JP2021172560A - Surface-coated boehmite, resin film composite, and carbon material composite - Google Patents
Surface-coated boehmite, resin film composite, and carbon material composite Download PDFInfo
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- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 109
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 109
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims description 21
- 239000003575 carbonaceous material Substances 0.000 title claims description 17
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 229920000867 polyelectrolyte Polymers 0.000 claims description 19
- 229920001448 anionic polyelectrolyte Polymers 0.000 claims description 17
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- OMSKWMHSUQZBRS-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)C1=CC=C(C=C)C=C1 OMSKWMHSUQZBRS-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 abstract description 5
- 229920006317 cationic polymer Polymers 0.000 abstract 2
- 229920006318 anionic polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000725 suspension Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 230000004520 agglutination Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920009405 Polyvinylidenefluoride (PVDF) Film Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、最外層がカチオン性高分子電解質となるように、アニオン性高分子電解質とカチオン性高分子電解質とによって交互に被覆された表面被覆ベーマイトに関する。また、本発明は、樹脂フィルムに当該表面被覆ベーマイトが付着した樹脂フィルム複合材料、及び炭素材に当該表面被覆ベーマイトが付着した炭素材複合材料にも関する。 The present invention relates to a surface-coated boehmite that is alternately coated with an anionic polyelectrolyte and a cationic polyelectrolyte so that the outermost layer becomes a cationic polyelectrolyte. The present invention also relates to a resin film composite material in which the surface coating boehmite is adhered to a resin film, and a carbon material composite material in which the surface coating boehmite is adhered to a carbon material.
ベーマイトは、ＡｌＯＯＨ又はＡｌ２Ｏ３・Ｈ２Ｏで表される組成式を有し、樹脂添加剤や研磨材として利用されている（特許文献１）。 Boehmite has a composition formula represented by AlOOH or Al 2 O 3 · H 2 O , is used as a resin additive or abrasive (Patent Document 1).
発明者らは、ベーマイトは、樹脂に対する付着力が低いという問題を有することを見出した。また、発明者らは、ベーマイトは、ｐＨ４程度の水溶液中での分散性は高いものの、水溶液のｐＨが６〜８程度になると、凝集が起こり、分散性が悪化するという問題を有することを見出した。 The inventors have found that boehmite has a problem of low adhesion to a resin. Further, the inventors have found that although boehmite has high dispersibility in an aqueous solution having a pH of about 4, agglutination occurs when the pH of the aqueous solution reaches about 6 to 8, and the dispersibility deteriorates. rice field.
本発明は上記課題に鑑み、樹脂に対する付着性が高く、且つ、広いｐＨ範囲にわたって高い分散性を有する表面被覆ベーマイトを提供することを目的とする。また、本発明は、樹脂フィルムに当該表面被覆ベーマイトが付着した樹脂フィルム複合材料、及び炭素材に当該表面被覆ベーマイトが付着した炭素材複合材料を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a surface-coated boehmite having high adhesiveness to a resin and high dispersibility over a wide pH range. Another object of the present invention is to provide a resin film composite material in which the surface-coated boehmite is adhered to a resin film, and a carbon material composite material in which the surface-coated boehmite is adhered to a carbon material.
本発明は、以下に掲げる態様の発明を提供する。
（項目１）
最外層がカチオン性高分子電解質となるように、アニオン性高分子電解質とカチオン性高分子電解質とによって交互に被覆されている、表面被覆ベーマイト。
The present invention provides the inventions of the following aspects.
(Item 1)
A surface-coated boehmite in which an anionic polyelectrolyte and a cationic polyelectrolyte are alternately coated so that the outermost layer becomes a cationic polyelectrolyte.
（項目２）
前記カチオン性高分子電解質は、ポリ（塩化ジアリルジメチルアンモニウム）、及びポリエチレンイミンの少なくとも一種である、
項目１に記載の表面被覆ベーマイト。
(Item 2)
The cationic polyelectrolyte is at least one of poly (diallyldimethylammonium chloride) and polyethyleneimine.
The surface-coated boehmite according to item 1.
