JP2010115919A - Composite structure and separator for electronic component including the same - Google Patents
Composite structure and separator for electronic component including the same Download PDFInfo
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- JP2010115919A JP2010115919A JP2009237294A JP2009237294A JP2010115919A JP 2010115919 A JP2010115919 A JP 2010115919A JP 2009237294 A JP2009237294 A JP 2009237294A JP 2009237294 A JP2009237294 A JP 2009237294A JP 2010115919 A JP2010115919 A JP 2010115919A
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000004760 aramid Substances 0.000 claims abstract description 61
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 61
- 239000000835 fiber Substances 0.000 claims abstract description 53
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 36
- 229920001410 Microfiber Polymers 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims description 24
- 230000008859 change Effects 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001523 electrospinning Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000003658 microfiber Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- -1 polyethylene Polymers 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000009987 spinning Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000003490 calendering Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
- Laminated Bodies (AREA)
- Nonwoven Fabrics (AREA)
- Paper (AREA)
Abstract
Description
本発明は、電気・電子部品内において導電部材間を隔離するのに有用であり、電解質もしくはイオンなどのイオン種が通過しうるセパレータに関する。さらに詳しくは、ナノオーダーの繊維径を有する芳香族ポリアミド極細繊維を含む複合構造体、および電子部品用セパレータに関する。 The present invention relates to a separator that is useful for isolating conductive members in an electric / electronic component and through which an ionic species such as an electrolyte or ions can pass. More specifically, the present invention relates to a composite structure including an aromatic polyamide ultrafine fiber having a nano-order fiber diameter, and a separator for electronic parts.
携帯通信機器や高速情報処理機器などの最近の進歩に象徴される、エレクトロニクス機器の小型軽量化、高性能化には目覚しいものがある。なかでも、小型、軽量、高容量で長期保存にも耐える高性能な電池、コンデンサー、電気二重層キャパシタへの期待は大きく、幅広く応用が図られ、部品開発が急速に進展している。これにこたえる為、部材、例えば電極間の隔壁材料であるセパレータに関しても、技術・品質開発の必要性が高まっている。セパレータに対する要求特性は、電解質を保持した状態での導電性、高い電極間遮蔽性、低内部抵抗などが挙げられる。 Remarkable progress has been made in reducing the size, weight, and performance of electronic devices as symbolized by recent advances in mobile communication devices and high-speed information processing devices. In particular, expectations are high for high-performance batteries, capacitors, and electric double layer capacitors that are compact, lightweight, have a high capacity and can withstand long-term storage, and are widely applied, and parts development is progressing rapidly. In order to respond to this, there is an increasing need for technical and quality development of members, for example, separators which are partition materials between electrodes. The required characteristics for the separator include conductivity in a state where an electrolyte is held, high inter-electrode shielding, low internal resistance, and the like.
従来、ポリエチレンやポリプロピレンなどのポリオレフィンを主成分とする多孔質膜（特許文献１）、同ポリマーを用いてシート化した不織布（特許文献２）溶融紡糸セルロースを主成分とする紙（特許文献３）などが用いられている。 Conventionally, a porous film mainly composed of a polyolefin such as polyethylene or polypropylene (Patent Document 1), a nonwoven fabric sheeted using the polymer (Patent Document 2), and a paper mainly composed of melt-spun cellulose (Patent Document 3) Etc. are used.
しかしながら、特許文献１に記載されたポリオレフィンを主成分とする多孔質膜は、密度が高いために保液性が悪く、内部抵抗が高くなる傾向にあり、その結果、容量不足、電圧低下などの問題を生じさせる。特許文献１、２ではポリオレフィンを主成分としているが、融点が１３０〜１６５℃程度と低く、耐熱性に問題がある。一方、特許文献３に記載された、溶融紡糸セルロースからなるセパレータでは、１５０℃以上の高温で長時間処理すると、セルロースが炭化することが知られており、１５０℃以下で長時間の乾燥処理が必要という問題点がある。 However, the porous film mainly composed of polyolefin described in Patent Document 1 has a high density and tends to have poor liquid retention and high internal resistance. Cause problems. In Patent Documents 1 and 2, polyolefin is the main component, but the melting point is as low as about 130 to 165 ° C., and there is a problem in heat resistance. On the other hand, in the separator made of melt-spun cellulose described in Patent Document 3, it is known that cellulose is carbonized when treated at a high temperature of 150 ° C. or higher for a long time, and a long drying treatment is performed at 150 ° C. or lower. There is a problem of necessity.
また、これらのセパレータは、電気・電子部品中の内部抵抗を低下させ、効率的に高いエネルギー密度を得るために、さらなる薄葉化が望まれている。しかしながら、薄葉化に伴う目付けの低下は、内部短絡の発生確率の上昇、電解液保液性の低下などの問題がある。 Further, these separators are desired to be further thinned in order to reduce internal resistance in electric / electronic parts and to obtain a high energy density efficiently. However, the decrease in the fabric weight associated with the thinning has problems such as an increase in the probability of occurrence of an internal short circuit and a decrease in electrolyte solution retention.
また、現在のセパレータに使用される素材や形態としては、ポリエチレンやポリプロピレンなどのポリオレフィンを主成分とする多孔質膜（特許文献４）が多く用いられ、かかる多孔質膜は、異常発生時に電池内部温度上昇が孔を閉塞させ、イオンの透過性を妨げることから（シャットダウン性能）、広く安全性が高いとの認識がある。しかしながら、１８０℃以上に電池内部温度が上昇した場合、セパレータが平面形態を保持することができずに電極が接触してしまうため、十分な短絡防止作用があるとは言えないものであった。また、ポリオレフィンは１００℃からでも収縮を開始するため、端部における電極接触の機会が増える恐れがある。 In addition, as a material and form used for the current separator, a porous film (Patent Document 4) mainly composed of polyolefin such as polyethylene or polypropylene is often used. It is widely recognized that safety is wide because the increase in temperature blocks the pores and impedes ion permeability (shutdown performance). However, when the internal temperature of the battery rises to 180 ° C. or higher, the separator cannot maintain a flat shape, and the electrodes come into contact with each other. In addition, since polyolefin starts to shrink even at 100 ° C., there is a possibility that the chance of electrode contact at the end increases.
