JP6016557B2 - Nonwoven fabric substrate for lithium ion secondary battery separator and method for producing the same - Google Patents
Nonwoven fabric substrate for lithium ion secondary battery separator and method for producing the same Download PDFInfo
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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
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- 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
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Description
本発明は、リチウムイオン二次電池セパレータに用いる不織布基材及びその製造方法に関する。 The present invention relates to a nonwoven fabric substrate used for a lithium ion secondary battery separator and a method for producing the same .
リチウムイオン二次電池（以下、「電池」と略記する場合がある）用のセパレータとしては従来、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂からなる多孔膜が用いられてきた。しかしかかる樹脂製多孔膜には、電池が異常発熱した場合に溶融・収縮し、正負極を隔離する機能が失われて著しい短絡を生じる問題があった。 As a separator for a lithium ion secondary battery (hereinafter sometimes abbreviated as “battery”), a porous film made of a polyolefin resin such as polyethylene or polypropylene has been conventionally used. However, such a porous resin membrane has a problem that it melts and contracts when the battery abnormally generates heat, and the function of isolating the positive and negative electrodes is lost, resulting in a significant short circuit.
電池が異常発熱した場合でも溶融・収縮を生じにくいセパレータとして、不織布基材に各種の無機顔料を塗工してなるセパレータが提案されている（例えば、特許文献１〜３参照）。 As a separator that hardly melts or shrinks even when a battery abnormally generates heat, a separator formed by applying various inorganic pigments to a nonwoven fabric substrate has been proposed (for example, see Patent Documents 1 to 3).
特許文献１のセパレータは、不織布基材に無機顔料を含む塗液を塗工して製造されるが、薄いセパレータを製造しようとする場合、塗液が不織布基材の裏面に滲出し、不織布基材を支持しているロールを汚すことがあり、塗工層にピンホールが生じやすかった。 The separator of Patent Document 1 is manufactured by applying a coating solution containing an inorganic pigment to a nonwoven fabric substrate. However, when a thin separator is to be manufactured, the coating solution oozes on the back surface of the nonwoven fabric substrate, The roll supporting the material could be soiled, and pinholes were likely to occur in the coating layer.
特許文献２のセパレータは、薄いセパレータを製造しようとする際、強度がやや不十分となる場合があり、塗工操作における破断等が生じる場合があった。特許文献３のセパレータは、薄いセパレータを製造しようとする際、密度がやや高くなる場合があり、塗工操作における塗液の裏抜けが見られる場合があった。 The separator of Patent Document 2 may have a slightly insufficient strength when attempting to produce a thin separator, and may cause breakage in a coating operation. When the separator of Patent Document 3 is intended to produce a thin separator, the density may be slightly high, and the coating liquid may be seen through in the coating operation.
本発明は、上記課題を解決しようとするものである。すなわち、リチウムイオン二次電池セパレータに用いる不織布基材において、無機顔料を含む塗液を塗工する際に、塗液が裏面に滲出しにくい基材を提供しようとするものである。 The present invention is intended to solve the above problems. That is, in the nonwoven fabric base material used for the lithium ion secondary battery separator, when applying a coating liquid containing an inorganic pigment, the base material is intended to provide a base material in which the coating liquid hardly oozes on the back surface.
本発明者らは、上記課題を解決するための手段として、
（１）リチウムイオン二次電池セパレータ用不織布基材であって、ポリエチレンテレフタレート繊維を主体としてなり、厚み１４μｍ以上３０μｍ以下、坪量／厚みで定義される密度が０．３９ｇ／ｃｍ ３ 以上０．５５ｇ／ｃｍ３以下、引張強度が８００Ｎ／ｍ以上１２９０Ｎ／ｍ以下であることを特徴とするリチウムイオン二次電池セパレータ用不織布基材、
（２）前記（１）記載のリチウムイオン二次電池セパレータ用不織布基材を製造するための、リチウムイオン二次電池セパレータ用不織布基材の製造方法において、湿式法により抄造されてなる原反を、加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０以下のロールとの間を通過させて処理することを特徴とするリチウムイオン二次電池セパレータ用不織布基材の製造方法、
を見出した。
As a means for solving the above problems, the present inventors have:
(1) A non-woven fabric substrate for lithium ion secondary battery separator, made mainly of polyethylene terephthalate fiber, thickness 14μm or 30μm or less, the density defined by the basis weight / thickness 0.39 g / cm 3 or more zero. A nonwoven fabric substrate for a lithium ion secondary battery separator, characterized by having a tensile strength of not less than 55 g / cm 3 and not less than 800 N / m and not more than 1290 N / m ,
(2) (1) for manufacturing a lithium ion secondary battery separator nonwoven substrate described, in the manufacturing method of a lithium ion secondary battery separator nonwoven substrate is papermaking by a wet method Do that raw a heated metal roll and, non-woven fabric characteristics and be Brighter lithium ion secondary battery separator that hardness measured by a durometer a defined in JIS K6253 is processed by passing between the 80 following roles Manufacturing method of substrate,
I found.