（項目３）
前記アニオン性高分子電解質は、ポリ（４−スチレンスルホン酸）ナトリウム、ポリアクリル酸、及びポリビニル硫酸の少なくとも一種である、
項目１又は２に記載の表面被覆ベーマイト。
(Item 3)
The anionic polyelectrolyte is at least one of poly (4-styrene sulfonic acid) sodium, polyacrylic acid, and polyvinyl sulfuric acid.
The surface-coated boehmite according to item 1 or 2.
（項目４）
樹脂フィルムに、項目１から３のいずれか１項に記載の表面被覆ベーマイトが付着した樹脂フィルム複合材料。
(Item 4)
A resin film composite material in which the surface-coated boehmite according to any one of items 1 to 3 is attached to the resin film.
（項目５）
炭素材に、項目１から３のいずれか１項に記載の表面被覆ベーマイトが付着した炭素材複合材料。
(Item 5)
A carbon material composite material in which the surface coating boehmite according to any one of items 1 to 3 is attached to the carbon material.
（項目６）
項目４に記載の樹脂フィルム複合材料、又は、項目５に記載の炭素材複合材料を使用した二次電池材料。
(Item 6)
A secondary battery material using the resin film composite material according to item 4 or the carbon material composite material according to item 5.
本発明の表面被覆ベーマイトは、樹脂に対する付着性が高く、且つ、広いｐＨ範囲にわたって高い分散性を有する。 The surface-coated boehmite of the present invention has high adhesion to a resin and high dispersibility over a wide pH range.
本発明の表面被覆ベーマイト、樹脂フィルム複合材料、及び炭素材複合材料について説明する。 The surface coating boehmite, the resin film composite material, and the carbon material composite material of the present invention will be described.
本発明は、ベーマイトの表面を、最外層がカチオン性高分子電解質となるように、アニオン性高分子電解質とカチオン性高分子電解質とによって交互に被覆した、表面被覆ベーマイトに関する。 The present invention relates to a surface-coated boehmite in which the surface of boehmite is alternately coated with an anionic polyelectrolyte and a cationic polyelectrolyte so that the outermost layer becomes a cationic polyelectrolyte.
被覆対象であるベーマイトの形状は特に限定されず、例えば、鱗片状、板状又は針状ベーマイトを使用することができる。 The shape of the boehmite to be covered is not particularly limited, and for example, scaly, plate-shaped or needle-shaped boehmite can be used.
カチオン性高分子電解質は、特に限定されないが、例えば、ポリ（塩化ジアリルジメチルアンモニウム）（ＰＤＤＡ）、及びポリエチレンイミン（ＰＥＩ）の少なくとも一種を使用することができる。 The cationic polyelectrolyte is not particularly limited, and for example, at least one of poly (diallyldimethylammonium chloride) (PDDA) and polyethyleneimine (PEI) can be used.
アニオン性高分子電解質は、特に限定されないが、例えば、ポリ（４−スチレンスルホン酸）ナトリウム（ＰＳＳ）、ポリアクリル酸（ＰＡＡ）、及びポリビニル硫酸（ＰＶＳ）の少なくとも一種を使用することができる。 The anionic polyelectrolyte is not particularly limited, and for example, at least one of poly (4-styrene sulfonic acid) sodium (PSS), polyacrylic acid (PAA), and polyvinyl sulfuric acid (PVS) can be used.
表面被覆ベーマイトを調製する際には、ベーマイトの表面を、まず、アニオン性高分子電解質で被覆する。次に、アニオン性高分子電荷質を、カチオン性高分子電解質で被覆する。なお、最外層がカチオン性高分子電解質となっていれば、被覆回数は、限定されない。したがって、例えば、カチオン性高分子電解質をさらにアニオン性高分子電解質で被覆した後、そのアニオン性高分子電解質をカチオン性高分子電解質でさらに被覆するようにしてもよい。また、アニオン性高分子電解質又はカチオン性高分子電解質を複数層設ける場合、それぞれ異なる種類のアニオン性高分子電解質又はカチオン性高分子電解質を使用してもよい。例えば、一層目のアニオン性高分子電解質と三層目のアニオン性高分子電解質とは、異なるアニオン性高分子電解質を使用してもよい。 When preparing the surface-coated boehmite, the surface of the boehmite is first coated with an anionic polyelectrolyte. The anionic polyelectrolyte is then coated with a cationic polyelectrolyte. As long as the outermost layer is a cationic polyelectrolyte, the number of coatings is not limited. Therefore, for example, the cationic polyelectrolyte may be further coated with the anionic polyelectrolyte, and then the anionic polyelectrolyte may be further coated with the cationic polyelectrolyte. Further, when a plurality of layers of anionic polyelectrolyte or cationic polyelectrolyte are provided, different types of anionic polyelectrolyte or cationic polyelectrolyte may be used. For example, different anionic polyelectrolytes may be used for the first-layer anionic polyelectrolyte and the third-layer anionic polyelectrolyte.