本発明の目的は、内部短絡を防止するために緻密な構造を有し、かつ薄葉であっても十分な内部抵抗値を備え、優れた耐熱性を有する電子部品用セパレータに適した複合構造体及びそれからなる電子部品用セパレータを提供することである。 An object of the present invention is to provide a composite structure suitable for a separator for electronic parts having a dense structure to prevent an internal short circuit and having a sufficient internal resistance value even in a thin leaf and having excellent heat resistance. And an electronic component separator comprising the same.
本発明者が鋭意検討したところ、上記課題は、以下に記載する複合構造体及び電子部品用セパレータにより、解決することができることを見出した。
すなわち、本発明は、２層以上からなる複合構造体であって、一方の層が、繊維径が１〜１０００ｎｍの芳香族ポリアミド極細繊維を含む繊維構造体からなり、他方の層が、芳香族ポリアミドフィブリッドまたは芳香族ポリアミドパルプを含む不織布からなることを特徴とする複合構造体である。また、他の本発明は、上記複合構造体からなることを特徴とする電子部品用セパレータである。
As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by the composite structure and the electronic component separator described below.
That is, the present invention is a composite structure composed of two or more layers, wherein one layer is composed of a fiber structure including an aromatic polyamide ultrafine fiber having a fiber diameter of 1-1000 nm, and the other layer is aromatic. A composite structure comprising a nonwoven fabric containing polyamide fibrid or aromatic polyamide pulp. Another aspect of the present invention is a separator for an electronic component comprising the composite structure.
本発明によれば、芳香族ポリアミド極細繊維と、芳香族ポリアミドフィブリッドまたは芳香族ポリアミドパルプが巧みに組み合わされた、電気・電子部品中の導電部材間の隔壁として好適に利用することができる複合構造体を提供することもできる。 ADVANTAGE OF THE INVENTION According to this invention, the composite which can be utilized suitably as a partition between the electrically-conductive members in an electric / electronic component which combined the aromatic polyamide extra fine fiber, the aromatic polyamide fibrid, or the aromatic polyamide pulp skillfully. A structure can also be provided.
また、芳香族ポリアミド極細繊維からなる繊維構造体に、カレンダー加工などによって、フィルム状部分を形成した複合構造体とすることにより、該繊維構造体の密度が向上して電極間の遮蔽性も高くなり、同時に芳香族ポリアミドフィブリッド等からなる不織布への該繊維構造体の密着性が向上するため、良好な取り扱い性をも達成することができる。 Further, by forming a composite structure in which a film-like portion is formed by calendering or the like on a fiber structure composed of aromatic polyamide ultrafine fibers, the density of the fiber structure is improved and the shielding property between the electrodes is high. At the same time, since the adhesion of the fiber structure to a nonwoven fabric made of aromatic polyamide fibrid or the like is improved, good handleability can also be achieved.
さらに、本発明の電子部品用セパレータを使用した電池、コンデンサーなどの電気・電子部品では、耐熱性を有することから高い安全性が期待でき、かつ薄葉であるため、電気自動車などの大電流環境下で有利に使用することができる。 Furthermore, since electric and electronic parts such as batteries and capacitors using the separator for electronic parts according to the present invention have heat resistance, high safety can be expected, and since it is thin, it can be used in a large current environment such as an electric vehicle. Can be advantageously used.
本発明における複合構造体は、２層以上からなる複合構造体であって、一方の層が、繊維径が１〜１０００ｎｍの芳香族ポリアミド極細繊維を含む繊維構造体からなり、他方の層が、芳香族ポリアミドフィブリッドまたは芳香族ポリアミドパルプを含む不織布からなることを特徴とする。 The composite structure in the present invention is a composite structure composed of two or more layers, wherein one layer is composed of a fiber structure containing an aromatic polyamide ultrafine fiber having a fiber diameter of 1-1000 nm, and the other layer is It consists of a nonwoven fabric containing an aromatic polyamide fibrid or an aromatic polyamide pulp.
本発明においては、上記構成の複合構造体であることにより、電気・電子部品中の内部抵抗を低下させ、効率的に高いエネルギー密度を得ることができ、極細繊維が構成成分として含まれていることから、薄葉であっても高い空隙率を有するため、電解液保液性を確保することができ、特に電子部品用セパレータに適した複合構造体となる。 In the present invention, the composite structure having the above-described configuration reduces internal resistance in the electric / electronic component, can efficiently obtain a high energy density, and contains ultrafine fibers as a constituent component. Therefore, even a thin leaf has a high porosity, so that the electrolyte solution retention can be secured, and a composite structure particularly suitable for a separator for electronic parts is obtained.
繊維構造体を構成する芳香族ポリアミド極細繊維の繊維径は、１〜１０００ｎｍである必要があるが、好ましくは１０〜６００ｎｍ、より好ましくは３０〜３００ｎｍである。繊維径が１ｎｍ未満であると得られる強力が著しく低下し、電子部材加工時に破損しやすくなり、一方、極細繊維の繊維径が１０００ｎｍを越えると、空隙のサイズが大きくなり内部短絡が発生する。 Although the fiber diameter of the aromatic polyamide ultrafine fiber which comprises a fiber structure needs to be 1-1000 nm, Preferably it is 10-600 nm, More preferably, it is 30-300 nm. When the fiber diameter is less than 1 nm, the obtained strength is remarkably reduced, and it is easy to break during processing of the electronic member. On the other hand, when the fiber diameter of the ultrafine fiber exceeds 1000 nm, the void size increases and an internal short circuit occurs.
