JP4530630B2 - Method for producing porous film and porous film - Google Patents
Method for producing porous film and porous film Download PDFInfo
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Description
本発明は、表面に実質的にスキン層（緻密層）を有さず、連続微小孔が多数形成された多孔性フィルムに関する。この多孔性フィルムは、精密濾過、分離濃縮等の膜分離技術や、その空孔特性をそのまま利用したり、または空孔を機能性材料で充填することにより、電池用セパレーター、電解コンデンサー、回路用基板等、広範囲な基板材料としての利用が可能である。 The present invention relates to a porous film that has substantially no skin layer (dense layer) on the surface and has a large number of continuous micropores. This porous film can be used for separators for batteries, electrolytic capacitors, circuits by utilizing membrane separation technologies such as microfiltration and separation / concentration, and the characteristics of the pores as they are, or by filling the pores with functional materials. It can be used as a wide range of substrate materials such as substrates.
従来、多孔性フィルムを構成する素材として、アミドイミド系ポリマーやイミド系ポリマー、スルホン系ポリマー、フッ素系ポリマー、オレフィン系ポリマーなどの高分子化合物が知られている。このような素材からなる多孔性フィルムを製造する方法として、例えば、上記高分子化合物を含む混合液をフィルム状に流延した後に凝固液に導く方法（相転換法）が知られている。しかし、上記高分子化合物を素材として前記方法により製造したフィルム表面にはスキン層（緻密層）が存在し、実質的な開孔部が存在しなかったり、また存在してもその開孔率が低かった。例えば、イミド系ポリマーを素材とした多孔性フィルムとして、ポリイミドからなる多孔膜やその製造方法が開示されているが（例えば、特許文献１〜３参照。）、これらは表面に孔を開けるために溶媒置換速度調整材を介して製造することが必要なために、その製造工程が複雑である上、充分な開孔率と透過性を有するものではないという不具合があった。 Conventionally, polymer compounds such as an amideimide polymer, an imide polymer, a sulfone polymer, a fluorine polymer, and an olefin polymer are known as materials constituting the porous film. As a method for producing a porous film made of such a material, for example, a method (phase change method) in which a mixed solution containing the above polymer compound is cast into a film and then led to a coagulating solution is known. However, there is a skin layer (dense layer) on the surface of the film produced by the above method using the above-mentioned polymer compound as a raw material, and there is no substantial opening portion, or even if it exists, the opening ratio is low. It was low. For example, as a porous film made of an imide-based polymer, a porous film made of polyimide and a method for producing the same have been disclosed (for example, refer to Patent Documents 1 to 3). Since it is necessary to manufacture via a solvent substitution rate adjusting material, the manufacturing process is complicated, and there is a problem that it does not have a sufficient porosity and permeability.
本発明の目的は、フィルム表面の開孔率が高く、且つフィルムの表面から内部にかけて均質な微小孔を有する多孔性フィルムを提供することにある。
本発明の他の目的は、上記多孔性フィルムを簡便に製造できる方法を提供することにある。
An object of the present invention is to provide a porous film having a high porosity on the film surface and having uniform micropores from the surface to the inside of the film.
Another object of the present invention is to provide a method by which the porous film can be easily produced.
本発明者らは、上記目的を達成するため鋭意検討した結果、高分子の表面張力と基板の表面張力との差が特定値以上である高分子及び基板を用いて、該高分子を含む混合溶液を該基板上へフィルム状に流延し相転換させることにより、基板に接触していた側のフィルム表面にも高い開孔率で均質な微小孔を有する多孔性フィルムが得られることを見いだし、本発明を完成した。 As a result of diligent investigations to achieve the above object, the inventors of the present invention have used a polymer and a substrate in which the difference between the surface tension of the polymer and the surface tension of the substrate is a specific value or more, and a mixture containing the polymer. It has been found that a porous film having uniform micropores with a high open area can be obtained on the film surface on the side in contact with the substrate by casting the solution on the substrate in the form of a film and performing phase conversion. The present invention has been completed.
すなわち、本発明は、素材がアミドイミド系ポリマー及びイミド系ポリマーから選択された少なくとも１種の高分子であり、連通性を有する微小孔が多数存在する多孔性フィルムであって、該フィルムの厚みが２０〜２００μｍ、透気度を表すガーレー値が０．２〜２９秒／１００ｃｃであり、フィルムの両表面について、表面の平均孔径が０．０５〜１０μｍ、表面の平均開孔率が４８％以上、表面の平均孔径Ａと内部の平均孔径Ｂとの比率Ａ／Ｂが０．３〜３、且つ表面の平均開孔率Ｃと内部の平均開孔率Ｄとの比率Ｃ／Ｄが０．７〜１．５であることを特徴とする多孔性フィルムを提供する。
本発明は、また、素材がアミドイミド系ポリマー及びイミド系ポリマーから選択された少なくとも１種の高分子であり、連通性を有する微小孔が多数存在する多孔性フィルムであって、該フィルムの厚みが２０〜２００μｍ、透気度を表すガーレー値が０．２〜２９秒／１００ｃｃであり、フィルムの両面の平均孔径Ａ 1 ，Ａ 2 が何れも０．０５〜１０μｍ、フィルムの両面の平均開孔率Ｃ 1 ，Ｃ 2 が何れも４８％以上であり、且つ一方の表面の平均孔径Ａ 1 と他方の表面の平均孔径Ａ 2 との比率Ａ 1 ／Ａ 2 が０．３〜３、一方の表面の平均開孔率Ｃ 1 と他方の表面の平均開孔率Ｃ 2 との比率Ｃ 1 ／Ｃ 2 が０．７〜１．５であることを特徴とする多孔性フィルムを提供する。
That is, the present invention is a porous film whose material is at least one polymer selected from an amide-imide polymer and an imide-based polymer, and in which a large number of micropores having communication exists, and the thickness of the film is 20 to 200 μm, Gurley value representing air permeability is 0.2 to 29 seconds / 100 cc, the average surface pore diameter is 0.05 to 10 μm, and the average surface area porosity is 48% or more for both surfaces of the film The ratio A / B of the surface average pore diameter A to the internal average pore diameter B is 0.3 to 3, and the ratio C / D of the surface average pore ratio C to the internal average pore ratio D is 0. The porous film is characterized by being 7 to 1.5.
The present invention is also a porous film in which the material is at least one polymer selected from an amide-imide polymer and an imide-based polymer, and there are a large number of micropores having connectivity, and the thickness of the film is 20 to 200 μm, Gurley value representing air permeability is 0.2 to 29 seconds / 100 cc, average pore diameters A 1 and A 2 on both sides of the film are both 0.05 to 10 μm, average aperture on both sides of the film The ratios C 1 and C 2 are both 48% or more, and the ratio A 1 / A 2 between the average pore diameter A 1 on one surface and the average pore diameter A 2 on the other surface is 0.3-3, the ratio C 1 / C 2 between the average porosity C 2 having an average porosity C 1 and the other surface of the surface to provide a porous film which is characterized in that 0.7 to 1.5.