本発明は、樹脂フィルムの表面に、上記の表面被覆ベーマイトが付着した樹脂フィルム複合材料にも関する。樹脂フィルムとしては、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）製のフィルムや、ポリエチレン（ＰＥ）製のフィルムが挙げられる。本発明の表面被覆ベーマイトを付着させることにより、樹脂フィルムの寸法を安定化させることができる。本発明の樹脂フィルム複合材料は、例えば、二次電池用のセパレータとして利用できる。 The present invention also relates to a resin film composite material in which the above-mentioned surface coating boehmite is adhered to the surface of the resin film. Examples of the resin film include a film made of polyvinylidene fluoride (PVDF) and a film made of polyethylene (PE). By adhering the surface coating boehmite of the present invention, the dimensions of the resin film can be stabilized. The resin film composite material of the present invention can be used, for example, as a separator for a secondary battery.
本発明は、炭素材の表面に、上記の表面被覆ベーマイトが付着した炭素材複合材料にも関する。炭素材としては、例えば、グラファイトが挙げられる。本発明の表面被覆ベーマイトを付着させることにより、炭素材の寸法を安定化させることができる。本発明の炭素材複合材料は、例えば、二次電池用の負極材として利用できる。 The present invention also relates to a carbon material composite material in which the above-mentioned surface coating boehmite is attached to the surface of the carbon material. Examples of the carbon material include graphite. By adhering the surface-coated boehmite of the present invention, the dimensions of the carbon material can be stabilized. The carbon material composite material of the present invention can be used, for example, as a negative electrode material for a secondary battery.
以下では、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
［ベーマイト試料の調製］
原料ベーマイトの特性、及び、最外層の高分子電解質の種類を表１に示す。図１は、原料ベーマイトの長径及び短径を説明する図であり、（長径／短径）はアスペクト比と呼ばれる。
[Preparation of boehmite sample]
Table 1 shows the characteristics of the raw material boehmite and the types of the polymer electrolyte in the outermost layer. FIG. 1 is a diagram for explaining the major axis and the minor axis of the raw material boehmite, and (major axis / minor axis) is called an aspect ratio.
＜実施例１＞
（１）イオン交換水にＰＳＳ（シグマアルドリッチ製）を加え、ＰＳＳの濃度が１ｗｔ％であるＰＳＳ水溶液を調製した。同様に、イオン交換水にＰＤＤＡ（シグマアルドリッチ製）を加え、ＰＤＤＡの濃度が１ｗｔ％であるＰＤＤＡ水溶液を調製した。
（２）ＰＳＳ水溶液、及び、ＰＤＤＡ水溶液に、０．５Ｍとなるように塩化ナトリウム（ナイカイ塩業株式会社製）を加えた。
（３）５０ｍＬの遠沈管に、一次粒子の中心粒子径が２μｍの板状ベーマイト（河合石灰工業株式会社製、アスペクト比：５）を１．０ｇ入れ、その遠沈管にＰＳＳ水溶液３０ｍＬを加えて懸濁液とした。
（４）ホモジナイザー（Ｓｏｎｉｃ＆Ｍａｔｅｒｉａｌｓ ｉｎｃ．製「ＶＣＸ−４００」）を用いて、懸濁液内のベーマイト凝集物を超音波解砕した。
（５）懸濁液の入った遠沈管をチューブローテータ（ＴＡＩＴＥＣ製「ＲＴ−５０」）にセットし、３０分振とうした。
（６）遠沈管を遠心分離機（ＫＵＢＯＴＡ製、高速冷却遠心分離機「６２００」）にセットし、回転数８０００ｒｐｍで１０分間遠心分離を行い、スラリー中のベーマイトを沈降させた。
（７）遠沈管内の上澄みを捨て、新たにイオン交換水３０ｍＬを加えた。
（８）ボルテックスミキサー（ＴＡＩＴＥＣ「Ｓｅ−０８」）を用いて遠沈管内を攪拌し、沈降していたベーマイトを分散させた。
（９）上記（６）から（８）を２回繰り返し、余分なＰＳＳを洗い流した。これにより、原料ベーマイトの表面がＰＳＳで被覆されたベーマイトが得られた。
（１０）遠沈管内の上澄みを捨て、ベーマイトが残った遠沈管にＰＤＤＡ水溶液３０ｍＬを加えて再び懸濁液とした。
（１１）上記懸濁液をボルテックスミキサーで攪拌し、ベーマイトを均一分散させた。
（１２）懸濁液の入った遠沈管をチューブローテータにセットし、３０分振とうした。
（１３）遠沈管を遠心分離機にセットし、回転数８０００ｒｐｍで１０分間遠心分離を行い、スラリー中のベーマイトを沈降させた。