繊維構造体は、極細繊維の繊維径として１〜１０００ｎｍを達成することが可能な、乾式不織布製造法により成形され、例えば、特開２００６−０３７２７６号公報の電界紡糸法などを好ましく挙げることができる。特に上記方法により成形された乾式不織布、中でも電界紡糸法により成形された不織布は、驚くべきことに、後述する低温加圧でも芳香族ポリアミド極細繊維が軟化し部分的なフィルム形状が形成され、不織布とより強固に接合することがわかった。 The fiber structure is formed by a dry nonwoven fabric manufacturing method capable of achieving a fiber diameter of ultrafine fibers of 1 to 1000 nm. For example, the electrospinning method of JP-A-2006-037276 can be preferably mentioned. . In particular, dry nonwoven fabrics formed by the above method, especially nonwoven fabrics formed by the electrospinning method, surprisingly, the aromatic polyamide ultrafine fibers soften and form a partial film shape even at a low-temperature pressurization described later. It was found that they were joined more firmly.
一方、不織布は、芳香族ポリアミドフィブリッド、もしくは芳香族ポリアミドパルプを含む必要がある。ここでいうフィブリッドとは、特公昭３７−５７３２公報で開示されているようなフィルム状の粒子を指し、パルプとは、特許第３２０２５９７号公報で開示されているような幅広い繊維径と繊維直径を有するパルプ状短繊維である。いずれも不織布成形の際に、フロック（塊状になっている繊維）と組み合わせて使用され、フィブリッド、パルプはバインダーとして優れた機能を有し、セパレータに必要な電気特性も発現することが可能である。 On the other hand, the nonwoven fabric needs to contain aromatic polyamide fibrids or aromatic polyamide pulp. Fibrid here refers to film-like particles as disclosed in JP-B-37-5732, and pulp refers to a wide range of fiber diameters and fiber diameters as disclosed in Japanese Patent No. 3202597. It is a pulp-like short fiber. Both are used in combination with flocks (fibers in the form of lumps) when forming nonwoven fabrics, and fibrids and pulps have an excellent function as a binder and can also exhibit the electrical properties necessary for separators. .
不織布の製造方法としては、それ自体既知の方法、例えば、芳香族ポリアミドフィブリッドおよび芳香族ポリアミドフロックを乾式ブレンドした後、気流を利用してシートを形成する乾式抄造法、熱可塑性ポリマーパルプと芳香族ポリアミドフロックおよび芳香族ポリアミドフロックを液体媒体中で分散混合した後、網またはベルト上に吐出していシート化し、液体を除いて乾燥する湿式抄造法などを適用することができるが、これらのなかでも水を媒体として使用する、いわゆる湿式抄造法が好適である。 Nonwoven fabrics can be produced by methods known per se, for example, dry blending of aromatic polyamide fibrids and aromatic polyamide flocs after dry blending to form a sheet using an air stream, thermoplastic polymer pulp and aroma. A wet papermaking method can be applied, in which an aromatic polyamide floc and an aromatic polyamide floc are dispersed and mixed in a liquid medium and then discharged onto a net or a belt to form a sheet and dried by removing the liquid. However, a so-called wet papermaking method using water as a medium is suitable.
さらに、不織布の構成材料が芳香族ポリアミドであることは、本質的に耐熱性、難燃性などの優れた特性を備えていることや、比重が１．４程度と小さく軽量であるため電気・電子部品の導電部材間の隔離壁として好ましく用いることができる、等、種々の優れた特性を有している。 Furthermore, the constituent material of the non-woven fabric is aromatic polyamide because it has inherently excellent characteristics such as heat resistance and flame retardancy, and its specific gravity is as small as about 1.4. It has various excellent properties, such as being able to be preferably used as a separating wall between conductive members of electronic components.
繊維構造体の目付けは、好ましくは０．１〜５．０ｇ／ｍ２、より好ましくは０．４〜３．０ｇ／ｍ２である。目付けが０．１ｇ／ｍ２未満であると、内部短絡が頻発し、不織布との接触面積が激減することから好ましくない。一方、上記目付けが、５．０ｇ／ｍ２を超えると、内部抵抗値が上がりやすくなるため、好ましくない。特に、加熱加圧処理等により繊維構造体の一部にフィルム状を形成した場合、密度が飛躍的に上昇し、内部抵抗値が著しく高くなりやすい。 The basis weight of the fiber structure is preferably 0.1 to 5.0 g / m 2 , more preferably 0.4 to 3.0 g / m 2 . If the basis weight is less than 0.1 g / m 2 , an internal short circuit occurs frequently and the contact area with the nonwoven fabric is drastically reduced, which is not preferable. On the other hand, if the basis weight exceeds 5.0 g / m 2 , the internal resistance value tends to increase, such being undesirable. In particular, when a film is formed on a part of the fiber structure by heat and pressure treatment or the like, the density dramatically increases and the internal resistance value tends to be extremely high.
不織布の目付けは、好ましくは５〜２５ｇ／ｍ２、より好ましくは８〜１５ｇ／ｍ２である。目付けが５ｇ／ｍ２未満であると、内部抵抗が頻発するため好ましくなく、２５ｇ／ｍ２を超えると、電解液保持性が低くなり、内部抵抗値が上昇するため、好ましくない。 The basis weight of the nonwoven fabric is preferably 5 to 25 g / m 2 , more preferably 8 to 15 g / m 2 . If the basis weight is less than 5 g / m 2 , the internal resistance frequently occurs, which is not preferable. If the basis weight exceeds 25 g / m 2 , the electrolytic solution retention becomes low and the internal resistance value increases, which is not preferable.
複合構造体の目付けは、好ましくは５．１〜３０ｇ／ｍ２、より好ましくは８〜２０ｇ／ｍ２である。また、複合構造体の平均厚さは、好ましくは５〜３０μｍ、より好ましくは１０〜２０μｍである。複合構造体の、目付けが５．1ｇ／ｍ２未満、平均厚さが５μｍ未満では、電子部材加工に必要な強度が不十分であったり、内部短絡を頻発したりして、セパレータとして好ましくない。また、目付けが３０ｇ／ｍ２より大きく、平均厚さが３０μｍより大きいと、後述する電池用セパレータのイオン導電度を示す指標であるマクミラン数１５以下でかつマクミラン数×複合構造体の平均厚さが２５０μｍ以下である複合構造体を得ることが困難となる。 The basis weight of the composite structure is preferably 5.1 to 30 g / m 2 , more preferably 8 to 20 g / m 2 . The average thickness of the composite structure is preferably 5 to 30 μm, more preferably 10 to 20 μm. When the weight per unit area of the composite structure is less than 5.1 g / m 2 and the average thickness is less than 5 μm, the strength necessary for processing the electronic member is insufficient or internal short-circuits occur frequently, which is not preferable as a separator. . Further, if the basis weight is larger than 30 g / m 2 and the average thickness is larger than 30 μm, the Macmillan number is 15 or less, which is an index indicating the ionic conductivity of the battery separator described later, and the Macmillan number × the average thickness of the composite structure. It is difficult to obtain a composite structure having a thickness of 250 μm or less.