本発明は、さらに、前記の多孔性フィルムの製造方法であって、アミドイミド系ポリマー及びイミド系ポリマーから選択された少なくとも１種の高分子成分を含む高分子溶液を基板上へフィルム状に流延し、相転換法により多孔性フィルムを製造するに際し、該多孔性フィルムを構成する高分子の表面張力Ｓａ［ｍＮ／ｍ］と基板の表面張力Ｓｂ［ｍＮ／ｍ］との差（Ｓａ−Ｓｂ）が−１０以上となる高分子及び基板を用い、多孔性フィルムを構成する素材となる高分子成分８〜２５重量％、水溶性ポリマー１０〜５０重量％、水０〜１０重量％、水溶性極性溶媒３０〜８２重量％からなる混合溶液を高分子溶液として基板上へフィルム状に流延したのち凝固液に導き、相転換させて多孔性フィルムを得る多孔性フィルムの製造方法を提供する。
本発明は、さらにまた、前記の多孔性フィルムの製造方法であって、アミドイミド系ポリマー及びイミド系ポリマーから選択された少なくとも１種の高分子成分を含む高分子溶液を基板上へフィルム状に流延し、相転換法により多孔性フィルムを製造するに際し、該多孔性フィルムを構成する高分子の表面張力Ｓａ［ｍＮ／ｍ］と基板の表面張力Ｓｂ［ｍＮ／ｍ］との差（Ｓａ−Ｓｂ）が−１０以上となる高分子及び基板を用い、多孔性フィルムを構成する高分子を水溶性極性溶媒に溶解した高分子溶液を基板上へフィルム状に流延する際に、該フィルムを相対湿度７０〜１００％、温度１５〜９０℃からなる雰囲気下に０．２〜１５分間保持した後、高分子成分の非溶剤からなる凝固液に導く工程を含む多孔性フィルムの製造方法を提供する。
本発明は、また、前記の多孔性フィルムの製造方法であって、アミドイミド系ポリマー及びイミド系ポリマーから選択された少なくとも１種の高分子成分を含む高分子溶液を基板上へフィルム状に流延し、相転換法により多孔性フィルムを製造するに際し、該多孔性フィルムを構成する高分子の表面張力Ｓａ［ｍＮ／ｍ］と基板の表面張力Ｓｂ［ｍＮ／ｍ］との差（Ｓａ−Ｓｂ）が−１０以上となる高分子及び基板を用い、多孔性フィルムを構成する素材となる高分子成分８〜２５重量％、水溶性ポリマー１０〜５０重量％、水０〜１０重量％、水溶性極性溶媒３０〜８２重量％からなる混合溶液を高分子溶液として基板上へフィルム状に流延する際に、該フィルムを相対湿度７０〜１００％、温度１５〜９０℃からなる雰囲気下に０．２〜１５分間保持した後、高分子成分の非溶剤からなる凝固液に導き、相転換させて多孔性フィルムを得る多孔性フィルムの製造方法を提供する。
The present invention further relates to a method for producing the porous film, wherein a polymer solution containing at least one polymer component selected from an amideimide polymer and an imide polymer is cast on a substrate in the form of a film. In producing a porous film by the phase change method, the difference between the surface tension Sa [mN / m] of the polymer constituting the porous film and the surface tension Sb [mN / m] of the substrate (Sa−Sb) ) Is a polymer and a substrate of -10 or more, the polymer component 8-25% by weight, water-soluble polymer 10-50% by weight, water 0-10% by weight, water-soluble Provided is a method for producing a porous film in which a mixed solution composed of 30 to 82% by weight of a polar solvent is cast as a polymer solution onto a substrate in the form of a film, guided to a coagulating liquid, and phase-converted to obtain a porous film. .
The present invention further provides a method for producing the porous film, wherein a polymer solution containing at least one polymer component selected from an amide-imide polymer and an imide-based polymer is flown onto a substrate in the form of a film. When the porous film is produced by the phase change method, the difference between the surface tension Sa [mN / m] of the polymer constituting the porous film and the surface tension Sb [mN / m] of the substrate (Sa− When a polymer solution in which the polymer constituting the porous film is dissolved in a water-soluble polar solvent using a polymer and a substrate in which Sb) is −10 or more is cast onto the substrate in the form of a film, Provided is a method for producing a porous film comprising a step of holding in an atmosphere composed of a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C. for 0.2 to 15 minutes, and then leading to a coagulating liquid composed of a non-solvent of a polymer component You .
The present invention is also a method for producing the above porous film, in which a polymer solution containing at least one polymer component selected from an amideimide polymer and an imide polymer is cast into a film on a substrate. In producing a porous film by the phase change method, the difference between the surface tension Sa [mN / m] of the polymer constituting the porous film and the surface tension Sb [mN / m] of the substrate (Sa−Sb) ) Is a polymer and a substrate of -10 or more, the polymer component 8-25% by weight, water-soluble polymer 10-50% by weight, water 0-10% by weight, water-soluble When a mixed solution composed of 30 to 82% by weight of a polar solvent is cast as a polymer solution onto a substrate in the form of a film, the film is placed in an atmosphere having a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C. 2 to After holding for 5 minutes, it introduced into a coagulating liquid made of a non-solvent for the polymer component, to provide a method of manufacturing a porous film to obtain a porous film by phase inversion.
本発明の製造方法によれば、高分子成分を含む混合溶液が基板上で良好な相分離構造をとるため、基板側表面の開孔率が向上し、均質な微小孔が形成された多孔性フィルムを簡便に得ることができる。このため、本発明の多孔性フィルムは、精密濾過、分離濃縮等の膜分離技術に利用できるほか、その空孔を機能性材料で充填することにより、電池用セパレータ、電解コンデンサー、回路用基板等、広範囲な基板材料としての利用が可能である。 According to the production method of the present invention, since the mixed solution containing the polymer component has a good phase separation structure on the substrate, the porosity on the substrate side surface is improved, and the porosity in which homogeneous micropores are formed is formed. A film can be easily obtained. For this reason, the porous film of the present invention can be used for membrane separation techniques such as microfiltration and separation / concentration, and by filling the pores with functional materials, battery separators, electrolytic capacitors, circuit boards, etc. It can be used as a wide range of substrate materials.
本発明の製造方法では、多孔性フィルムを構成する素材となる高分子成分を含む高分子溶液を基板上へフィルム状に流延し、相転換法により多孔性フィルムを製造する。 In the production method of the present invention, a polymer solution containing a polymer component as a material constituting the porous film is cast onto a substrate in the form of a film, and the porous film is produced by a phase change method.
高分子成分としては、例えば、アミドイミド系ポリマー、イミド系ポリマー、アミド系ポリマー、スルホン系ポリマー、セルロース系ポリマー、アクリル系ポリマー、フッ素系ポリマー、オレフィン系ポリマーなどのポリマーが挙げられるがこれらに限定されるものではない。好ましくは、水溶性の極性溶媒に溶解性を有し相転換法によりフィルムを形成しうるものが用いられる。具体的には、アミドイミド系ポリマー、イミド系ポリマー、ポリエーテルスルホン、ポリスルホン、アクリル系ポリマー、セルロースアセテート等が好適である。これらの高分子成分は単独又は２種以上組み合わせて用いることも可能である。 Examples of the polymer component include, but are not limited to, polymers such as amideimide polymers, imide polymers, amide polymers, sulfone polymers, cellulose polymers, acrylic polymers, fluorine polymers, and olefin polymers. It is not something. Preferably, those having solubility in a water-soluble polar solvent and capable of forming a film by a phase change method are used. Specifically, amidoimide polymers, imide polymers, polyethersulfone, polysulfone, acrylic polymers, cellulose acetate, and the like are suitable. These polymer components can be used alone or in combination of two or more.
基板としては、例えば、ガラス板；ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン系樹脂、ナイロン、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル、ポリカーボネート、スチレン系樹脂、ＰＴＦＥ（ポリテトラフルオロエチレン）、ＰＶＤＦ（ポリフッ化ビニリデン）等のフッ素系樹脂、塩化ビニル樹脂、その他の樹脂からなるプラスチックシート；ステンレス板、アルミニウム板等の金属板などが挙げられる。なお、表面素材と内部素材とを違うもので組み合わせた複合板でもよい。 Examples of the substrate include glass plates; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyesters such as nylon and polyethylene terephthalate (PET); polycarbonates, styrene resins, PTFE (polytetrafluoroethylene), and PVDF (polypropylene). A plastic sheet made of a fluororesin such as vinylidene chloride), a vinyl chloride resin, or other resin; a metal plate such as a stainless steel plate or an aluminum plate. In addition, the composite board which combined the surface material and the internal material with a different thing may be sufficient.
本発明の主な特徴は、多孔性フィルムを構成する高分子の表面張力Ｓａ［ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）］と基板の表面張力Ｓｂ［ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）］との差（Ｓａ−Ｓｂ）が−１０以上となる高分子と基板とを用いて多孔性フィルムを製造する点にある。なお、基板が、表面素材と内部素材が異なった複合板である場合は、前記高分子との接触面を形成する素材の表面張力が上記関係を満たしていればよい。前記（Ｓａ−Ｓｂ）が−１０未満の場合には、高分子と基板の界面に高分子が凝集して緻密相が形成されるため、表面開孔率が低く実用に耐えないフィルムとなる。 The main features of the present invention are the surface tension Sa [mN / m (= dyn / cm)] of the polymer constituting the porous film and the surface tension Sb [mN / m (= dyn / cm)] of the substrate. A porous film is manufactured using a polymer and a substrate having a difference (Sa−Sb) of −10 or more. When the substrate is a composite plate having a different surface material and internal material, the surface tension of the material forming the contact surface with the polymer should satisfy the above relationship. When (Sa-Sb) is less than -10, the polymer aggregates at the interface between the polymer and the substrate to form a dense phase, so that the surface porosity is low and the film cannot be used practically.