（１４）遠沈管内の上澄みを捨て、新たにイオン交換水３０ｍＬを加えた。
（１５）ボルテックスミキサーを用いて遠沈管内を攪拌し、沈降していたベーマイトを分散させた。
（１６）上記（１３）から（１５）を２回繰り返し、余分なＰＤＤＡを洗い流した。
（１７）洗浄工程後の沈降したベーマイトを回収し、６０℃の乾燥機で２４時間乾燥させた。このようにして、最外層がＰＤＤＡである表面被覆ベーマイトが得られた。
<Example 1>
(1) PSS (manufactured by Sigma-Aldrich) was added to ion-exchanged water to prepare a PSS aqueous solution having a PSS concentration of 1 wt%. Similarly, PDDA (manufactured by Sigma-Aldrich) was added to ion-exchanged water to prepare a PDDA aqueous solution having a PDDA concentration of 1 wt%.
(2) Sodium chloride (manufactured by Naikai Salt Industries Co., Ltd.) was added to the PSS aqueous solution and the PDDA aqueous solution so as to have a concentration of 0.5 M.
(3) Put 1.0 g of plate-shaped boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 5) having a central particle diameter of 2 μm into a 50 mL centrifuge tube, and add 30 mL of PSS aqueous solution to the centrifuge tube. It was made into a suspension.
(4) Using a homogenizer (“VCX-400” manufactured by Sonic & Materials Inc.), boehmite agglutination in the suspension was ultrasonically crushed.
(5) The centrifuge tube containing the suspension was set in a tube rotator (“RT-50” manufactured by TAITEC) and shaken for 30 minutes.
(6) The centrifuge tube was set in a centrifuge (manufactured by KUBOTA, high-speed cooling centrifuge "6200"), and centrifugation was performed at a rotation speed of 8000 rpm for 10 minutes to settle boehmite in the slurry.
(7) The supernatant in the centrifuge tube was discarded, and 30 mL of ion-exchanged water was newly added.
(8) The inside of the centrifuge tube was stirred using a vortex mixer (TAITEC "Se-08") to disperse the sedimented boehmite.
(9) The above (6) to (8) were repeated twice to wash away excess PSS. As a result, boehmite in which the surface of the raw material boehmite was coated with PSS was obtained.
(10) The supernatant in the centrifuge tube was discarded, and 30 mL of the PDDA aqueous solution was added to the centrifuge tube in which boehmite remained to make a suspension again.
(11) The suspension was stirred with a vortex mixer to uniformly disperse boehmite.
(12) The centrifuge tube containing the suspension was set in a tube rotator and shaken for 30 minutes.
(13) The centrifuge tube was set in a centrifuge, and centrifugation was performed at a rotation speed of 8000 rpm for 10 minutes to settle boehmite in the slurry.
(14) The supernatant in the centrifuge tube was discarded, and 30 mL of ion-exchanged water was newly added.
(15) The inside of the centrifuge tube was stirred using a vortex mixer to disperse the sedimented boehmite.
(16) The above (13) to (15) were repeated twice to wash away excess PDDA.