本発明においては、繊維構造体には、芳香族ポリアミド極細繊維が繊維形状を有している部分と、複数の芳香族ポリアミド極細繊維が軟化して一体化しフィルム形状を有している部分とが存在し、該フィルム形状を有している部分と、他方の層を構成する不織布とが少なくとも一部において接合一体化していることが好ましい。これにより、繊維構造体と不織布との密着性が向上し、層間の剥離が起こりにくい。また、繊維構造体の密度が向上して電極間の遮蔽性も高くなる。 In the present invention, the fiber structure includes a portion in which the aromatic polyamide ultrafine fibers have a fiber shape and a portion in which a plurality of aromatic polyamide ultrafine fibers are softened and integrated to have a film shape. It is preferable that the part which exists and has this film shape and the nonwoven fabric which comprises the other layer are joined and integrated at least partially. Thereby, the adhesiveness of a fiber structure and a nonwoven fabric improves, and peeling between layers does not occur easily. In addition, the density of the fiber structure is improved and the shielding property between the electrodes is increased.
なおここで、フィルム形状とは、複数の極細繊維が軟化して一体化し、繊維形状を留めず、表面がフィルムのように平滑となっている状態をいい、該フィルム形状は厚み斑があっても空隙を有していてもよい。 Here, the film shape means a state in which a plurality of ultrafine fibers are softened and integrated, the fiber shape is not fixed, and the surface is smooth like a film. May have voids.
以上に説明した本発明の複合構造体は、例えば以下の方法により製造することができる。一つの方法としては、全芳香族ポリアミド溶液を、高電圧を印加して不織布上にスプレーして極細繊維を形成する方法を好ましく例示することができる。また、得られる極細繊維の繊維径は印加電圧、溶液濃度、スプレーの飛散距離等に依存し、これらの条件を調整することで任意の繊維径とすることができる。溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシドなどを用いることができる。 The composite structure of the present invention described above can be produced, for example, by the following method. As one method, a method of forming an ultrafine fiber by spraying a wholly aromatic polyamide solution on a nonwoven fabric while applying a high voltage can be preferably exemplified. The fiber diameter of the obtained ultrafine fiber depends on the applied voltage, the solution concentration, the spray scattering distance, and the like, and can be set to an arbitrary fiber diameter by adjusting these conditions. As the solvent, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like can be used.
具体的には、全芳香族ポリアミドポリマーと溶媒とを１：９９〜１６：８４の重量比で溶解させたポリマー溶液を調製し、５〜７０ｋＶの電圧下で、紡糸距離を５．０〜５０ｃｍとし、単位距離あたりの電圧に換算すると０．５〜７．０ｋｖ／ｃｍとして電界紡糸を行うことにより前述した繊維径を有する芳香族ポリアミド極細繊維を作製することができる。 Specifically, a polymer solution in which a wholly aromatic polyamide polymer and a solvent are dissolved at a weight ratio of 1:99 to 16:84 is prepared, and the spinning distance is 5.0 to 50 cm under a voltage of 5 to 70 kV. Then, when converted into a voltage per unit distance, an aromatic polyamide ultrafine fiber having the above-described fiber diameter can be produced by performing electrospinning at 0.5 to 7.0 kv / cm.
また、紡糸溶液の安定性付与など、必要に応じ、アルカリ金属塩及び／又はアルカリ土類金属塩を、全芳香族ポリアミドポリマーを含む紡糸溶液に対し、０．０５〜５重量％含んでいても良い。 Moreover, even if it contains 0.05 to 5 weight% of alkali metal salt and / or alkaline-earth metal salt with respect to the spinning solution containing a wholly aromatic polyamide polymer as needed, such as providing stability of the spinning solution. good.
紡糸溶液の供給は、ノズルや口金から押し出す方法や、紡糸溶液中に浸した円盤やドラムに、必要量となるように紡糸溶液を付着させ、連続回転させることにより供給する方法が挙げられる。 Examples of the spinning solution supply include a method of extruding from a nozzle and a base, and a method of supplying the spinning solution by attaching it to a disk or drum immersed in the spinning solution so that it becomes a required amount and continuously rotating it.
また、繊維構造体を構成する極細繊維は、メタ型芳香族ポリアミドであることが好ましい。メタ型芳香族ポリアミドは耐熱性、耐薬品性などに優れており、産業資材用途に広く使用されているものである。極細繊維を成形しやすい高分子には、ポリビニルアルコールやナイロンなどがあるが、これらは後述する加熱加圧処理や高温雰囲気下にて溶融、劣化するため、内部抵抗が上昇したり、内部短絡が発生したり、といった欠点が生じる。 Moreover, it is preferable that the ultrafine fiber which comprises a fiber structure is meta type | mold aromatic polyamide. Meta-type aromatic polyamides are excellent in heat resistance and chemical resistance, and are widely used for industrial materials. Polymers that are easy to mold ultrafine fibers include polyvinyl alcohol and nylon, but these melt and deteriorate in the heat and pressure treatment described below and in a high temperature atmosphere, increasing internal resistance and causing internal short circuits. The fault that occurs occurs.
さらに、繊維構造体に、芳香族ポリアミド極細繊維が繊維形状を有している部分と、フィルム形状を有している部分とが存在する前記複合構造体を製造するには、以下の方法を採用することができる。 Furthermore, the following method is adopted to manufacture the composite structure in which the aromatic polyamide ultrafine fiber has a fiber shape portion and a film shape portion in the fiber structure. can do.