上記条件を満たす高分子と基板を用いることにより、流延時には該高分子を含む混合溶液が該基板上で海−島構造を有する相分離を生じ、これがフィルムの微小孔の発生源となる。このため、特に、フィルムの基板と接触している側の表面（「フィルムの基板側表面」と称する場合がある）の開孔率が高い多孔性フィルムを得ることができる。特に、前記（Ｓａ−Ｓｂ）が０を超える場合には、相転換法により凝集した高分子が基板の表面を濡らすことができずはじかれるため、より効果的に開孔することができる点で好ましく、より好ましくは３以上、さらに好ましくは７以上であり、１３以上が最も好適である。（Ｓａ−Ｓｂ）の値の上限は特に制限されず、例えば１００程度であってもよい。 By using a polymer and a substrate satisfying the above conditions, a mixed solution containing the polymer causes phase separation having a sea-island structure on the substrate during casting, which becomes a source of micropores in the film. For this reason, in particular, a porous film having a high porosity on the surface of the film in contact with the substrate (sometimes referred to as “film substrate-side surface”) can be obtained. In particular, when (Sa-Sb) exceeds 0, the polymer aggregated by the phase conversion method cannot repel the surface of the substrate and is repelled, so that the holes can be more effectively opened. Preferably, it is 3 or more, more preferably 7 or more, and most preferably 13 or more. The upper limit of the value of (Sa−Sb) is not particularly limited, and may be about 100, for example.
本発明において、流延に付す高分子溶液としては、例えば、多孔性フィルムを構成する素材となる高分子成分８〜２５重量％、水溶性ポリマー１０〜５０重量％、水０〜１０重量％、水溶性極性溶媒３０〜８２重量％からなる混合溶液などが好ましい。この際に、高分子成分の濃度が低すぎるとフィルムの強度が弱くなり、また高すぎると空孔率が小さくなる。水溶性ポリマーは、フィルム内部を均質なスポンジ状の多孔構造にするために添加するが、この際に濃度が低すぎるとフィルム内部に１０μｍを超えるような巨大ボイドが発生し均質性が低下する。また水溶性ポリマーの濃度が高すぎると溶解性が悪くなる他、５０重量％を超える場合には、フィルム強度が弱くなるなどの不具合が生じやすい。 In the present invention, the polymer solution to be cast is, for example, 8 to 25% by weight of a polymer component as a material constituting the porous film, 10 to 50% by weight of a water-soluble polymer, 0 to 10% by weight of water, A mixed solution composed of 30 to 82% by weight of a water-soluble polar solvent is preferred. At this time, if the concentration of the polymer component is too low, the strength of the film becomes weak, and if it is too high, the porosity becomes small. The water-soluble polymer is added to make the inside of the film a uniform sponge-like porous structure. If the concentration is too low at this time, a huge void exceeding 10 μm is generated inside the film and the homogeneity is lowered. In addition, if the concentration of the water-soluble polymer is too high, the solubility becomes worse, and if it exceeds 50% by weight, problems such as weak film strength tend to occur.
水溶性極性溶媒としては、例えば、ジメチルスルホキシド，Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、２−ピロリドン及びこれらの混合物などが挙げられ、前記高分子成分として使用するポリマーの化学骨格に応じて溶解性を有するもの（高分子成分の良溶媒）を使用することができる。これらの溶媒は単独又は２種以上組み合わせて用いることもできる。 Examples of the water-soluble polar solvent include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 2-pyrrolidone, and mixtures thereof. In addition, those having solubility (good solvent for the polymer component) can be used according to the chemical skeleton of the polymer used as the polymer component. These solvents can be used alone or in combination of two or more.
また、膜構造をスポンジ状に多孔化するためには、水溶性ポリマーや水を加えて、流延時の相分離構造を制御することが効果がある。水溶性ポリマーとしては、例えば、ポリエチレングリコール、ポリビニルピロリドン、ポリエチレンオキサイド、ポリビニルアルコール、ポリアクリル酸、多糖類等やその誘導体などが挙げられる。これらの水溶性ポリマーは単独で又は２種以上を組み合わせて使用できる。これらの中でも、フィルムに存在する微小孔の連通性の点から、ポリビニルピロリドンが特に好ましい。多孔化のためには、水溶性ポリマーの分子量は１０００以上が良く、好ましくは５０００以上、特に好ましくは１万以上（例えば、１万〜２０万程度）である。水の添加量はボイド径の調整に用いることができ、添加量を増やすことで径を大きくすることが可能となる。 In order to make the membrane structure porous like a sponge, it is effective to add a water-soluble polymer or water to control the phase separation structure during casting. Examples of the water-soluble polymer include polyethylene glycol, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, polyacrylic acid, polysaccharides, and derivatives thereof. These water-soluble polymers can be used alone or in combination of two or more. Among these, polyvinylpyrrolidone is particularly preferable from the viewpoint of the connectivity of the micropores present in the film. For porosity formation, the molecular weight of the water-soluble polymer is preferably 1000 or more, preferably 5000 or more, particularly preferably 10,000 or more (for example, about 10,000 to 200,000). The added amount of water can be used to adjust the void diameter, and the diameter can be increased by increasing the added amount.
上記のような組成を有する混合溶液を高分子溶液として用い、これを基板上へフィルム状に流延したのち凝固液に導き、相転換させることにより微小孔を均質に形成することができる。 By using a mixed solution having the above composition as a polymer solution, casting it in a film form on a substrate, guiding it to a coagulating liquid, and performing phase conversion, micropores can be formed uniformly.
本発明においては、高分子溶液をフィルム状に流延する際に、該フィルムを相対湿度７０〜１００％、温度１５〜９０℃からなる雰囲気下に０．２〜１５分間保持した後、高分子成分の非溶剤からなる凝固液に導くのが望ましい。より好ましい条件としては、相対湿度９０〜１００％、温度３０〜８０℃、特に好ましい条件は、相対湿度約１００％（例えば、９５〜１００％）、温度４０〜７０℃である。空気中の水分量がこれよりも少ない場合は、フィルムの開孔率が充分でなくなる不具合がある。 In the present invention, when the polymer solution is cast into a film, the film is held for 0.2 to 15 minutes in an atmosphere composed of a relative humidity of 70 to 100% and a temperature of 15 to 90 ° C. It is desirable to lead to a coagulating liquid consisting of non-solvent components. More preferable conditions are a relative humidity of 90 to 100% and a temperature of 30 to 80 ° C, and particularly preferable conditions are a relative humidity of about 100% (for example, 95 to 100%) and a temperature of 40 to 70 ° C. When the amount of moisture in the air is less than this, there is a problem that the aperture ratio of the film is not sufficient.
流延後のフィルムを上記条件におくことにより、特に、該フィルムの基板側表面の反対の表面（「フィルムの空気側表面」と称する場合がある）の開孔率を向上させることができる。開孔率が向上する理由としては、加湿下に置くことにより水分がフィルム表面から内部へと侵入し、混合溶液の相分離を効率的に促進するためと考えられる。 By setting the film after casting to the above-mentioned conditions, it is possible to improve the aperture ratio of the surface opposite to the substrate side surface of the film (sometimes referred to as “the air side surface of the film”). The reason why the open area ratio is improved is considered to be that moisture is infiltrated from the surface of the film into the interior by placing it under humidification, thereby effectively promoting phase separation of the mixed solution.
相転換法に用いる凝固液としては、高分子成分を凝固させる溶剤であればよく、高分子成分として使用するポリマーの種類によって適宜選択されるが、例えば、水；メタノール、エタノール等の１価アルコール、グリセリン等の多価アルコールなどのアルコール；ポリエチレングリコール等の水溶性高分子；これらの混合物などが使用できる。 The coagulation liquid used in the phase conversion method may be any solvent that coagulates the polymer component, and is appropriately selected depending on the type of polymer used as the polymer component. For example, water; monohydric alcohols such as methanol and ethanol And alcohols such as polyhydric alcohols such as glycerin; water-soluble polymers such as polyethylene glycol; and mixtures thereof.
本発明の製造方法によれば、開孔率が高く、しかも均質な微小孔が形成された多孔質フィルムを得ることができる。以下に、本発明の製造方法により得られる多孔性フィルムについて説明する。 According to the production method of the present invention, it is possible to obtain a porous film having a high aperture ratio and in which uniform micropores are formed. Below, the porous film obtained by the manufacturing method of this invention is demonstrated.