(17) The precipitated boehmite after the washing step was collected and dried in a dryer at 60 ° C. for 24 hours. In this way, a surface-coated boehmite having an outermost layer of PDDA was obtained.
＜実施例２＞
カチオン性高分子電解質をＰＤＤＡからＰＥＩに変更した以外は、実施例１と同じ方法により、表面被覆ベーマイトを調製した。
<Example 2>
Surface-coated boehmite was prepared by the same method as in Example 1 except that the cationic polyelectrolyte was changed from PDDA to PEI.
＜実施例３＞
原料ベーマイトを、一次粒子の中心粒子径が５μｍの鱗片状ベーマイト（河合石灰工業株式会社製、アスペクト比：２０）に変更した以外は、実施例１と同じ方法により、表面被覆ベーマイトを調製した。
<Example 3>
A surface-coated boehmite was prepared by the same method as in Example 1 except that the raw material boehmite was changed to scaly boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 20) having a central particle diameter of 5 μm.
＜実施例４＞
原料ベーマイトを、一次粒子の中心粒子径が２μｍの鱗片状ベーマイト（河合石灰工業株式会社製、アスペクト比：４０）に変更した以外は、実施例１と同じ方法により、表面被覆ベーマイトを調製した。
<Example 4>
A surface-coated boehmite was prepared by the same method as in Example 1 except that the raw material boehmite was changed to scaly boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 40) having a central particle diameter of 2 μm.
＜実施例５＞
原料ベーマイトを、一次粒子の中心粒子径が３．５μｍの針状ベーマイト（河合石灰工業株式会社製、アスペクト比：３０）に変更した以外は、実施例１と同じ方法により、表面被覆ベーマイトを調製した。
<Example 5>
Surface-coated boehmite was prepared by the same method as in Example 1 except that the raw material boehmite was changed to needle-shaped boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 30) having a central particle diameter of 3.5 μm. bottom.
＜比較例１＞
（１）５０ｍＬの遠沈管に、一次粒子の中心粒子径が２μｍの板状ベーマイト（河合石灰工業株式会社製、アスペクト比：５）を１．０ｇ入れ、その遠沈管にイオン交換水３０ｍＬを加えて懸濁液とした。
（２）ホモジナイザーを用いて、懸濁液内のベーマイト凝集物を超音波解砕した。
（３）遠沈管を遠心分離機にセットし、回転数８０００ｒｐｍで１０分間遠心分離を行い、スラリー中のベーマイトを沈降させた。なお、比較例１では、この遠心分離処理は１回だけしか行っていない。
（４）遠沈管内の上澄みを捨て、沈降したベーマイトを回収し、６０℃で２４時間乾燥した。
（５）上記手順により、表面が高分子電解質で被覆されていないベーマイトを得た。
<Comparative example 1>
(1) Put 1.0 g of plate-shaped boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 5) having a central particle diameter of 2 μm into a 50 mL centrifuge tube, and add 30 mL of ion-exchanged water to the centrifuge tube. To make a suspension.
(2) Using a homogenizer, the boehmite agglutination in the suspension was ultrasonically crushed.
(3) The centrifuge tube was set in a centrifuge and centrifuged at a rotation speed of 8000 rpm for 10 minutes to settle boehmite in the slurry. In Comparative Example 1, this centrifugation treatment was performed only once.
(4) The supernatant in the centrifuge tube was discarded, and the settled boehmite was collected and dried at 60 ° C. for 24 hours.
(5) By the above procedure, boehmite whose surface was not coated with a polymer electrolyte was obtained.