すなわち、上記方法で得られた、繊維径が１〜１０００ｎｍの芳香族ポリアミド極細繊維を含む繊維構造体と、芳香族ポリアミドフィブリッドまたは芳香族ポリアミドパルプを含む不織布とからなる複合構造体を、温度が３０〜３５０℃、線圧が５０〜３００ｋｇｆ／ｃｍの加熱加圧処理を施すことにより製造することができる。上記加熱加圧処理の条件において、温度は１００〜３５０℃、線圧は１５０〜３００ｋｇｆ／ｃｍであることがより好ましい。ここで、加熱温度および加圧力が低すぎると、極細繊維間の接着力が弱くなり、一方、加熱温度および加圧力が高すぎると繊維構造体を構成する繊維同士または不織布を構成する繊維同士が融着などを起こして目が潰れるなどし、電解液保持性が悪くなったり、内部抵抗値があがり易くなったりするため、好ましくない。 That is, a composite structure comprising a fiber structure containing an aromatic polyamide ultrafine fiber having a fiber diameter of 1 to 1000 nm and a nonwoven fabric containing an aromatic polyamide fibrid or an aromatic polyamide pulp, obtained by the above method, Can be produced by applying a heat and pressure treatment at 30 to 350 ° C. and a linear pressure of 50 to 300 kgf / cm. In the conditions of the heat and pressure treatment, it is more preferable that the temperature is 100 to 350 ° C. and the linear pressure is 150 to 300 kgf / cm. Here, if the heating temperature and the applied pressure are too low, the adhesive force between the ultrafine fibers is weakened. On the other hand, if the heating temperature and the applied pressure are too high, the fibers constituting the fiber structure or the fibers constituting the nonwoven fabric are This is not preferable because it causes fusion or the like and the eyes are crushed, resulting in poor electrolytic solution retention and increased internal resistance.
また、上記の加熱加圧処理を施すことにより、繊維構造体と不織布との密着性が向上し、加工性が向上する。さらに、繊維構造体の密度が向上し、電極間の遮蔽性も高くなることから、電気・電子部品中の導電部材間の隔壁として利用することができ、同時に不織布への繊維構造体の密着性が向上するため、良好な取り扱い性を提供することもできる。また、本発明のセパレータを使用した電池、コンデンサーなどの電気・電子部品は、耐熱性を有し、かつ薄葉であるため、電気自動車などの大電流環境下で有利に使用することができる。 Moreover, by performing said heat-pressing process, the adhesiveness of a fiber structure and a nonwoven fabric improves, and workability improves. Furthermore, since the density of the fiber structure is improved and the shielding property between the electrodes is increased, it can be used as a partition between conductive members in electrical and electronic parts, and at the same time, the adhesion of the fiber structure to the nonwoven fabric Therefore, it is possible to provide good handleability. In addition, since electric and electronic parts such as batteries and capacitors using the separator of the present invention have heat resistance and are thin, they can be advantageously used in a large current environment such as an electric vehicle.
本発明の複合構造体においては、透気度が、ＪＩＳ Ｐ８１１７ガーレー試験機法で測定して、１００秒／３００ｃｍ３以下、特に５０秒／３００ｃｍ３以下であることが好ましい。１００秒／３００ｍ３を超えるセパレータは、電解液をセパレータに含浸浸透させる場合に、十分な浸透充填が達成できない可能性があり、内部抵抗が高くなる可能性があることから好ましくない。 In the composite structure of the present invention, the air permeability is preferably 100 seconds / 300 cm 3 or less, particularly 50 seconds / 300 cm 3 or less, as measured by the JIS P8117 Gurley tester method. A separator exceeding 100 seconds / 300 m 3 is not preferable because, when the electrolyte is impregnated and permeated into the separator, sufficient permeation filling may not be achieved and internal resistance may be increased.
複合構造体のマクミラン数は、好ましくは１５以下、より好ましく１０以下である。また、マクミラン数×複合構造体の平均厚さは、好ましくは２５０μｍ以下、より好ましくは２００μｍ以下である。ここで、マクミラン数は電池用セパレータのイオン導電度を示す指標であり、複合構造体に電解液を含浸させたときのインピーダンスと電解液のみのインピーダンスとの比であることから、内部抵抗の指標として使用することができ、低いほど好ましい。ここでは２５℃において測定されたマクミラン数を採用している。 The Macmillan number of the composite structure is preferably 15 or less, more preferably 10 or less. The average thickness of Macmillan number × composite structure is preferably 250 μm or less, more preferably 200 μm or less. Here, the Macmillan number is an index indicating the ionic conductivity of the battery separator, and is the ratio of the impedance when the composite structure is impregnated with the electrolyte and the impedance of the electrolyte only. The lower the better. Here, the Macmillan number measured at 25 ° C. is adopted.
以上に説明した本発明の複合構造体は、内部抵抗値が著しく上昇することなく、高空隙率を有し、かつ薄葉でも内部短絡を防止することが可能であることから、電子部品用セパレータに好ましく用いることができる。 The composite structure of the present invention described above has a high porosity without significantly increasing the internal resistance value, and can prevent an internal short circuit even with a thin leaf. It can be preferably used.
本発明においては、３０℃から昇温速度１０℃／分で昇温したときの２５０℃における複合構造体の縦方向及び横方向の寸法変化率はいずれも好ましくは５％未満であり、さらに好ましくは３％未満である。複合構造体の寸法変化としては昇温により収縮する場合と伸長する場合が有り得るが、寸法変化率が５％を超えると、セパレータとして用いた複合構造体が、収縮した場合には短絡を生じやすくなり、伸張した場合には繊維構造体に疎と密の部分が生じて、疎の部分にイオン透過が集中して負荷がかかりやすくなるため、好ましくない。 In the present invention, the dimensional change rate in the longitudinal direction and the transverse direction of the composite structure at 250 ° C. when the temperature is increased from 30 ° C. at a rate of temperature increase of 10 ° C./min is preferably less than 5%, more preferably Is less than 3%. As the dimensional change of the composite structure, there is a case where it contracts due to temperature rise and a case where the composite structure expands. However, if the dimensional change rate exceeds 5%, the composite structure used as a separator is likely to cause a short circuit when contracted. When stretched, sparse and dense portions are formed in the fiber structure, and ion permeation concentrates on the sparse portions and a load is easily applied.