多孔性フィルムの厚みは、例えば５〜２００μｍ、好ましくは１０〜１００μｍ、さらに好ましくは２０〜８０μｍである。厚みが薄くなりすぎるとフィルムの機械強度が充分でなくなり、一方厚すぎる場合には孔径分布を均一に制御することが困難となる。 The thickness of the porous film is, for example, 5 to 200 μm, preferably 10 to 100 μm, and more preferably 20 to 80 μm. If the thickness is too thin, the mechanical strength of the film will be insufficient, while if it is too thick, it will be difficult to control the pore size distribution uniformly.
多孔性フィルムに存在する微小孔の平均孔径（＝フィルム表面の平均孔径）は、その用途により好適なサイズが異なるが、通常０．０１〜１０μｍであり、好ましくは０．０５〜５μｍである。サイズが小さすぎる場合には透過性能が劣り、大きすぎる場合は分離濃縮の効率が落ちるなどの不具合がある。また多孔部に機能性材料を充填する場合にはサブミクロン〜ミクロン単位の分解能で充填できることが好ましいことから、上述の平均孔径が好ましく、小さすぎると機能性材料を充填できないなどの不具合が生じたり、一方、大きすぎるとサブミクロン〜ミクロン単位の制御が困難となる。また、フィルム表面の最大孔径は１５μｍ以下が好ましい。 The average pore diameter of the micropores present in the porous film (= average pore diameter on the film surface) varies depending on the application, but is usually from 0.01 to 10 μm, preferably from 0.05 to 5 μm. If the size is too small, the permeation performance is inferior, and if it is too large, the separation and concentration efficiency is reduced. In addition, when the porous material is filled with a functional material, it is preferable that the porous material can be filled with submicron to micron resolution, so that the average pore diameter described above is preferable, and if it is too small, the functional material cannot be filled. On the other hand, if it is too large, control in submicron to micron units becomes difficult. The maximum pore diameter on the film surface is preferably 15 μm or less.
多孔性フィルムの内部の平均開孔率（空孔率）は、例えば３０〜８０％であり、好ましくは４０〜８０％、さらに好ましくは４５〜８０％である。空孔率が低すぎると、透過性能が十分でなかったり、機能性材料を充填しても機能が発揮できないことがある。一方、空孔率が高すぎると、機能的強度に劣る可能性がある。また、フィルムの表面の平均開孔率（表面開孔率）は、例えば４８％以上（例えば４８〜８０％）であり、好ましくは６０〜８０％程度である。表面開孔率が低すぎると透過性能が十分でなかったり、機能性材料を充填してもその機能が充分に発揮できないことがある。一方、表面開孔率が高すぎると機械的強度が低下しやすくなる。 The average open area ratio (porosity) inside the porous film is, for example, 30 to 80%, preferably 40 to 80%, and more preferably 45 to 80%. If the porosity is too low, the permeation performance may not be sufficient, or the function may not be exhibited even if a functional material is filled. On the other hand, if the porosity is too high, the functional strength may be inferior. Moreover, the average open area ratio (surface open area ratio) of the surface of a film is 48% or more (for example, 48-80%), for example, Preferably it is about 60-80%. If the surface area ratio is too low, the permeation performance may not be sufficient, or the function may not be sufficiently exhibited even if a functional material is filled. On the other hand, if the surface area ratio is too high, the mechanical strength tends to decrease.
また、フィルムに存在する微小孔の連通性は、例えば透気度を表すガーレー値、及び純水透過速度などを指標とすることができる。多孔性フィルムのガーレー値は、例えば０．２〜２９秒／１００ｃｃ、好ましくは１〜２５秒／１００ｃｃ、特に好ましくは１〜１８秒／１００ｃｃである。これよりも数値が大きいと、実用上の透過性能が十分でなかったり、機能性材料を十分に充填できないためにその機能が発揮できないことがある。一方、数値がこれよりも小さいと、機械的強度に劣る可能性がある。また、純水透過速度は、例えば１．３×１０-9〜１．１×１０-7ｍ・ｓｅｃ-1・Ｐａ-1［＝８〜７００リットル／（ｍ2・ｍｉｎ・ａｔｍ）］、好ましくは３．３×１０-9〜１．１×１０-7ｍ・ｓｅｃ-1・Ｐａ-1［＝２０〜７００リットル／（ｍ2・ｍｉｎ・ａｔｍ）］であり、さらに好ましくは４．９×１０-9〜８．２×１０-8ｍ・ｓｅｃ-1・Ｐａ-1［＝３０〜５００リットル／（ｍ2・ｍｉｎ・ａｔｍ）］である。これよりも純水透過速度が低いと、実用上の透過性能が充分でなかったり、機能性材料を充分に充填できないためにその機能が発揮できないことがある。一方、数値がこれよりも大きいと、機械的強度に劣る可能性がある。 Further, the connectivity of the micropores present in the film can be determined by using, for example, a Gurley value representing air permeability and a pure water permeation rate. The Gurley value of the porous film is, for example, 0.2 to 29 seconds / 100 cc, preferably 1 to 25 seconds / 100 cc, particularly preferably 1 to 18 seconds / 100 cc. If the numerical value is larger than this, the practical permeation performance may not be sufficient, or the functional material may not be sufficiently filled and the function may not be exhibited. On the other hand, if the numerical value is smaller than this, the mechanical strength may be inferior. The pure water permeation rate is, for example, 1.3 × 10 −9 to 1.1 × 10 −7 m · sec −1 · Pa −1 [= 8 to 700 liters / (m 2 · min · atm)], It is preferably 3.3 × 10 −9 to 1.1 × 10 −7 m · sec −1 · Pa −1 [= 20 to 700 liters / (m 2 · min · atm)], more preferably 4. 9 × 10 −9 to 8.2 × 10 −8 m · sec −1 · Pa −1 [= 30 to 500 liters / (m 2 · min · atm)]. If the pure water permeation rate is lower than this, the practical permeation performance may not be sufficient, or the functional material may not be sufficiently filled, and the function may not be exhibited. On the other hand, if the value is larger than this, the mechanical strength may be inferior.
好ましい多孔性フィルムは、連通性を有する微小孔が多数存在する多孔性フィルムであって、該フィルムの厚みが５〜２００μｍであり、フィルムの両表面について、表面の平均孔径が０．０１〜１０μｍ、表面の平均孔径Ａと内部の平均孔径Ｂとの比率Ａ／Ｂが０．３〜３、且つ表面の平均開孔率Ｃと内部の平均開孔率Ｄとの比率Ｃ／Ｄが０．７〜１．５であることを特徴とする多孔性フィルムである。 A preferred porous film is a porous film in which a large number of micropores having communication properties exist, the thickness of the film is 5 to 200 μm, and the average pore diameter of the surface is 0.01 to 10 μm on both surfaces of the film. The ratio A / B of the surface average pore diameter A to the internal average pore diameter B is 0.3 to 3, and the ratio C / D of the surface average pore ratio C to the internal average pore ratio D is 0. It is 7-1.5, It is a porous film characterized by the above-mentioned.
表面の平均孔径Ａと内部の平均孔径Ｂとの比率Ａ／Ｂ、及び表面の平均開孔率Ｃと内部の平均開孔率Ｄとの比率Ｃ／Ｄは、好ましくはＡ／Ｂが０．５〜２であってＣ／Ｄが０．７５〜１．４、より好ましくはＡ／Ｂが０．６〜１．５であってＣ／Ｄが０．８〜１．３である。これらの比率が小さすぎる場合は、透過性能が劣ったり、機能性材料を十分に充填できない場合がある。また、大きすぎる場合には、分離特性に劣ったり、機能性材料の充填が不均一になるなどの不都合が発生する可能性がある。 The ratio A / B between the average pore diameter A on the surface and the average average pore diameter B and the ratio C / D between the average average aperture ratio C on the surface and the average average aperture ratio D on the surface are preferably set so that A / B is 0.00. 5 to 2, C / D is 0.75 to 1.4, more preferably A / B is 0.6 to 1.5, and C / D is 0.8 to 1.3. When these ratios are too small, the transmission performance may be inferior or the functional material may not be sufficiently filled. On the other hand, if it is too large, there is a possibility that inconveniences such as inferior separation characteristics and non-uniform filling of the functional material may occur.