＜比較例２＞
（１）５０ｍＬの遠沈管に、一次粒子の中心粒子径が２μｍの板状ベーマイト（河合石灰工業株式会社製、アスペクト比：５）を１．０ｇ入れ、その遠沈管に、実施例１と同じ方法で調製したＰＤＤＡ溶液３０ｍＬを加えて懸濁液とした。
（２）ホモジナイザーを用いて、懸濁液内のベーマイト凝集物を超音波解砕した。
（３）懸濁液の入った遠沈管をチューブローテータにセットし、３０分振とうした。
（４）遠沈管を遠心分離機にセットし、回転数８０００ｒｐｍで１０分間遠心分離を行い、スラリー中のベーマイトを沈降させた。
（５）遠沈管内の上澄みを捨て、新たにイオン交換水３０ｍＬを加えた。
（６）ボルテックスミキサーを用いて遠沈管内を攪拌し、沈降していたベーマイトを分散させた。
（７）上記（４）から（６）を２回繰り返し、余分なＰＤＤＡを洗い流した。洗浄工程後の沈降したベーマイトを回収し、６０℃で２４時間乾燥した。
（８）上記手順により、原料ベーマイトの表面がＰＤＤＡで被覆されたベーマイト試料が得られた。
<Comparative example 2>
(1) 1.0 g of plate-shaped boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 5) having a central particle diameter of 2 μm of primary particles is placed in a 50 mL centrifuge tube, and the same as in Example 1 is placed in the centrifuge tube. 30 mL of the PDDA solution prepared by the method was added to prepare a suspension.
(2) Using a homogenizer, the boehmite agglutination in the suspension was ultrasonically crushed.
(3) The centrifuge tube containing the suspension was set in a tube rotator and shaken for 30 minutes.
(4) The centrifuge tube was set in a centrifuge, and centrifugation was performed at a rotation speed of 8000 rpm for 10 minutes to settle boehmite in the slurry.
(5) The supernatant in the centrifuge tube was discarded, and 30 mL of ion-exchanged water was newly added.
(6) The inside of the centrifuge tube was stirred using a vortex mixer to disperse the sedimented boehmite.
(7) The above (4) to (6) were repeated twice to wash away excess PDDA. The precipitated boehmite after the washing step was recovered and dried at 60 ° C. for 24 hours.
(8) By the above procedure, a boehmite sample in which the surface of the raw material boehmite was coated with PDDA was obtained.
＜比較例３＞
原料ベーマイトを、一次粒子の中心粒子径が５μｍの鱗片状ベーマイト（河合石灰工業株式会社製、アスペクト比：２０）に変更した以外は、比較例１と同じ方法により、ベーマイト試料を調製した。
<Comparative example 3>
A boehmite sample was prepared by the same method as in Comparative Example 1 except that the raw material boehmite was changed to scaly boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 20) having a central particle size of 5 μm.
＜比較例４＞
原料ベーマイトを、一次粒子の中心粒子径が２μｍの鱗片状ベーマイト（河合石灰工業株式会社製、アスペクト比：４０）に変更した以外は、比較例１と同じ方法により、ベーマイト試料を調製した。
<Comparative example 4>
A boehmite sample was prepared by the same method as in Comparative Example 1 except that the raw material boehmite was changed to scaly boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 40) having a central particle size of 2 μm.
＜比較例５＞
原料ベーマイトを、一次粒子の中心粒子径が３．５μｍの針状ベーマイト（河合石灰工業株式会社製、アスペクト比：３０）に変更した以外は、比較例１と同じ方法により、ベーマイト試料を調製した。
<Comparative example 5>
A boehmite sample was prepared by the same method as in Comparative Example 1 except that the raw material boehmite was changed to needle-shaped boehmite (manufactured by Kawai Lime Industry Co., Ltd., aspect ratio: 30) having a central particle diameter of 3.5 μm. ..
