WO2015108114A1 - ポリアミドイミド溶液、多孔質ポリアミドイミドフィルム、およびその製造方法 - Google Patents
ポリアミドイミド溶液、多孔質ポリアミドイミドフィルム、およびその製造方法 Download PDFInfo
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- the present invention relates to a polyamideimide solution and a production method thereof, a porous polyamideimide film obtained from the polyamideimide solution, and a production method thereof (hereinafter, polyamideimide may be abbreviated as “PAI”).
- PAI polyamideimide
- Polyimide-based porous films use electronic materials and optical materials, lithium secondary battery separators, filters, separation membranes, wire coatings, and other industrial materials and medical materials by utilizing their excellent heat resistance and high porosity. It is used in the field of materials.
- thermosetting polyimides (PI) using a polyimide precursor (polyamic acid) among polyimide porous films an amide solvent and an ether solvent are used as a method for producing this porous film.
- a PI precursor solution contained as a solvent is applied on a substrate having a heat resistance of 300 ° C. or higher, and then dried to induce a phase separation phenomenon, and then thermoset at a high temperature of about 300 ° C. to be porous.
- Patent Document 1 a method for obtaining a high quality PI film (hereinafter, this method may be abbreviated as “dry pore forming process”) (Patent Document 1).
- This method is different from a wet porous process in which a coating film formed on a substrate is immersed in a coagulating liquid containing a poor solvent to produce a porous film when producing a porous PI film.
- a coagulation bath for conversion. Therefore, since no waste liquid is generated from the coagulation bath during the production of the porous PI film, the dry porosification process is an excellent method with good environmental compatibility.
- the PI precursor coating film formed on the base material contracts during thermosetting, which limits the range of application in some cases. There was.
- the present inventors have found that the above problems can be solved by setting the PAI solution to a specific composition, particularly a specific solvent content, and have completed the present invention.
- the present invention has the following objects.
- a PAI solution containing a nitrogen-containing polar solvent and an ether solvent The solid content concentration of the PAI is 25% by mass or less based on the mass of the PAI solution, The content of the nitrogen-containing polar solvent is 15% by mass or more based on the mass of the PAI solution, The PAI solution, wherein the content of the ether solvent is more than 30% by mass with respect to the mass of the PAI solution.
- a porous PAI film can be easily obtained from the PAI solution of the present invention by a simple process at a low temperature.
- the obtained porous PAI film has excellent heat resistance, high porosity, excellent permeability, and good mechanical properties based on excellent uniformity of pores. It can be suitably used in the fields of industrial materials such as secondary battery separators, filters, separation membranes, wire coatings, and medical materials.
- FIG. 2 is an enlarged SEM image of a cross section of the porous PAI film in FIG. 1. It is a SEM image of the porous PAI film surface of this invention.
- the present invention relates to a PAI solution and a production method thereof, a porous PAI film obtained from the PAI solution, and a production method thereof.
- aromatic tricarboxylic acid component examples include a benzene tricarboxylic acid component and a naphthalene tricarboxylic acid component.
- benzenetricarboxylic acid component examples include, for example, trimellitic acid, hemimellitic acid, anhydrides thereof, and monochlorides thereof.
- naphthalene tricarboxylic acid component examples include, for example, 1,2,3-naphthalene tricarboxylic acid, 1,6,7-naphthalene tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, and anhydrides and monochlorides thereof. Is mentioned.
- aromatic tricarboxylic acid components are preferred.
- aromatic tricarboxylic acid components trimellitic acid and trimellitic anhydride chloride (TAC) are preferred.
- the tricarboxylic acid component may be used alone or in combination of two or more.
- As the tricarboxylic acid component a part of which is substituted with a component such as pyromellitic acid, benzophenone tetracarboxylic acid, or biphenyl tetracarboxylic acid may be used.
- the diamine component of PAI is an organic compound having two primary amino groups (including derivatives thereof) and one or more aromatic rings or aliphatic rings per molecule.
- a diamine component shall be used by the concept including an aromatic diamine component and an alicyclic diamine component.
- aromatic diamine component examples include, for example, 4,4′-diaminodiphenyl ether (DADE), m-phenylenediamine (MDA), p-phenylenediamine, 4,4′-diphenylmethanediamine (DMA), 4,4 ′. -Diphenyl ether diamine, diphenyl sulfone-4,4'-diamine, diphenyl-4,4'-diamine, o-tolidine, 2,4-tolylenediamine, 2,6-tolylenediamine, xylylenediamine, naphthalenediamine, and These diisocyanate derivatives are mentioned.