好ましい多孔性フィルムの他の態様は、連通性を有する微小孔が多数存在する多孔性フィルムであって、該フィルムの厚みが５〜２００μｍ、フィルムの両面の平均孔径Ａ1，Ａ2が何れも０．０１〜１０μｍ、フィルムの両面の平均開孔率Ｃ1，Ｃ2が何れも４８％以上であり、且つ一方の表面（例えば基板側表面）の平均孔径Ａ1と他方の表面（例えば空気側表面）の平均孔径Ａ2との比率Ａ1／Ａ2が０．３〜３、一方の表面の平均開孔率Ｃ1と他方の表面の平均開孔率Ｃ2との比率Ｃ1／Ｃ2が０．７〜１．５である。 Another aspect of the preferred porous film is a porous film in which a large number of communicating micropores are present, the thickness of the film being 5 to 200 μm, and the average pore diameters A 1 and A 2 on both sides of the film are both 0.01 to 10 μm, the average open area ratios C 1 and C 2 on both sides of the film are 48% or more, and the average pore diameter A 1 on one surface (for example, substrate side surface) and the other surface (for example, air) The ratio A 1 / A 2 to the average pore diameter A 2 of the side surface) is 0.3 to 3, and the ratio C 1 / of the average aperture ratio C 1 of one surface to the average aperture ratio C 2 of the other surface C 2 is 0.7 to 1.5.
一方の表面の平均孔径Ａ1と他方の表面の平均孔径Ａ2との比率Ａ1／Ａ2、及び一方の表面の平均開孔率Ｃ1と他方の表面の平均開孔率Ｃ2との比率Ｃ1／Ｃ2は、好ましくはＡ1／Ａ2が０．５〜２であってＣ1／Ｃ2が０．７５〜１．４、より好ましくはＡ1／Ａ2が０．６〜１．５であってＣ1／Ｃ2が０．８〜１．３である。これらの比率が小さすぎる場合は、透過性能が劣ったり、機能性材料を十分に充填できない場合がある。また、大きすぎる場合には、分離特性に劣ったり、機能性材料の充填が不均一になるなどの不都合が発生する可能性がある。 The ratio A 1 / A 2 between the average pore diameter A 1 of one surface and the average pore diameter A 2 of the other surface, and the average aperture ratio C 1 of one surface and the average aperture ratio C 2 of the other surface The ratio C 1 / C 2 is preferably such that A 1 / A 2 is 0.5 to 2 and C 1 / C 2 is 0.75 to 1.4, more preferably A 1 / A 2 is 0.6. a 1.5 by C 1 / C 2 is 0.8 to 1.3. When these ratios are too small, the transmission performance may be inferior or the functional material may not be sufficiently filled. On the other hand, if it is too large, there is a possibility that inconveniences such as inferior separation characteristics and non-uniform filling of the functional material may occur.
多孔性フィルムの微小孔の径、空孔率、透気度、開孔率は、上記のように、用いる基板、水溶性ポリマーの種類や量、水の使用量、流延時の湿度、温度及び時間などを適宜選択することにより所望の値に調整することができる。 As described above, the micropore diameter, porosity, air permeability, and porosity of the porous film are the substrate used, the type and amount of the water-soluble polymer, the amount of water used, the humidity during casting, the temperature, and It can be adjusted to a desired value by appropriately selecting time and the like.
本発明の方法によれば、特に、平均孔径及び平均開孔率について、表面と内部との比率や基板側表面と空気側表面との比率が上記範囲内であるという特性を有する多孔性フィルムを容易に得ることができる。 According to the method of the present invention, a porous film having the characteristics that the ratio of the surface to the inside and the ratio of the substrate side surface to the air side surface are within the above ranges, particularly with respect to the average pore diameter and the average porosity. Can be easily obtained.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお、表面張力の測定、及び得られたフィルムの評価は次のようにして行った。これらの結果を表１に示す。表１中、「Sa-Sb」は、フィルムを構成する高分子の表面張力Saと基板の表面張力Sbとの差を示している。また、「−」は、微小孔が不定形なため算出不能であったことを示している。なお、実施例４〜５は参考例として記載する。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the measurement of surface tension and evaluation of the obtained film were performed as follows. These results are shown in Table 1. In Table 1, “Sa-Sb” indicates the difference between the surface tension Sa of the polymer constituting the film and the surface tension Sb of the substrate. Further, “−” indicates that the calculation is impossible because the micropore is indefinite. Examples 4 to 5 are described as reference examples.
表面張力
POLYMER HANDBOOK (THIRD EDITION, JOHN WILEY&SONS)、化学工学便覧（改訂五版、丸善株式会社）に掲載されている値を使用した。この本に記載されていない物質については、ポリマー単体（又はポリマーブレンド）の均一フィルムを作成し、ＪＩＳ Ｋ６７６８に準じて測定した。実施例中、後者の方法により測定した表面張力を示す場合には「：測定値」と付記した。
surface tension
The values listed in POLYMER HANDBOOK (THIRD EDITION, JOHN WILEY & SONS) and Chemical Engineering Handbook (5th revised edition, Maruzen Co., Ltd.) were used. For substances not described in this book, a uniform film of polymer alone (or polymer blend) was prepared and measured according to JIS K6768. In Examples, when the surface tension measured by the latter method is shown, “: measured value” is added.
透気度
YOSHIMITSU社製のGurley's Densometerを用い、ＪＩＳ Ｐ８１１７に準じて測定した。但し、測定面積が標準の１／１０の装置を使用したので、ＪＩＳ Ｐ８１１７の付属書１に準じて標準のガーレー値に換算して求めた。
Air permeability
Measurement was performed according to JIS P8117 using a Gurley's Densometer manufactured by YOSHIMITSU. However, since an apparatus having a measurement area of 1/10 of the standard was used, the standard Gurley value was calculated according to Appendix 1 of JIS P8117.
純水透過速度
Amicon社製のSTIRRED ULTRAFILTRATION CELLS MODELS 8200の平膜用濾過器を用いて評価した。透過面積は２８．７ｃｍ2であった。なお、評価の際に、透過側には濾紙をスペーサー代わりに配置し、透過側の抵抗をできるだけ排除した。圧力は０．５ｋｇ／ｃｍ2で測定し換算した。測定温度は２５℃である。
Pure water transmission rate
Evaluation was carried out using a STIRRED ULTRAFILTRATION CELLS MODELS 8200 flat membrane filter manufactured by Amicon. Permeation area was 28.7 cm 2. In the evaluation, a filter paper was arranged on the permeate side instead of a spacer, and resistance on the permeate side was eliminated as much as possible. The pressure was measured and converted at 0.5 kg / cm 2 . The measurement temperature is 25 ° C.
表面の平均孔径Ａ
電子顕微鏡写真から、フィルム表面の任意の３０点以上の孔についてその面積を測定し、まずその平均値を平均孔面積Ｓaveとした。次に、次式からその孔が真円であると仮定した時の孔径に換算し、その値を平均孔径とした。ここでπは円周率を表す。
表面の平均孔径Ａ＝２×（Ｓave／π）1/2
Surface average pore size A
From the electron micrograph, the area of any 30 or more holes on the film surface was measured, and the average value was first defined as the average hole area Save . Next, it converted into the hole diameter when it assumed that the hole was a perfect circle from the following formula, and the value was made into the average hole diameter. Here, π represents a circumference ratio.
Surface average pore diameter A = 2 × (S ave / π) 1/2
内部の平均孔径Ｂ
まず、フィルムを液体窒素温度で破断してフィルム断面を露出させた。該方法によりフィルムが破断できない場合には、あらかじめフィルムを水により湿潤にした状態で液体窒素温度で破断させてフィルム断面を露出させた。得られたフィルム断面を電子顕微鏡用サンプルとして、上述の表面の平均孔径の求め方と同様の方法を用いて平均孔径を求めた。
Internal average pore diameter B
First, the film was broken at liquid nitrogen temperature to expose the film cross section. When the film could not be broken by this method, the film was previously wetted with water and was broken at liquid nitrogen temperature to expose the film cross section. Using the obtained film cross section as an electron microscope sample, the average pore diameter was determined using the same method as the above-described method for determining the average pore diameter of the surface.
表面の最大孔径
フィルム表面の電子顕微鏡写真から、任意の２０×２０μｍの面積を５箇所選び、その中に存在する孔を真円であると仮定したときの孔径に換算し、その中で最も大きくなるものを最大孔径とした。なお、換算には次式を使用した。ここでＳmaxは観察された孔のうちで最大面積を有するものの値である。πは円周率を表す。
孔径＝２×（Ｓmax／π）1/2
Maximum pore diameter on the surface From the electron micrograph of the film surface, select an arbitrary 20 × 20 μm area, convert it to the hole diameter when assuming that the hole existing in it is a perfect circle, and the largest among them This was the maximum pore size. The following formula was used for conversion. Here, Smax is the value of the observed hole having the largest area. π represents the circumference ratio.