また、複合構造体の２００℃にて１時間加熱した際の透気度の変化率は好ましくは５％未満であり、より好ましくは３％未満である。透気度は、前述したＪＩＳ Ｐ８１１７ガーレー試験機法に準じて測定した数値を指すが、数値が増加することは密な構造、数値が減少することは、疎な構造に変化していることを意味する。透気度の数値が５％を超えて上昇、すなわち密な構造となると、内部抵抗が上昇するため好ましくない。一方、透気度の数値が５％を越えて減少し、疎な構造となると、極細繊維の破損する割合が高くなり、短絡防止の効果が低下するため好ましくない。 Further, the rate of change of the air permeability when the composite structure is heated at 200 ° C. for 1 hour is preferably less than 5%, more preferably less than 3%. The air permeability refers to a numerical value measured in accordance with the above-mentioned JIS P8117 Gurley test machine method. An increase in the numerical value indicates a dense structure, and a decrease in the numerical value indicates a change to a sparse structure. means. If the value of the air permeability exceeds 5%, that is, if it has a dense structure, the internal resistance increases, which is not preferable. On the other hand, if the air permeability value is decreased to exceed 5% and a sparse structure is obtained, the ratio of damage to the ultrafine fibers increases, and the effect of preventing short circuit is reduced, which is not preferable.
以上に説明した本発明の複合構造体は、内部抵抗値が著しく上昇することなく、高空隙率を有し、かつ薄葉でも内部短絡を防止することが可能であることから、電子部品用セパレータとしてそのまま好ましく用いることができる。 The composite structure of the present invention described above has a high porosity without significantly increasing the internal resistance value, and can prevent an internal short circuit even with a thin leaf. It can be preferably used as it is.
また、従来のセパレータには、電池内部温度が上昇した場合、セパレータが平面形態を保持することができず、また、セパレータ端部においても電極接触の機会が増えるため、十分な短絡防止作用が得られないといった課題が有り、本発明は、前記の寸法変化率、透気度の変化率を同時に満足させることでこれを解決できることに着目したものであるが、本発明の複合構造体およびそれからなるセパレータはかかる性能を十分に満たし前記課題をも克服するものである。 In addition, when the battery internal temperature rises, the conventional separator cannot maintain a flat form, and the chance of electrode contact also increases at the end of the separator. The present invention focuses on the fact that this can be solved by satisfying the above dimensional change rate and air permeability change rate at the same time. The separator satisfies such performance sufficiently and overcomes the above-mentioned problems.
以下、実施例に基づいて本発明をさらに詳細に説明する。しかし、以下の例によって、本発明が限定されることはない。 Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited by the following examples.
（１）繊維径
極細繊維を任意に１００本サンプリングし、走査型電子顕微鏡ＪＳＭ６３３０Ｆ（ＪＥＯＬ社製）にて測定し、繊維径の平均値を求めた。なお測定は、３０，０００倍の倍率で行った。
(1) Fiber diameter 100 ultrafine fibers were arbitrarily sampled and measured with a scanning electron microscope JSM6330F (manufactured by JEOL), and the average value of the fiber diameters was obtained. The measurement was performed at a magnification of 30,000 times.
（２）複合構造体の平均厚さ
ＯＮＯ ＳＯＫＫＩ ＤＧ−９２５ ディジタルリニアゲージを用い、任意に選択した２０箇所において厚さを測定し、平均値を求めた。
(2) Average thickness of composite structure ONO SOKKI DG-925 Using a digital linear gauge, thickness was measured at 20 arbitrarily selected locations, and an average value was obtained.
（３）透気度
ＪＩＳ Ｐ８１１７に従って測定した。
(3) Air permeability Measured according to JIS P8117.
（４）マクミラン数
得られた複合構造体を２００ｍｍφに切り出し、２枚のＳＵＳ電極に挟み、１０ｋＨｚでの交流インピーダンスから算出した伝導度で電解液のイオン伝導度を除し、算出する。電解液は１Ｍ ＬｉＢＦ４ＥＣ／ＰＣを重量比で１／１に調整したものを用い、測定温度は２５℃とする。この数値が低いほど、イオン透過が良く好ましい。
(4) Macmillan number The obtained composite structure is cut into 200 mmφ, sandwiched between two SUS electrodes, and calculated by dividing the ionic conductivity of the electrolyte by the conductivity calculated from the AC impedance at 10 kHz. The electrolyte is 1M LiBF 4 EC / PC adjusted to a weight ratio of 1/1, and the measurement temperature is 25 ° C. The lower this value, the better the ion permeation.
（５）寸法変化率
得られた複合構造体から任意に１０ヶ所選んで、縦、横方向にそれぞれ５ｍｍ×２５ｍｍの試験片を切り出して用い、ＴＭＡ４０００ＳＡ（Ｂｒｕｋｅｒ ＡＸＳ社製）により、試験長２０ｍｍ、荷重２ｇ、昇温速度１０℃／分として、３０℃から昇温しながら試験長２０ｍｍに対する寸法変化率（％）を連続して測定し、表１には２５０℃における寸法変化率（％）を示した。
(5) Dimensional change rate Ten arbitrary positions were selected from the obtained composite structure, and test pieces of 5 mm × 25 mm were cut and used in the vertical and horizontal directions, respectively, using TMA4000SA (manufactured by Bruker AXS), a test length of 20 mm, The dimensional change rate (%) for a test length of 20 mm was continuously measured while raising the temperature from 30 ° C. with a load of 2 g and a heating rate of 10 ° C./min. Indicated.
（６）透気度変化率
得られた複合構造体を２０ｃｍ×２０ｃｍに切り出し、２００℃に設定した乾燥機に、その壁面に複合構造体が接触しないように吊り下げた状態で、１時間加熱処理を実施し、前記（３）と同様にして透気度を測定した。さらに、加熱処理前後の透気度差の、加熱処理前の透気度に対する変化率を算出した。
(6) Permeability change rate The obtained composite structure was cut into 20 cm × 20 cm and heated for 1 hour in a dryer set at 200 ° C. so that the composite structure was not in contact with the wall surface. The treatment was carried out, and the air permeability was measured in the same manner as in the above (3). Furthermore, the change rate with respect to the air permeability before heat processing of the air permeability difference before and behind heat processing was computed.