- DADE 4,4′-diaminodiphenyl ether
- MDA m-phenylenediamine
- DMA 4,4′-diphenylmethanediamine
- DADE 4,4′. -Diphenyl ether diamine, diphenyl sulfone-4,4'-
- aromatic diamine components are preferred.
- DADE, MDA and DMA are preferred.
- the diamine component may be used alone or in combination of two or more.
- PAI usually has a glass transition temperature of 200 ° C. or higher.
- a value measured by DSC differential thermal analysis
- PAI is different from thermosetting polyimide that requires a high temperature of about 300 ° C. in order to imidize its precursor polyamic acid during molding.
- the PAI solution of the present invention is a solution containing a mixed solvent containing a nitrogen-containing polar solvent and an ether solvent, wherein the solid content concentration of the PAI is 25% by mass or less with respect to the mass of the PAI solution,
- the content of the polar solvent is 15% by mass or more with respect to the mass of the PAI solution, and the content of the ether solvent is more than 30% by mass with respect to the mass of the PAI solution.
- the content of the nitrogen-containing polar solvent is preferably 17% by mass or more based on the mass of the PAI solution.
- the upper limit of the content of the nitrogen-containing polar solvent is not particularly limited, but from the viewpoint of further increasing the porosity of the film, it is 50% by mass or less, particularly 30% by mass or less, based on the mass of the PAI solution. It is preferable that
- the content of the ether solvent is preferably more than 40% by mass, more preferably more than 50% by mass, and more preferably more than 60% by mass with respect to the mass of the PAI solution.
- the upper limit of the content of the ether solvent is not particularly limited, but from the viewpoint of further increasing the porosity of the film, it is 80% by mass or less, particularly 75% by mass or less, based on the mass of the PAI solution. Preferably there is.
- the ether solvent (poor solvent) remaining in the coating film acts at a temperature of 200 ° C. or lower. Phase separation occurs efficiently. Accordingly, a PAI film having a high porosity can be obtained.
- an amide solvent or a urea solvent can be used as the nitrogen-containing polar solvent used in the present invention.
- amide solvents include N-methyl-2-pyrrolidone (NMP boiling point: 202 ° C.), N, N-dimethylformamide (boiling point: 153 ° C.), and N, N-dimethylacetamide (DMAc boiling point: 166 ° C.).
- urea solvents include tetramethylurea (TMU boiling point: 177 ° C) and dimethylethyleneurea (boiling point: 220 ° C).
- TMP and DMAc are preferably used, and NMP is particularly preferable.
- ether solvent used in the present invention a solvent having a boiling point higher than that of the nitrogen-containing polar solvent is preferably used.
- the boiling point difference is preferably 5 ° C or higher, more preferably 20 ° C or higher, and 50 ° C or higher. Further preferred.
- ether solvents alone are poor solvents that cannot dissolve PAI.
- examples of the ether solvent include diethylene glycol dimethyl ether (DEGM boiling point: 162 ° C), triethylene glycol dimethyl ether (TRGM boiling point: 216 ° C), tetraethylene glycol dimethyl ether (TEGM boiling point: 275 ° C), diethylene glycol (DEG boiling point: 244 ° C).
- solvents such as triethylene glycol (TEG boiling point: 287 ° C.). These may be used alone or in combination of two or more. Among these, TRGM and TEGM are preferably used, and TEGM is particularly preferable.
- the mixed solvent may contain other solvents as long as the effects of the present invention are not impaired.
- the PAI solution of the present invention is preferably produced, for example, by the following production method. That is, solid PAI is dissolved in the mixed solvent to obtain a PAI solution.
- solid PAI for example, commercially available PAI powder (for example, Torlon 4000T series, Torlon 4000TF, Torlon AI-10 series, etc. manufactured by Solvay Advanced Polymers Co., Ltd.) can be used.
- PAI powder for example, Torlon 4000T series, Torlon 4000TF, Torlon AI-10 series, etc. manufactured by Solvay Advanced Polymers Co., Ltd.
- the production method using the solid PAI as described above is preferable, but the tricarboxylic acid component and the diamine component as raw materials are blended in approximately equimolar amounts, A solution obtained by polymerization reaction in a mixed solvent can also be used.
- a polymerization reaction is obtained only in a nitrogen-containing polar solvent to obtain a solution, and then an ether solvent is added thereto, or a suspension is obtained by polymerization reaction only in an ether solvent, and then contained in this.