Pore size = 2 × (Smax / π) 1/2
内部の最大孔径
まず、フィルムを液体窒素温度で破断してフィルム断面を露出させた。該方法によりフィルムが破断できない場合には、あらかじめフィルムを水により湿潤にした状態で液体窒素温度で破断させてフィルム断面を露出させた。得られたフィルム断面を電子顕微鏡用サンプルとして、上述の表面の最大孔径の求め方と同様の方法を用いて最大孔径を求めた。
Internal maximum pore diameter First, the film was broken at liquid nitrogen temperature to expose the film cross section. When the film could not be broken by this method, the film was previously wetted with water and was broken at liquid nitrogen temperature to expose the film cross section. Using the obtained film cross section as a sample for an electron microscope, the maximum pore diameter was determined using the same method as the above-described method for determining the maximum pore diameter on the surface.
表面の平均開孔率Ｃ
表面の平均開孔率は、フィルム表面の電子顕微鏡写真から、任意の２０×２０μｍの面積を選び、その中に存在する孔の合計面積が全体に占める比率を算出した。この操作を任意の５箇所について実施し平均値を求めた。
Average surface area C
For the average surface area porosity, an arbitrary 20 × 20 μm area was selected from an electron micrograph of the film surface, and the ratio of the total area of the pores present therein to the whole was calculated. This operation was carried out at any five locations and the average value was determined.
内部の平均開孔率Ｄ（＝空孔率）
フィルムの内部の平均開孔率は次式より求めた。ここでＶはフィルムの体積、Ｗはフィルムの重量、ρはフィルム素材の密度であり、ポリアミドイミドの密度は１．４５（ｇ／ｃｍ3）、ポリエーテルスルホンの密度は１．３７（ｇ／ｃｍ3）、後述の実施例６に用いたポリアミドイミドとポリエーテルスルホンとのブレンド品の密度は１．４３（ｇ／ｃｍ3）とした。
内部の平均開孔率Ｄ（％）＝１００−１００×Ｗ／（ρ・Ｖ）
Internal average open area ratio D (= porosity)
The average aperture ratio inside the film was determined from the following equation. Here, V is the volume of the film, W is the weight of the film, ρ is the density of the film material, the density of polyamideimide is 1.45 (g / cm 3 ), and the density of polyethersulfone is 1.37 (g / cm 3 ), the density of the blend of polyamideimide and polyethersulfone used in Example 6 described later was 1.43 (g / cm 3 ).
Internal average open area ratio D (%) = 100-100 × W / (ρ · V)
なお、上記評価方法における平均孔径、最大孔径、及び平均開孔率は、電子顕微鏡写真の最も手前に見えている微小孔のみを対象として求められており、写真奥に見えている微小孔は対象外とした。 The average pore size, maximum pore size, and average open area ratio in the above evaluation method are obtained only for the micropores that are visible in the foreground of the electron micrograph, and the micropores that are visible in the back of the photo are the targets. It was outside.
実施例１
東洋紡績社製の商品名「バイロマックスＨＲ１１ＮＮ」（アミドイミド系ポリマー、ポリマー単体の表面張力４２ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値、固形分濃度１５重量％、溶剤ＮＭＰ、溶液粘度２０ｄＰａ・ｓ／２５℃）を使用し、この溶液１００重量部に対し、水溶性ポリマーとしてポリビニルピロリドン（分子量５万）を３０重量部加えて製膜用の原液とした。この原液を２５℃とし、フィルムアプリケーターを使用してテフロン（登録商標）製の基板上（表面張力２４ｍＮ／ｍ（＝ｄｙｎ／ｃｍ））にキャストした。キャストは３０℃、８０％ＲＨ雰囲気で実施し、キャスト後速やかに湿度約１００％、温度４５℃の容器中に４分間保持した。その後、水中に浸漬して凝固させ、次いで乾燥することによって多孔性フィルムを得た。この操作ではキャスト時のフィルムプリケーターとテフロン（登録商標）基板とのギャップは１２７μｍとし、得られたフィルムの厚みは約５０μｍとなった。
得られたフィルムの膜構造を観察したところ、キャスト時に基板と接触していたフィルム表面（フィルムの基板側表面）に存在する孔の平均孔径Ａ1は約０．９μｍ、最大孔径は２．５μｍで平均開孔率Ｃ1は約６５％、キャスト時に基板と接触していなかったフィルム表面（フィルムの空気側表面）に存在する孔の平均孔径Ａ2は約１．１μｍ、最大孔径は２．７μｍで平均開孔率Ｃ2は約７０％、フィルム内部はほぼ均質で、全域に亘って平均孔径Ｂ約１．０μｍ、最大孔径１．８μｍの連通性を持つ微小孔が存在していた。また、フィルムの内部の平均開孔率Ｄは７０％であった。透過性能を測定したところ、ガーレー透気度で９．５秒、純水透過速度で９．８×１０-9ｍ・ｓｅｃ-1・Ｐａ-1［＝６０リットル／（ｍ2・ｍｉｎ・ａｔｍ at ２５℃）］という優れた性能を示した。
Example 1
Trade name “Vilomax HR11NN” manufactured by Toyobo Co., Ltd. (amideimide polymer, surface tension of polymer alone 42 mN / m (= dyn / cm): measured value, solid content concentration 15% by weight, solvent NMP, solution viscosity 20 dPa · s And 25 parts by weight of polyvinyl pyrrolidone (molecular weight 50,000) as a water-soluble polymer was added to 100 parts by weight of this solution to form a stock solution for film formation. The stock solution was brought to 25 ° C. and cast on a Teflon (registered trademark) substrate (surface tension 24 mN / m (= dyn / cm)) using a film applicator. The casting was carried out in an atmosphere of 30 ° C. and 80% RH, and immediately after the casting, it was kept in a container having a humidity of about 100% and a temperature of 45 ° C. for 4 minutes. Then, the porous film was obtained by being immersed in water, solidifying, and then drying. In this operation, the gap between the film precursor at the time of casting and the Teflon (registered trademark) substrate was 127 μm, and the thickness of the obtained film was about 50 μm.
When the film structure of the obtained film was observed, the average hole diameter A 1 of the holes present on the film surface (the substrate side surface of the film) that was in contact with the substrate at the time of casting was about 0.9 μm, and the maximum hole diameter was 2.5 μm. The average hole area ratio C 1 is about 65%, the average hole diameter A 2 of the holes existing on the film surface (the air side surface of the film) that is not in contact with the substrate at the time of casting is about 1.1 μm, and the maximum hole diameter is 2. At 7 μm, the average aperture ratio C 2 was about 70%, the inside of the film was almost homogeneous, and micropores having an average pore diameter B of about 1.0 μm and a maximum pore diameter of 1.8 μm existed over the entire area. Moreover, the average opening ratio D inside the film was 70%. When the permeation performance was measured, the Gurley air permeability was 9.5 seconds, and the pure water permeation rate was 9.8 × 10 −9 m · sec −1 · Pa −1 [= 60 liters / (m 2 · min · atm. at 25 ° C.)].
実施例２
実施例１において、キャスト用基板として、テフロン（登録商標）製基板の代わりにポリプロピレン製の基板（表面張力２９ｍＮ／ｍ（＝ｄｙｎ／ｃｍ））を用いた以外は、実施例１と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約０．７μｍ、最大孔径は１．８μｍで平均開孔率Ｃ1は約５０％、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約１．０μｍ、最大孔径は２．５μｍで平均開孔率Ｃ2は約７０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約１．０μｍ、最大孔径２．０μｍの連通性を持つ微小孔が存在していた。また、フィルムの内部の平均開孔率Ｄは約７０％であった。透過性能を測定したところ、ガーレー透気度で１０．０秒、純水透過速度で９．０×１０-9ｍ・ｓｅｃ-1・Ｐａ-1［＝５５リットル／（ｍ2・ｍｉｎ・ａｔｍ at ２５℃）］という優れた性能を示した。
Example 2
In Example 1, the same operation as in Example 1 was used except that a polypropylene substrate (surface tension 29 mN / m (= dyn / cm)) was used instead of the Teflon (registered trademark) substrate as the casting substrate. To obtain a film.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 0.7 μm, the maximum pore diameter was 1.8 μm, and the average aperture ratio C 1 was about 50%. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 1.0 μm, the maximum pore diameter is 2.5 μm, the average aperture ratio C 2 is about 70%, the inside of the film is almost homogeneous, and the average over the entire area There were micropores having a pore size B of about 1.0 μm and a maximum pore size of 2.0 μm. The average opening ratio D inside the film was about 70%. When the permeation performance was measured, the Gurley air permeability was 10.0 seconds, and the pure water permeation rate was 9.0 × 10 −9 m · sec −1 · Pa −1 [= 55 liters / (m 2 · min · atm. at 25 ° C.)].