［樹脂に対する付着性の評価］
以下の手順により、実施例１から５及び比較例１から５のベーマイト試料の、樹脂サンプル片に対する付着性を評価した。付着性の結果を、表１に示す。表１において、「○」は、樹脂サンプル片に、ベーマイト試料が十分に付着していることを意味し、「×」は、樹脂サンプル片に、ベーマイト試料がほとんど付着していないことを意味する。付着状態を示す一例として、図２に、実施例１及び比較例１のベーマイト試料を使用した付着試験後の樹脂サンプル片のＳＥＭ（走査型電子顕微鏡）画像を示す。
（１）容器にイオン交換水９．０ｇ、工業用アルコール１．０ｇ（今津薬品工業製「クリンエースハイ」）、及びベーマイト試料０．１ｇを加え、懸濁液を調製した。
（２）ホモジナイザーを用いて、懸濁液内のベーマイト試料の凝集物を超音波解砕した。
（３）篩を用意し、その上に樹脂サンプル片を置き、樹脂サンプル片に上記の懸濁液をまんべんなく垂らした。樹脂サンプル片としては、ポリフッ化ビニリデン（ＰＶＤＦ）のフィルム（近江オドエアーサービス株式会社製、ＰＶＤＦバッグ）、及びポリエチレン（ＰＥ）のフィルム（生産日本社製、ユニパック（登録商標）Ｄ−４）を使用した。なお、樹脂サンプル片の表面電荷は負である。
（４）イオン交換水を用いて、篩上の樹脂サンプル片を念入りに洗浄した。
（５）樹脂サンプル片を６０℃の乾燥機内で２４時間乾燥させた。
（６）乾燥後の樹脂サンプル片の表面を走査型電子顕微鏡（ＪＥＯＬ製「ＪＳＭ−７５００ＦＡ」）で観察した。
[Evaluation of adhesiveness to resin]
The adhesiveness of the boehmite samples of Examples 1 to 5 and Comparative Examples 1 to 5 to the resin sample pieces was evaluated by the following procedure. The adhesiveness results are shown in Table 1. In Table 1, "○" means that the boehmite sample is sufficiently adhered to the resin sample piece, and "x" means that the boehmite sample is hardly adhered to the resin sample piece. .. As an example showing the adhesion state, FIG. 2 shows SEM (scanning electron microscope) images of the resin sample pieces after the adhesion test using the boehmite samples of Example 1 and Comparative Example 1.
(1) 9.0 g of ion-exchanged water, 1.0 g of industrial alcohol (“Clean Ace High” manufactured by Imazu Pharmaceutical Co., Ltd.), and 0.1 g of boehmite sample were added to a container to prepare a suspension.
(2) Using a homogenizer, agglomerates of boehmite samples in the suspension were ultrasonically crushed.
(3) A sieve was prepared, a resin sample piece was placed on the sieve, and the above suspension was evenly dropped on the resin sample piece. As resin sample pieces, polyvinylidene fluoride (PVDF) film (PVDF bag manufactured by Omi Odo Air Service Co., Ltd.) and polyethylene (PE) film (manufactured by Japan, Unipack (registered trademark) D-4) are used. used. The surface charge of the resin sample piece is negative.
(4) The resin sample piece on the sieve was thoroughly washed with ion-exchanged water.
(5) The resin sample piece was dried in a dryer at 60 ° C. for 24 hours.
(6) The surface of the dried resin sample piece was observed with a scanning electron microscope (“JSM-7500FA” manufactured by JEOL).
［分散安定性の評価］
以下の手順により、実施例１から５及び比較例１から５のベーマイト試料の、イオン交換水中における分散安定性について評価した。分散安定性の結果を表１に示す。表１において、「○」は、ベーマイト試料の分散状態が維持されていることを意味し、「△」は、ベーマイト試料の一部が沈降していることを意味し、「×」は、ベーマイト試料が完全に沈降していることを意味する。実施例１〜３及び比較例１〜３の結果は、測定開始から１０分後の結果であり、実施例４及び比較例４の結果は、測定開始から１８０分後の結果であり、実施例５及び比較例５の結果は、測定開始から９０分後の結果である。分散状態を示す一例として、図３に、ｐＨ６〜８における、実施例１、比較例１及び比較例２の分散安定性試験の写真を示す。
（１）容器にイオン交換水１０．０ｇとベーマイト試料０．１ｇを加え、懸濁液を調製した。
（２）ホモジナイザーを用いて、懸濁液内におけるベーマイト試料の凝集物を超音波解砕した。
（３）懸濁液を所定のｐＨに調整した。ｐＨを低下させる場合には、硝酸の希釈溶液を懸濁液に加え、ｐＨを上昇させる場合には、水酸化ナトリウムの希釈溶液を懸濁液に加えた。
（４）ｐＨを調整した懸濁液を１０ｍＬメスシリンダーに移し、ベーマイト試料の沈降具合を目視により確認した。
[Evaluation of dispersion stability]
The dispersion stability of the boehmite samples of Examples 1 to 5 and Comparative Examples 1 to 5 in ion-exchanged water was evaluated by the following procedure. The results of dispersion stability are shown in Table 1. In Table 1, "○" means that the dispersed state of the boehmite sample is maintained, "△" means that a part of the boehmite sample is settled, and "x" means boehmite. It means that the sample is completely settled. The results of Examples 1 to 3 and Comparative Examples 1 to 3 are the results 10 minutes after the start of measurement, and the results of Examples 4 and 4 are the results 180 minutes after the start of measurement. The results of 5 and Comparative Example 5 are the results 90 minutes after the start of measurement. As an example showing the dispersed state, FIG. 3 shows photographs of dispersion stability tests of Example 1, Comparative Example 1 and Comparative Example 2 at pH 6 to 8.