- a PAI solution can be obtained by adding a nitrogen polar solvent, a method using a solid PAI as described above is preferred.
- PAI solution of the present invention known additives such as various surfactants and organic silane coupling agents may be added to the PAI solution of the present invention as long as the effects of the present invention are not impaired. Moreover, you may add other polymers other than PAI to a PAI solution in the range which does not impair the effect of this invention as needed.
- the porous PAI film of the present invention can be produced by a low-temperature dry porosity process using the PAI solution. That is, the PAI solution of the present invention is applied to the surface of a substrate and dried at 80 to 200 ° C., preferably 100 to 160 ° C. for 10 to 60 minutes, so that the porosity is 40 to 90% by volume. A quality PAI film can be formed. Thereafter, the porous PAI film can be peeled from these substrates to form a porous PAI film alone. Moreover, the porous PAI film formed on the base material can be used by being laminated and integrated with the base material without peeling from the base material. In addition, since the porous PAI film is excellent in heat resistance, after the drying, heat treatment may be performed at a temperature of 200 ° C. or higher, for example, about 300 ° C.
- the substrate examples include a metal foil, a metal wire, a glass plate, a thermoplastic resin film (a thermoplastic resin film having a melting point or a softening point of 300 ° C. or less such as polyester, polypropylene, polycarbonate), a thermosetting resin such as polyimide.
- a film, various textiles, various nonwoven fabrics, etc. are mentioned.
- As the metal gold, silver, copper, platinum, aluminum, or the like can be used.
- the substrate may be porous or non-porous. Among these, a polyester film is preferable, and a polyethylene terephthalate (PET melting point: 260 ° C.) film is particularly preferable.
- the PET film may be subjected to surface treatment such as corona discharge treatment.
- a dip coater, a bar coater, a spin coater, a die coater, a spray coater or the like can be used, and the coating can be applied continuously or batchwise.
- the porosity of the porous PAI film obtained by the production method is preferably 40 to 90% by volume, more preferably 45 to 85% by volume, and still more preferably 60 to 85% by volume. .
- the porous PAI film having the porosity set in this way can ensure good mechanical properties and permeability at the same time, and can be used for a separator for a lithium secondary battery, a filter, and the like.
- the porosity of the porous PAI film is a value calculated from the apparent density of the porous PAI film and the true density (specific gravity) of the PAI constituting the porous PAI film. Specifically, the porosity (volume%) is calculated by the following formula when the apparent density of the porous PAI film is A (g / cm 3 ) and the true density of the PAI is B (g / cm 3 ).
- the average pore diameter of the pores of the porous PAI film is preferably from 0.1 to 10 ⁇ m, more preferably from 0.5 to 5 ⁇ m.
- the formed pores may be continuous pores or independent pores, but are preferably continuous pores.
- pores are preferably formed on the film surface.
- the thickness of the porous PAI film is preferably 1 to 300 ⁇ m, more preferably 10 to 100 ⁇ m.
- the porosity and pore diameter can be adjusted by selecting the type and amount of the mixed solvent (nitrogen-containing polar solvent and ether solvent) in the PAI solution.
- a porous PAI film can be easily obtained from the PAI solution of the present invention. Since this porous PAI film manufacturing method is based on a dry porous process, waste liquid from a coagulation bath containing a poor solvent is not generated during pore formation. Therefore, the environmental compatibility is good and the process is very simple. The resulting porous PAI film has high porosity and good mechanical properties.
- This solution was applied onto a PET film (Unitika Ltd. thickness: 100 ⁇ m) whose surface was subjected to corona discharge treatment, dried at 130 ° C. for 30 minutes, and then peeled off the coating film from the PET film to give a porous film having a thickness of 50 ⁇ m.
- a quality PAI film was obtained.
- the measurement results of the porosity of this porous PAI film are shown in Table 1. 1 to 3 show SEM images of the cross section and the surface (PET film contact surface) of the porous PAI film. It can be seen that uniform continuous pores having a pore diameter of about 2 to 3 ⁇ m are formed over the entire cross section, and pores are also formed on the surface.
- this porous PAI film When the mechanical properties of this porous PAI film were evaluated based on the provisions of JIS-C-2151, the tensile strength was 14.1 MPa and the elongation was 38.8%. Was confirmed. Furthermore, when the Gurley value of this porous PAI film was measured based on the provisions of JIS-P8117, it was 1580 seconds, and it was confirmed that the film showed good permeability based on continuous pores.