実施例３
実施例１において、キャスト用基板として、テフロン（登録商標）製基板の代わりに帝人デュポン社製ＰＥＴシート（Ｓタイプ、表面張力３９ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値）を用いた以外は、実施例１と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約０．９μｍ、最大孔径は２．５μｍで平均開孔率Ｃ1は約７０％、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約１．０μｍ、最大孔径は２．７μｍで平均開孔率Ｃ2は約７０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約１．０μｍ、最大孔径２．０μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。透過性能を測定したところ、ガーレー透気度で１０．０秒、純水透過速度で９．０×１０-9ｍ・ｓｅｃ-1・Ｐａ-1［＝５５リットル／（ｍ2・ｍｉｎ・ａｔｍ at ２５℃）］という優れた性能を示した。
Example 3
In Example 1, a Teijin DuPont PET sheet (S type, surface tension 39 mN / m (= dyn / cm): measured value) was used as the casting substrate instead of the Teflon (registered trademark) substrate. The same operation as in Example 1 was performed to obtain a film.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 0.9 μm, the maximum pore diameter was 2.5 μm, and the average aperture ratio C 1 was about 70%. The average hole diameter A 2 of the holes present on the air side surface of the film is about 1.0 μm, the maximum hole diameter is 2.7 μm, the average opening ratio C 2 is about 70%, the inside of the film is almost homogeneous, and the average over the entire area There were micropores having a pore size B of about 1.0 μm and a maximum pore size of 2.0 μm. The average opening ratio D inside the film was about 70%. When the permeation performance was measured, the Gurley air permeability was 10.0 seconds, and the pure water permeation rate was 9.0 × 10 −9 m · sec −1 · Pa −1 [= 55 liters / (m 2 · min · atm. at 25 ° C.)].
実施例４
実施例２において、製膜用の原液として、ポリエーテルスルホン（住友化学社製、商品名「５２００Ｐ」；表面張力４６ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値）１５重量部に、ポリビニルピロリドン（分子量３６万）１０重量部、及びＮＭＰ７５重量部を加えたものを用いた以外は、実施例２と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約１．３μｍ、最大孔径は２．５μｍで平均開孔率Ｃ1は約６５％、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約０．８μｍで、最大孔径は１．７μｍで平均開孔率Ｃ2は約５０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約２．０μｍ、最大孔径３．０μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。透過性能を測定したところ、ガーレー透気度で２９秒、純水透過速度で３．３×１０-9ｍ・ｓｅｃ-1・Ｐａ-1［＝２０リットル／（ｍ2・ｍｉｎ・ａｔｍ at ２５℃）］という優れた性能を示した。
Example 4
In Example 2, as a stock solution for forming a film, 15 parts by weight of polyethersulfone (manufactured by Sumitomo Chemical Co., Ltd., trade name “5200P”; surface tension 46 mN / m (= dyn / cm): measured value) A film was obtained in the same manner as in Example 2 except that 10 parts by weight of molecular weight 360,000) and 75 parts by weight of NMP were used.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 1.3 μm, the maximum pore diameter was 2.5 μm, and the average aperture ratio C 1 was about 65%. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 0.8 μm, the maximum pore diameter is 1.7 μm, the average aperture ratio C 2 is about 50%, and the inside of the film is almost homogeneous and covers the entire area. Micropores having an average pore diameter B of about 2.0 μm and a maximum pore diameter of 3.0 μm were present. The average opening ratio D inside the film was about 70%. When the permeation performance was measured, the Gurley air permeability was 29 seconds, and the pure water permeation rate was 3.3 × 10 −9 m · sec −1 · Pa −1 [= 20 liters / (m 2 · min · atm at 25 C))].
実施例５
実施例４において、キャスト用基板として、ポリプロピレン製基板の代わりに帝人デュポン社製ＰＥＴシート（Ｓタイプ、表面張力３９ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値）を用いた以外は、実施例４と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約２．３μｍ、最大孔径は３．６μｍで平均開孔率Ｃ1は約６５％、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約０．８μｍ、最大孔径１．７μｍで平均開孔率Ｃ2は約５０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約２．０μｍ、最大孔径５．１μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。透過性能を測定したところ、ガーレー透気度で２７秒、純水透過性能で３．９×１０-9ｍ・ｓｅｃ-1・Ｐａ-1［＝２４リットル／（ｍ2・ｍｉｎ・ａｔｍ at ２５℃）］という優れた性能を示した。
Example 5
In Example 4, a PET sheet (S type, surface tension 39 mN / m (= dyn / cm): measured value) manufactured by Teijin DuPont was used instead of the polypropylene substrate as the casting substrate. The same operation was performed to obtain a film.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 2.3 μm, the maximum pore diameter was 3.6 μm, and the average aperture ratio C 1 was about 65%. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 0.8 μm, the maximum pore diameter is 1.7 μm, the average aperture ratio C 2 is about 50%, the inside of the film is almost homogeneous, and the average pore diameter over the entire area. There existed micropores having a communication capacity of about 2.0 μm B and a maximum pore size of 5.1 μm. The average opening ratio D inside the film was about 70%. When the permeation performance was measured, the Gurley permeability was 27 seconds, and the pure water permeation performance was 3.9 × 10 −9 m · sec −1 · Pa −1 [= 24 liters / (m 2 · min · atm at 25 C))].
実施例６
ポリアミドイミド（東洋紡績社製、商品名「バイロマックスＨＲ１１ＮＮ」、表面張力４２ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値、固形分濃度１５重量％、溶剤ＮＭＰ、溶液粘度２０ｄＰａ・ｓ／２５℃）１００重量部に、ポリビニルピロリドン（分子量５万）２５重量部を加えたものをＡ液とした。ポリエーテルスルホン（住友化学社製、商品名「５２００Ｐ」；表面張力４６ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値）１５重量部にＮＭＰ８５重量部を加えて得られた混合液１００重量部に、ポリビニルピロリドン（分子量５万）２５重量部を加えたものをＢ液とした。
実施例２において、製膜用の原液として、ポリアミドイミドとポリエーテルスルホン（Ａ液：Ｂ液＝３：１（重量比）；ポリアミドイミド：ポリエーテルスルホン＝３：１（重量比））との混合液（ブレンドポリマーの表面張力４５ｍＮ／ｍ（＝ｄｙｎ／ｃｍ）：測定値）を用いた以外は、実施例２と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約０．９μｍ、最大孔径は１．８μｍで平均開孔率Ｃ1は約７０％、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約２．０μｍで、最大孔径は４．４μｍで平均開孔率Ｃ2は約７０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約２．０μｍ、最大孔径３．０μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。透過性能を測定したところ、ガーレー透気度で９．３秒、純水透過速度で１．１×１０-8ｍ・ｓｅｃ-1・Ｐａ-1［＝６５リットル／（ｍ2・ｍｉｎ・ａｔｍ at ２５℃）］という優れた性能を示した。
Example 6
Polyamideimide (Toyobo Co., Ltd., trade name “Vilomax HR11NN”, surface tension 42 mN / m (= dyn / cm): measured value, solid content concentration 15% by weight, solvent NMP, solution viscosity 20 dPa · s / 25 ° C.) A solution obtained by adding 25 parts by weight of polyvinyl pyrrolidone (molecular weight: 50,000) to 100 parts by weight was used as Liquid A. To 100 parts by weight of a mixture obtained by adding 85 parts by weight of NMP to 15 parts by weight of polyethersulfone (trade name “5200P” manufactured by Sumitomo Chemical Co., Ltd .; surface tension 46 mN / m (= dyn / cm): measured value) Liquid B was prepared by adding 25 parts by weight of polyvinylpyrrolidone (molecular weight 50,000).