［実施例１］
特許第３２０２５９７号公報に準じ、メタ型芳香族ポリアミドパルプを作製した。得られたメタ型芳香族ポリアミドパルプを、水１．５Ｌとともに公知の離解機にて離解し、２５×２５ｃｍ角のＴＡＰＰＩ式手漉きマシーンを用いて抄造した。さらに１２０℃で５時間乾燥させて湿式不織布を得た。その後、得られた湿式不織布に、上ローラが金属製加熱フラットローラ、下ローラが金属製フラットローラであるカレンダー装置により、上下ローラの温度を３３０℃、線圧を３００ｋｇｆ／ｃｍとして１回目のカレンダー加工を施し、さらに、上下ローラの温度を２５０℃、線圧を３００ｋｇｆ／ｃｍとして２回目のカレンダー加工を施し、メタ型芳香族ポリアミドパルプからなる不織布を得た。
また、特公昭４７−１０８６３号公報実施例１記載の方法に準じ、界面重合法によりメタ型芳香族ポリアミドを主成分とする芳香族ポリアミド粉末状体を製造した。得られた芳香族ポリアミド粉末状体、溶媒Ｎ，Ｎ−ジメチルアセトアミドを１０：９０の重量比で溶解させたポリマー溶液を調製した。このポリマー溶液を電解紡糸法にて印加電圧２０ｋＶ下にて芳香族ポリアミド極細繊維を成形し、目付が１．５ｇ／ｍ２となるように、上記のメタ型芳香族ポリアミドパルプからなる不織布上に積層させ、複合構造体を得た。得られた複合構造体を用い、セパレータとしての性能評価を行った。結果を表１に示す。
[Example 1]
A meta-type aromatic polyamide pulp was produced according to Japanese Patent No. 3202597. The obtained meta-type aromatic polyamide pulp was disaggregated with 1.5 L of water using a known disaggregator, and papermaking was performed using a 25 × 25 cm square TAPPI-type hand machine. Furthermore, it was dried at 120 ° C. for 5 hours to obtain a wet nonwoven fabric. Thereafter, the obtained wet nonwoven fabric was subjected to a first calendar by a calender device in which the upper roller was a metal heating flat roller and the lower roller was a metal flat roller with the upper and lower rollers at a temperature of 330 ° C. and a linear pressure of 300 kgf / cm. The nonwoven fabric was made of a meta-type aromatic polyamide pulp by applying a second calendering process with the upper and lower rollers at a temperature of 250 ° C. and a linear pressure of 300 kgf / cm.
Further, according to the method described in Example 1 of Japanese Examined Patent Publication No. 47-10863, an aromatic polyamide powder containing a meta-type aromatic polyamide as a main component was produced by an interfacial polymerization method. A polymer solution was prepared by dissolving the obtained aromatic polyamide powder and solvent N, N-dimethylacetamide in a weight ratio of 10:90. An aromatic polyamide ultrafine fiber is formed by applying an electrospinning method to this polymer solution at an applied voltage of 20 kV, and is formed on the nonwoven fabric made of the above-mentioned meta-type aromatic polyamide pulp so that the basis weight is 1.5 g / m 2. Lamination was performed to obtain a composite structure. The obtained composite structure was used to evaluate the performance as a separator. The results are shown in Table 1.
［実施例２］
不織布を、カレンダー加工を実施しない以外は、実施例１記載の方法と同様にして、不織布を得た。
また、実施例１記載の方法と同様にして、芳香族ポリアミド極細繊維からなる繊維構造体を上記不織布上に成形し、積層体を得た。得られた積層体を、上ローラが金属製加熱フラットローラ、下ローラが金属製フラットローラであるカレンダー装置により、上下ローラの温度を３３０℃、線圧を３００ｋｇｆ／ｃｍとして１回目のカレンダー加工を施し、さらに、上下ローラの温度を２５０℃、線圧を３００ｋｇｆ／ｃｍとして２回目のカレンダー加工を施し、複合構造体を得た。得られた複合構造体は、芳香族ポリアミド極細繊維が繊維形状を有している部分と、複数の芳香族ポリアミド極細繊維が軟化して一体化しフィルム形状を有している部分とが存在していた。また、フィルム形状を有している部分と、不織布とが接合一体化していた。得られた複合構造体を用い、セパレータとしての性能評価を行った。結果を表１に示す。
[Example 2]
A nonwoven fabric was obtained in the same manner as in Example 1 except that the nonwoven fabric was not calendered.
In addition, in the same manner as in the method described in Example 1, a fiber structure composed of aromatic polyamide ultrafine fibers was formed on the nonwoven fabric to obtain a laminate. The obtained laminate was calendered for the first time using a calender device in which the upper roller was a metal heating flat roller and the lower roller was a metal flat roller, with the upper and lower rollers at a temperature of 330 ° C. and a linear pressure of 300 kgf / cm. Further, the calendering process was performed for the second time with the temperature of the upper and lower rollers being 250 ° C. and the linear pressure being 300 kgf / cm to obtain a composite structure. The obtained composite structure has a portion in which the aromatic polyamide ultrafine fibers have a fiber shape and a portion in which a plurality of aromatic polyamide ultrafine fibers are softened and integrated to have a film shape. It was. Moreover, the part which has a film shape, and the nonwoven fabric were joined and integrated. The obtained composite structure was used to evaluate the performance as a separator. The results are shown in Table 1.
［実施例３］
芳香族ポリアミド粉末状体、溶媒Ｎ，Ｎ−ジメチルアセトアミドを７：９３の重量比で溶解させたポリマー溶液を使用した以外は、実施例２と同様にして複合構造体を得、セパレータとしての性能評価を行った。結果を表１に示す。
[Example 3]
A composite structure was obtained in the same manner as in Example 2 except that an aromatic polyamide powder and a polymer solution in which the solvent N, N-dimethylacetamide was dissolved at a weight ratio of 7:93 were used, and the performance as a separator was obtained. Evaluation was performed. The results are shown in Table 1.