- Examples 2 to 8 In the same manner as in Example 1, PAI solutions (A-2 to A-8) were prepared with the compositions shown in Table 1. From these solutions, porous PAI films were obtained under the same conditions as in Example 1. Table 1 shows the measurement results of the porosity of these porous PAI films.
- Example 9 As PAI powder, PAI powder obtained by polymerizing TAC and DMA (Tolon AI-10 manufactured by Solvay Advanced Polymers Co., Ltd., glass transition temperature 272 ° C.) was used in the same manner as in Example 1. Thus, a PAI solution (A-9) was prepared. From this solution, a porous PAI film was obtained under the same conditions as in Example 1. Table 1 shows the porosity measurement results of this porous PAI film.
- a PAI solution (B-10) was prepared according to the description in Example 1 of JP2013-187029 (Patent Document 2). That is, by adding 51.2 g of TRGM to 200 g of a commercially available PAI solution (manufactured by Hitachi Chemical Co., Ltd .: HI-406, PAI solid content: 32 mass%, solvent: NMP, PAI glass transition temperature: 288 ° C.), PAI A uniform PAI solution (B-10) having a solid content concentration of about 25% by mass with respect to the PAI solution and an ether solvent content ratio of about 21% by mass with respect to the PAI solution was obtained. From this solution, a porous PAI film was obtained under the same conditions as in Example 1. The results of measuring the porosity of this PAI film are shown in Table 1.
- a PAI solution (B-10) was prepared according to the description in Example 2 of JP2013-210493 (Patent Document 3). That is, NMP 15 g, TRGM 10 g, and TEGM 30 g are added to 200 g of a commercially available PAI solution (manufactured by Hitachi Chemical Co., Ltd .: HI-406, PAI solid content: 32 mass%, solvent: NMP, glass transition temperature of PAI: 288 ° C.).
- a uniform PAI solution (B-11) having a PAI solid content concentration of about 25% by mass in the PAI solution ratio and an ether solvent content ratio of about 16% by mass in the PAI solution ratio was obtained. From this solution, a porous PAI film was obtained under the same conditions as in Example 1. The results of measuring the porosity of this PAI film are shown in Table 1.
- the porous PAI film obtained from the PAI solution of the present invention has a high porosity (40% by volume or more), and can be suitably used for secondary battery separators, filters, and the like. I know that there is. On the other hand, the porosity (less than 40 volume%) of the porous PAI film obtained from the PAI solution shown in the comparative example is low, and it can be seen that application to a secondary battery separator, a filter or the like is difficult.
