeres poreuses et de membranes polymeres composites WO1989008679A1 (fr)

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US07/769,169 US5238636A (en) 1988-03-07 1991-09-30 Processes for producing porous polymer films and composite films

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JP5329088 1988-03-07
JP63/53290 1988-03-07

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007518867A (ja) * 2004-01-20 2007-07-12 バウンドレス・コーポレーシヨン 高度に微孔質なポリマー及びそれらの製法及び使用法
JP2021030666A (ja) * 2019-08-29 2021-03-01 トヨタ自動車株式会社 非水溶性高分子の多孔質体の製造方法
JP2021059687A (ja) * 2019-10-09 2021-04-15 トヨタ自動車株式会社 多孔質体の製造方法
CN114369282A (zh) * 2020-10-15 2022-04-19 泰星能源解决方案有限公司 树脂多孔体的制造方法
CN114369283A (zh) * 2020-10-15 2022-04-19 泰星能源解决方案有限公司 树脂多孔体的制造方法

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JPS4856279A (fr) * 1971-11-18 1973-08-07
JPS5790028A (en) * 1980-11-22 1982-06-04 Kanegafuchi Chem Ind Co Ltd Production of microporous sheet
JPS5816823A (ja) * 1981-07-23 1983-01-31 Nippon Telegr & Teleph Corp <Ntt> 白濁した高分子薄膜の製造方法
JPS6219203B2 (fr) * 1981-02-24 1987-04-27 Tokuyama Soda Kk

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4856279A (fr) * 1971-11-18 1973-08-07
JPS5790028A (en) * 1980-11-22 1982-06-04 Kanegafuchi Chem Ind Co Ltd Production of microporous sheet
JPS6219203B2 (fr) * 1981-02-24 1987-04-27 Tokuyama Soda Kk
JPS5816823A (ja) * 1981-07-23 1983-01-31 Nippon Telegr & Teleph Corp <Ntt> 白濁した高分子薄膜の製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007518867A (ja) * 2004-01-20 2007-07-12 バウンドレス・コーポレーシヨン 高度に微孔質なポリマー及びそれらの製法及び使用法
JP2021030666A (ja) * 2019-08-29 2021-03-01 トヨタ自動車株式会社 非水溶性高分子の多孔質体の製造方法
JP2021059687A (ja) * 2019-10-09 2021-04-15 トヨタ自動車株式会社 多孔質体の製造方法
JP7281086B2 (ja) 2019-10-09 2023-05-25 トヨタ自動車株式会社 多孔質体の製造方法
CN114369282A (zh) * 2020-10-15 2022-04-19 泰星能源解决方案有限公司 树脂多孔体的制造方法
CN114369283A (zh) * 2020-10-15 2022-04-19 泰星能源解决方案有限公司 树脂多孔体的制造方法
JP2022065253A (ja) * 2020-10-15 2022-04-27 プライムプラネットエナジー＆ソリューションズ株式会社 樹脂多孔質体の製造方法
JP2022065255A (ja) * 2020-10-15 2022-04-27 プライムプラネットエナジー＆ソリューションズ株式会社 樹脂多孔質体の製造方法
CN114369283B (zh) * 2020-10-15 2023-08-18 泰星能源解决方案有限公司 树脂多孔体的制造方法
CN114369282B (zh) * 2020-10-15 2023-08-18 泰星能源解决方案有限公司 树脂多孔体的制造方法
US11795288B2 (en) 2020-10-15 2023-10-24 Prime Planet Energy & Solutions, Inc. Production method of resin porous material
US11926723B2 (en) 2020-10-15 2024-03-12 Prime Planet Energy & Solutions, Inc. Production method of resin porous material

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