［実施例４］
芳香族ポリアミド粉末状体、溶媒Ｎ，Ｎ−ジメチルアセトアミドを１５：８５の重量比で溶解させたポリマー溶液を使用した以外は、実施例２と同様にして複合構造体を得、セパレータとしての性能評価を行った。結果を表１に示す。
[Example 4]
A composite structure was obtained in the same manner as in Example 2 except that an aromatic polyamide powder and a polymer solution in which the solvent N, N-dimethylacetamide was dissolved at a weight ratio of 15:85 were used. Evaluation was performed. The results are shown in Table 1.
［実施例５］
特公昭３７−５７３２公報実施例１に準じて得られたメタ型芳香族ポリアミドフィブリッドにより不織布を成形した以外は、実施例２記載の方法に準じて複合繊維構造体を得た。結果を表１に示す。
[Example 5]
A composite fiber structure was obtained in accordance with the method described in Example 2, except that a non-woven fabric was formed from the meta-type aromatic polyamide fibrid obtained in accordance with Example 1 of JP-B-37-5732. The results are shown in Table 1.
［比較例１］
ポリビニルアルコール（ＰＶＡ）（株式会社クラレ製）、を１７：８５の重量比で水に溶解させたポリマー溶液を調製して芳香族ポリアミドポリマー溶液の代わりに用いた以外は、実施例１と同様にして複合構造体を得た。得られた複合構造体を用い、セパレータとしての性能評価を行った。結果を表１に示す。
[Comparative Example 1]
A polymer solution prepared by dissolving polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd.) in water at a weight ratio of 17:85 was used in the same manner as in Example 1 except that it was used instead of the aromatic polyamide polymer solution. Thus, a composite structure was obtained. The obtained composite structure was used to evaluate the performance as a separator. The results are shown in Table 1.
［比較例２］
ポリビニルアルコール（ＰＶＡ）（株式会社クラレ製）、を１７：８５の重量比で水に溶解させたポリマー溶液を調製して芳香族ポリアミドポリマー溶液の代わりに用い、カレンダー加工において、上下ローラの温度を１回目、２回目ともに１００℃、線圧を１回目、２回目ともに３００ｋｇｆ／ｃｍに変更した以外は、実施例２と同様にして複合構造体を得た。得られた複合構造体を用い、セパレータとしての性能評価を行った。結果を表１に示す。
[Comparative Example 2]
A polymer solution in which polyvinyl alcohol (PVA) (manufactured by Kuraray Co., Ltd.) was dissolved in water at a weight ratio of 17:85 was prepared and used in place of the aromatic polyamide polymer solution. A composite structure was obtained in the same manner as in Example 2 except that the first time and the second time were changed to 100 ° C., and the linear pressure was changed to 300 kgf / cm for the first time and the second time. The obtained composite structure was used to evaluate the performance as a separator. The results are shown in Table 1.
［比較例３］
不織布として、目付けが１７ｇ／ｍ２のポリプロピレンスパンボンド不織布（日本不織布製）を用い、カレンダー加工において、上下ローラの温度を１回目、２回目ともに１００℃、線圧を１回目、２回目ともに３００ｋｇｆ／ｃｍに変更した以外は、実施例２と同様にして複合構造体を得た。得られた複合構造体を用い、セパレータとしての性能評価を行った。結果を表１に示す。
[Comparative Example 3]
As a nonwoven fabric, a polypropylene spunbond nonwoven fabric (manufactured by Japan nonwoven fabric) with a basis weight of 17 g / m 2 was used. A composite structure was obtained in the same manner as in Example 2 except for changing to / cm. The obtained composite structure was used to evaluate the performance as a separator. The results are shown in Table 1.
［比較例４］
ポリプロピレン（ＰＰ）微多孔膜（セルガードＴＭ２４００、Ｃｅｌｇａｒｄ社製）を用い、セパレータとしての性能評価を行った。結果を表１に示す。
[Comparative Example 4]
Using a polypropylene (PP) microporous membrane (Celgard TM2400, manufactured by Celgard), performance evaluation as a separator was performed. The results are shown in Table 1.
本発明によれば、耐熱性などの高機能を有する芳香族ポリアミド極細繊維を使用し、加熱加圧処理工程を経ることによって、薄葉で、優れた耐熱性を有する電子部品用セパレータを提供することができる。 According to the present invention, by using an aromatic polyamide ultrafine fiber having high functions such as heat resistance, and through a heat and pressure treatment step, a thin leaf and an electronic component separator having excellent heat resistance is provided. Can do.
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| JP2012197644A (en) * | 2011-03-23 | 2012-10-18 | Nisshinbo Holdings Inc | Heat insulator |
| JP2012209181A (en) * | 2011-03-30 | 2012-10-25 | Teijin Techno Products Ltd | Separator |
| JP2013181263A (en) * | 2012-03-02 | 2013-09-12 | Teijin Ltd | Aromatic polyamide nanofiber structure and separator composed thereof |
| JP2013251063A (en) * | 2012-05-30 | 2013-12-12 | Teijin Ltd | Ultrafine fiber structure |
| JP2021073646A (en) * | 2010-08-02 | 2021-05-13 | セルガード エルエルシー | High-melting point microporous battery separator |
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| JP2005307360A (en) * | 2004-04-16 | 2005-11-04 | Du Pont Teijin Advanced Paper Kk | Aramid tissue material and electrical and electronic part using the same |
| JP2006336173A (en) * | 2005-06-06 | 2006-12-14 | Teijin Techno Products Ltd | Composite structure and manufacturing method thereof |
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| JP2012011754A (en) * | 2010-07-05 | 2012-01-19 | Teijin Techno Products Ltd | Composite, and electric and electronic component including the same |
| JP2021073646A (en) * | 2010-08-02 | 2021-05-13 | セルガード エルエルシー | High-melting point microporous battery separator |
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| JP2013251063A (en) * | 2012-05-30 | 2013-12-12 | Teijin Ltd | Ultrafine fiber structure |
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