本発明の不織布基材は、無機顔料の塗液を塗工した際の裏抜けが少なく、もって高い生産性で不織布基材に無機顔料を塗工したリチウムイオン二次電池セパレータを製造することができるようになる。 The non-woven fabric substrate of the present invention is capable of producing a lithium ion secondary battery separator in which an inorganic pigment is coated on a non-woven fabric substrate with high productivity, with little see-through when an inorganic pigment coating solution is applied. become able to.
すなわち、ポリエチレンテレフタレート繊維を主体としてなる不織布基材の密度が０．５５ｇ／ｃｍ３以下であることによって、塗液を不織布基材内部に保持する能力が高くなり、塗液の裏抜けを生じにくくすることができる。また、引張強度が８００Ｎ／ｍ以上であることによって、塗工操作における破断等が生じにくく、生産性を高くすることができる。なお、厚みが３０μｍを超える厚みの厚い不織布基材は、本発明によらなくても、塗液の裏抜けが生じにくく、本発明の効果が発現しづらいが、セパレータの薄膜化が難しくなる。 That is, when the density of the nonwoven fabric substrate mainly composed of polyethylene terephthalate fiber is 0.55 g / cm 3 or less, the ability to hold the coating liquid inside the nonwoven fabric substrate is increased, and the back-through of the coating liquid is unlikely to occur. can do. Moreover, when the tensile strength is 800 N / m or more, breakage or the like in the coating operation hardly occurs, and productivity can be increased. In addition, even if it is not according to the present invention, a thick nonwoven fabric substrate having a thickness of more than 30 μm is less likely to cause the coating liquid to fall through, and the effects of the present invention are difficult to be exhibited, but it is difficult to reduce the thickness of the separator.
本発明の不織布基材は、湿式法により抄造された原反を、加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０以下のロールとの間を通過させて処理することが、密度が０．５５ｇ／ｃｍ３以下、かつ引張強度が８００Ｎ／ｍ以上の不織布基材を製造する上で好ましい。 In the nonwoven fabric substrate of the present invention, the raw material made by a wet method is passed between a heated metal roll and a roll having a hardness measured by a durometer A defined in JIS K6253 of 80 or less. It is preferable to treat the nonwoven fabric substrate with a density of 0.55 g / cm 3 or less and a tensile strength of 800 N / m or more.
本発明のリチウムイオン二次電池セパレータ用不織布基材（以下、「不織布基材」と略記する場合がある）は、ポリエチレンテレフタレート繊維を主体としてなる。不織布基材におけるポリエチレンテレフタレート繊維の含有量は７０質量％以上が好ましく、８０質量％以上がより好ましく、９０質量％以上がさらに好ましい。ポリエチレンテレフタレートの含有量が７０質量％よりも少ない場合、強度が弱くなる場合がある。 The nonwoven fabric base material for lithium ion secondary battery separators of the present invention (hereinafter sometimes abbreviated as “nonwoven fabric base material”) mainly comprises polyethylene terephthalate fibers. 70 mass% or more is preferable, as for content of the polyethylene terephthalate fiber in a nonwoven fabric base material, 80 mass% or more is more preferable, and 90 mass% or more is further more preferable. When the content of polyethylene terephthalate is less than 70% by mass, the strength may be weakened.