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Abstract
Description
<1> 含窒素極性溶媒およびエーテル系溶媒を含有するPAI溶液であって、
前記PAIの固形分濃度が、PAI溶液質量に対し25質量%以下であり、
前記含窒素極性溶媒の含有量が、PAI溶液質量に対し15質量%以上であり、
前記エーテル系溶媒の含有量が、PAI溶液質量に対し30質量%超であることを特徴とするPAI溶液。
<2> 固体状のPAIを、含窒素極性溶媒およびエーテル系溶媒を含む混合溶媒に溶解させることを特徴とする<1>に記載のPAI溶液の製造方法。
<3> <1>に記載のPAI溶液を基材上に塗布後、200℃以下の温度で乾燥することにより相分離現象を誘起せしめ多孔質化することを特徴とする多孔質PAIフィルムの製造方法。
<4> 基材がポリエステルフィルムであることを特徴とする<3>に記載の多孔質PAIフィルムの製造方法。
<5> <3>または<4>に記載の方法によって製造された多孔質PAIフィルム。
本発明はPAI溶液およびその製造方法、このPAI溶液から得られる多孔質PAIフィルム、およびその製造方法に関するものである。
PAIは、主鎖にイミド結合とアミド結合の両方を有する耐熱性高分子であり、例えば、原料であるトリカルボン酸成分とジアミン成分との重縮合反応を行うことにより得ることができる。
芳香族トリカルボン酸成分の中では、トリメリット酸および無水トリメリット酸クロライド(TAC)が好ましい。
芳香族ジアミン成分の中では、DADE、MDAおよびDMAが好ましい。
本発明の多孔質PAIフィルムは、前記PAI溶液を用いて低温乾式多孔化プロセスにより製造することができる。すなわち、本発明の前記PAI溶液を、基材の表面に塗布し、80~200℃、好ましくは100~160℃で、10~60分乾燥することにより、気孔率が40~90体積%の多孔質PAIフィルムを形成することができる。その後、これらの基材から多孔質PAIフィルムを剥離して多孔質PAIフィルム単体とすることができる。また、基材上に形成された多孔質PAIフィルムは、基材から剥離することなく、基材と積層一体化して使用することもできる。なお、多孔質PAIフィルムは、耐熱性に優れるので、前記乾燥後、200℃以上の温度、例えば300℃程度で熱処理を行っても良い。
TACと、DADEおよびMDAとを共重合(共重合モル比:DADE/MDA=7/3)して得られるPAI粉体(ソルベイアドバンストポリマーズ株式会社製トーロン4000T-HV、ガラス転移温度280℃)15gを、NMP25gとTEGM60gとからなる混合溶媒に、30℃で溶解して、PAIの固形分濃度が対PAI溶液比で15質量%であり、エーテル系溶媒の含有比率が対PAI溶液比で60質量%の均一なPAI溶液(A-1)を得た。
実施例1と同様にして、表1に示す組成で、PAI溶液(A-2~A-8)を作成した。これらの溶液から、実施例1と同様の条件で多孔質PAIフィルムを得た。これらの多孔質PAIフィルムの気孔率測定結果を表1に示す。
PAI粉体として、TACと、DMAとを重合して得られるPAI粉体(ソルベイアドバンストポリマーズ株式会社製トーロンAI-10、ガラス転移温度272℃)を用いたこと以外は、実施例1と同様にして、PAI溶液(A-9)を作成した。この溶液から、実施例1と同様の条件で多孔質PAIフィルムを得た。この多孔質PAIフィルムの気孔率測定結果を表1に示す。
実施例1と同様にして、表1に示す組成で、PAI溶液(B-1~B-6)を作成した。これらの溶液から、実施例1と同様の条件で多孔質PAIフィルムを得た。これらの多孔質PAIフィルムの気孔率測定結果を表1に示す。
表1に示した組成で、実施例1と同様にしてPAI溶液(B-7~B-9)を作成しようとしたが、均一な溶液を得ることができなかった。
特開2013-187029(特許文献2)実施例1の記載に従って、PAI溶液(B-10)を作成した。すなわち、市販のPAI溶液(日立化成工業株式会社製:HI-406、PAI固形分:32質量%、溶媒:NMP、PAIのガラス転移温度:288℃)200gにTRGM51.2gを加えることにより、PAIの固形分濃度が対PAI溶液比で約25質量%であり、エーテル系溶媒の含有比率が対PAI溶液比で約21質量%の均一なPAI溶液(B-10)を得た。この溶液から、実施例1と同様の条件で多孔質PAIフィルムを得た。このPAIフィルムの気孔率測定結果を表1に示す。
特開2013-210493(特許文献3)実施例2の記載に従って、PAI溶液(B-10)を作成した。すなわち、市販のPAI溶液(日立化成工業株式会社製:HI-406、PAI固形分:32質量%、溶媒:NMP、PAIのガラス転移温度:288℃)200gに、NMP15g,TRGM10g、TEGM30gを加えることにより、PAIの固形分濃度が対PAI溶液比で約25質量%であり、エーテル系溶媒の含有比率が対PAI溶液比で約16質量%の均一なPAI溶液(B-11)を得た。この溶液から、実施例1と同様の条件で多孔質PAIフィルムを得た。このPAIフィルムの気孔率測定結果を表1に示す。
Claims (5)
- 含窒素極性溶媒およびエーテル系溶媒を含有するポリアミドイミド溶液であって、
前記ポリアミドイミドの固形分濃度が、ポリアミドイミド溶液質量に対し25質量%以下であり、
前記含窒素極性溶媒の含有量が、ポリアミドイミド溶液質量に対し15質量%以上であり、
前記エーテル系溶媒の含有量が、ポリアミドイミド溶液質量に対し30質量%超であることを特徴とするポリアミドイミド溶液。 - 固体状のポリアミドイミドを、含窒素極性溶媒およびエーテル系溶媒を含む混合溶媒に溶解させることを特徴とする請求項1に記載のポリアミドイミド溶液の製造方法。
- 請求項1に記載のポリアミドイミド溶液を基材上に塗布後、200℃以下の温度で乾燥することにより相分離現象を誘起せしめ多孔質化することを特徴とする多孔質ポリアミドイミドフィルムの製造方法。
- 基材がポリエステルフィルムであることを特徴とする請求項3に記載の多孔質ポリアミドイミドフィルムの製造方法。
- 請求項3または4に記載の方法によって製造された多孔質ポリアミドイミドフィルム。
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