In Example 2, as a stock solution for film formation, polyamideimide and polyethersulfone (A solution: B solution = 3: 1 (weight ratio); polyamideimide: polyethersulfone = 3: 1 (weight ratio)) A film was obtained in the same manner as in Example 2 except that the mixed liquid (blend polymer surface tension 45 mN / m (= dyn / cm): measured value) was used.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 0.9 μm, the maximum pore diameter was 1.8 μm, and the average aperture ratio C 1 was about 70%. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 2.0 μm, the maximum pore diameter is 4.4 μm, the average aperture ratio C 2 is about 70%, and the inside of the film is almost homogeneous and covers the entire area. Micropores having an average pore diameter B of about 2.0 μm and a maximum pore diameter of 3.0 μm were present. The average opening ratio D inside the film was about 70%. When the permeation performance was measured, the Gurley air permeability was 9.3 seconds, and the pure water permeation rate was 1.1 × 10 −8 m · sec −1 · Pa −1 [= 65 liters / (m 2 · min · atm. at 25 ° C.)].
比較例１
実施例１において、キャスト用基板として、テフロン（登録商標）製基板の代わりにガラス製基板（表面張力１００ｍＮ／ｍ（＝ｄｙｎ／ｃｍ））を用いた以外は、実施例１と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約０．３μｍ、最大孔径は０．６μｍで平均開孔率Ｃ1は約４０％、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約１．０μｍ、最大孔径は２．５μｍで平均開孔率Ｃ2は約７０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約１．０μｍ、最大孔径２．０μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。以上より、フィルムの基板側表面に存在する微小孔は、フィルムの空気側表面及び内部に存在する微小孔と比較して小さく、且つ開孔率が低く、フィルム全体としての均質性に欠けていた。
Comparative Example 1
In Example 1, the same operation as in Example 1 was performed except that a glass substrate (surface tension 100 mN / m (= dyn / cm)) was used instead of the Teflon (registered trademark) substrate as the casting substrate. A film was obtained.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 0.3 μm, the maximum pore diameter was 0.6 μm, and the average aperture ratio C 1 was about 40%. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 1.0 μm, the maximum pore diameter is 2.5 μm, the average aperture ratio C 2 is about 70%, the inside of the film is almost homogeneous, and the average over the entire area There were micropores having a pore size B of about 1.0 μm and a maximum pore size of 2.0 μm. The average opening ratio D inside the film was about 70%. From the above, the micropores present on the substrate side surface of the film were small compared to the micropores present on the air side surface and inside of the film, and the aperture ratio was low, and the film as a whole lacked homogeneity. .
比較例２
実施例１において、キャスト用基板として、テフロン（登録商標）製基板の代わりにアルミニウム製基板（表面張力９１４ｍＮ／ｍ（＝ｄｙｎ／ｃｍ））を用いた以外は、実施例１と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔は平均孔径Ａ1を算出するのは困難であるほど不定形であった。また、その平均開孔率Ｃ1は１０％以下と推定された。フィルムの空気側表面に存在する孔の平均孔径Ａ2は約１．３μｍ、最大孔径は２．７μｍで平均開孔率Ｃ2は約７０％、フィルム内部はほぼ均質であり全域に亘って平均孔径Ｂ約１．２μｍ、最大孔径２．２μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。以上より、フィルムの空気側表面及び内部と比較して、フィルムの基板側表面は開孔率が低く、且つ特異な様相を呈しており、フィルム全体としての均質性に欠けていた。
Comparative Example 2
In Example 1, the same operation as in Example 1 was performed except that an aluminum substrate (surface tension 914 mN / m (= dyn / cm)) was used instead of the Teflon (registered trademark) substrate as the casting substrate. A film was obtained.
When the film structure of the obtained film was observed, the holes present on the substrate side surface of the film were so irregular that it was difficult to calculate the average hole diameter A 1 . Further, the average opening ratio C 1 was estimated to be 10% or less. The average hole diameter A 2 of the holes present on the air side surface of the film is about 1.3 μm, the maximum hole diameter is 2.7 μm, the average opening ratio C 2 is about 70%, the inside of the film is almost homogeneous, and the average over the entire area There existed micropores having a pore size B of about 1.2 μm and a maximum pore size of 2.2 μm. The average opening ratio D inside the film was about 70%. From the above, the substrate-side surface of the film has a low porosity and exhibits a unique aspect as compared with the air-side surface and the inside of the film, and lacks uniformity as a whole film.
比較例３
実施例４において、キャスト用基板としてガラス製基板（表面張力１００ｍＮ／ｍ（＝ｄｙｎ／ｃｍ））を用いた以外は、実施例４と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔の平均孔径Ａ1は約１．２μｍ、最大孔径は２．０μｍで平均開孔率Ｃ1は１０％以下、フィルムの空気側表面に存在する孔の平均孔径Ａ2は約０．８μｍ、最大孔径は１．９μｍで平均開孔率Ｃ2は約５０％、フィルム内部は全域に亘って平均孔径Ｂ約２．０μｍ、最大孔径３．５μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。以上より、フィルムの基板側表面は、開孔率が低く、フィルム全体としての均質性に欠けていた。
Comparative Example 3
In Example 4, a film was obtained by performing the same operation as in Example 4 except that a glass substrate (surface tension 100 mN / m (= dyn / cm)) was used as the casting substrate.
When the film structure of the obtained film was observed, the average pore diameter A 1 of the holes present on the substrate side surface of the film was about 1.2 μm, the maximum pore diameter was 2.0 μm, and the average aperture ratio C 1 was 10% or less. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 0.8 μm, the maximum pore diameter is 1.9 μm, the average aperture ratio C 2 is about 50%, and the average pore diameter B is about 2 over the entire area inside the film. There were micropores having a communication capacity of 0.0 μm and a maximum pore diameter of 3.5 μm. The average opening ratio D inside the film was about 70%. From the above, the substrate-side surface of the film had a low hole area ratio and lacked homogeneity as a whole film.
比較例４
実施例４において、キャスト用基板としてアルミニウム製基板（表面張力９１４ｍＮ／ｍ（＝ｄｙｎ／ｃｍ））を用いた以外は、実施例４と同様の操作を行ってフィルムを得た。
得られたフィルムの膜構造を観察したところ、フィルムの基板側表面に存在する孔は平均孔径Ａ1を算出するのは困難であるほど不定形であった。また、その平均開孔率Ｃ1は１０％以下と推定された。フィルムの空気側表面に存在する孔の平均孔径Ａ2は約０．９μｍ、最大孔径は２．１μｍで平均開孔率Ｃ2は約５０％、フィルム内部は全域に亘って平均孔径Ｂ約２．２μｍ、最大孔径３．６μｍの連通性を持つ微小孔が存在していた。また、フィルム内部の平均開孔率Ｄは約７０％であった。以上より、フィルムの空気側表面及び内部と比較して、フィルムの基板側表面は開孔率が低く、且つ特異な様相を呈しており、フィルム全体としての均質性に欠けていた。
Comparative Example 4
In Example 4, except for using the A aluminum-made substrate (surface tension 914mN / m (= dyn / cm )) as a casting substrate to obtain a film by performing the same operations as in Example 4.
When the film structure of the obtained film was observed, the holes present on the substrate side surface of the film were so irregular that it was difficult to calculate the average hole diameter A 1 . Further, the average opening ratio C 1 was estimated to be 10% or less. The average pore diameter A 2 of the pores existing on the air side surface of the film is about 0.9 μm, the maximum pore diameter is 2.1 μm, the average aperture ratio C 2 is about 50%, and the inside of the film has an average pore diameter B of about 2 over the entire area. There were micropores having a communication capacity of 0.2 μm and a maximum pore size of 3.6 μm. The average opening ratio D inside the film was about 70%. From the above, the substrate-side surface of the film has a low porosity and exhibits a unique aspect as compared with the air-side surface and the inside of the film, and lacks uniformity as a whole film.
本発明の多孔性フィルムは、精密濾過、分離濃縮等の膜分離技術に利用できるほか、その空孔を機能性材料で充填することにより、電池用セパレータ、電解コンデンサー、回路用基板等、広範囲な基板材料として利用できる。 The porous film of the present invention can be used for membrane separation techniques such as microfiltration and separation / concentration, and by filling the pores with functional materials, a wide range of battery separators, electrolytic capacitors, circuit boards, etc. It can be used as a substrate material.
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| JP6395144B2 (en) * | 2014-04-09 | 2018-09-26 | ユニチカ株式会社 | Polyimide resin porous body and method for producing the same |
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