(1) 10.0 g of ion-exchanged water and 0.1 g of boehmite sample were added to the container to prepare a suspension.
(2) Using a homogenizer, agglomerates of boehmite samples in the suspension were ultrasonically crushed.
(3) The suspension was adjusted to a predetermined pH. A diluted solution of nitric acid was added to the suspension to lower the pH, and a diluted solution of sodium hydroxide was added to the suspension to raise the pH.
(4) The pH-adjusted suspension was transferred to a 10 mL measuring cylinder, and the sedimentation condition of the boehmite sample was visually confirmed.
表１及び図２に示すように、実施例１〜５の表面被覆ベーマイトは、ＰＶＤＦフィルム及びＰＥフィルムに対する付着性が高かった。これに対し、比較例１〜５のベーマイト試料は、ＰＶＤＦフィルム及びＰＥフィルムにほとんど付着しなかった。したがって、本発明の表面被覆ベーマイトが付着した樹脂フィルム複合材料は、高い寸法安定性を有し、例えば、二次電池用のセパレータとして有用である。 As shown in Table 1 and FIG. 2, the surface-coated boehmite of Examples 1 to 5 had high adhesion to the PVDF film and the PE film. On the other hand, the boehmite samples of Comparative Examples 1 to 5 hardly adhered to the PVDF film and the PE film. Therefore, the resin film composite material to which the surface-coated boehmite of the present invention is attached has high dimensional stability and is useful as a separator for, for example, a secondary battery.
表１及び図３に示すように、実施例１〜５の表面被覆ベーマイトは、ｐＨ６〜８であっても、分散性が高かった。これに対し、比較例１〜５のベーマイト試料は、ｐＨ６〜８において、その一部又は全部が沈降していた。 As shown in Table 1 and FIG. 3, the surface-coated boehmite of Examples 1 to 5 had high dispersibility even at pH 6 to 8. On the other hand, the boehmite samples of Comparative Examples 1 to 5 had some or all of them precipitated at pH 6 to 8.
比較例２のベーマイト試料は、ＰＤＤＡで被覆されているものの、ｐＨ６〜８における分散性は良好ではなかった。このことから、本発明のように、ベーマイトを、アニオン性高分子電解質とカチオン性高分子電解質とによって交互に被覆することが、分散性を向上させる上で有効であることが分かる。 Although the boehmite sample of Comparative Example 2 was coated with PDDA, the dispersibility at pH 6 to 8 was not good. From this, it can be seen that it is effective to alternately coat the boehmite with the anionic polyelectrolyte and the cationic polyelectrolyte as in the present invention in order to improve the dispersibility.
一般に、ベーマイトを、液体と混合して使用する場合（例えば、スラリー）、廃液処理など様々な観点から、液体は中性に調製されることが好ましい。本発明の表面被覆ベーマイトは、中性付近（ｐＨ６〜８）でも高い分散性を有しているため、幅広い用途で利用可能である。 In general, when boehmite is mixed with a liquid and used (for example, a slurry), the liquid is preferably prepared to be neutral from various viewpoints such as waste liquid treatment. Since the surface-coated boehmite of the present invention has high dispersibility even near neutrality (pH 6 to 8), it can be used in a wide range of applications.
Claims (6)
請求項１に記載の表面被覆ベーマイト。 The cationic polyelectrolyte is at least one of poly (diallyldimethylammonium chloride) and polyethyleneimine.
The surface-coated boehmite according to claim 1.
請求項１又は２に記載の表面被覆ベーマイト。 The anionic polyelectrolyte is at least one of poly (4-styrene sulfonic acid) sodium, polyacrylic acid, and polyvinyl sulfuric acid.
The surface-coated boehmite according to claim 1 or 2.
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