本発明におけるポリエチレンテレフタレート繊維の平均繊維径は０．１〜２０μｍが好ましく、０．１〜１５μｍがより好ましく、０．１〜１０μｍがさらに好ましい。平均繊維径が０．１μｍ未満では、繊維が細すぎて、不織布基材から脱落する場合があり、平均繊維径が２０μｍより太いと、不織布基材の厚みを薄くすることが困難になる場合がある。 The average fiber diameter of the polyethylene terephthalate fiber in the present invention is preferably 0.1 to 20 μm, more preferably 0.1 to 15 μm, and further preferably 0.1 to 10 μm. If the average fiber diameter is less than 0.1 μm, the fibers may be too thin and fall off from the nonwoven fabric substrate. If the average fiber diameter is greater than 20 μm, it may be difficult to reduce the thickness of the nonwoven fabric substrate. is there.
本発明における平均繊維径は、不織布基材の走査型電子顕微鏡写真より、不織布基材を形成する繊維の繊維径を計測し、無作為に選んだ１００本の平均値である。 The average fiber diameter in the present invention is an average value of 100 fibers randomly selected by measuring the fiber diameter of the fibers forming the nonwoven fabric substrate from a scanning electron micrograph of the nonwoven fabric substrate.
本発明におけるポリエチレンテレフタレート繊維の繊維長は１〜１５ｍｍが好ましく、２〜１０ｍｍがより好ましく、３〜５ｍｍがさらに好ましい。繊維長が１ｍｍより短いと、不織布基材から脱落することがあり、１５ｍｍより長いと、繊維がもつれてダマになることがあり、厚みむらが生じる場合がある。 1-15 mm is preferable, as for the fiber length of the polyethylene terephthalate fiber in this invention, 2-10 mm is more preferable, and 3-5 mm is further more preferable. When the fiber length is shorter than 1 mm, the nonwoven fabric substrate may fall off. When the fiber length is longer than 15 mm, the fibers may be entangled and become lumpy, resulting in uneven thickness.
本発明の不織布基材は、ポリエチレンテレフタレート繊維以外の繊維を含有しても良い。例えば、溶剤紡糸セルロースや再生セルロースの短繊維、天然セルロース繊維、天然セルロース繊維のパルプ化物やフィブリル化物、ポリオレフィン、アクリル、全芳香族ポリエステル、全芳香族ポリエステルアミド、ポリアミド、半芳香族ポリアミド、全芳香族ポリアミド、全芳香族ポリエーテル、全芳香族ポリカーボネート、全芳香族ポリアゾメジン、ポリイミド、ポリアミドイミド（ＰＡＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリ−ｐ−フェニレンベンゾビスオキサゾール（ＰＢＯ）、ポリベンゾイミダゾール（ＰＢＩ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、エチレン−ビニルアルコール共重合体などの樹脂からなる単繊維や複合繊維、これらをフィブリル化したものを適量単独で含有しても良いし、２種類以上の組み合わせで含有しても良い。また、各種の分割型複合繊維を分割させたものを含有しても良い。 The nonwoven fabric substrate of the present invention may contain fibers other than polyethylene terephthalate fibers. For example, solvent-spun cellulose and regenerated cellulose short fiber, natural cellulose fiber, pulped and fibrillated natural cellulose fiber, polyolefin, acrylic, wholly aromatic polyester, wholly aromatic polyester amide, polyamide, semi-aromatic polyamide, wholly aromatic Polyamide, wholly aromatic polyether, wholly aromatic polycarbonate, wholly aromatic polyazomedin, polyimide, polyamideimide (PAI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), poly-p-phenylenebenzobisoxazole ( Single fibers and composite fibers made of resins such as PBO), polybenzimidazole (PBI), polytetrafluoroethylene (PTFE), and ethylene-vinyl alcohol copolymer, and fibrillated ones are suitable. It alone may contain may contain a combination of two or more. Moreover, you may contain what divided | segmented various split type composite fibers.
半芳香族とは、主鎖の一部に例えば脂肪鎖などを有するものを指す。全芳香族ポリアミドはパラ型、メタ型いずれでも良い。 Semi-aromatic refers to those having, for example, a fatty chain as part of the main chain. The wholly aromatic polyamide may be para-type or meta-type.
本発明の不織布基材は、厚み３０μｍ以下、坪量／厚みで定義される密度が０．５５ｇ／ｃｍ３以下、引張強度が８００Ｎ／ｍ以上である。厚みが３０μｍを超える厚みの厚い不織布基材は、本発明によらなくても塗液の裏抜けが生じにくく、本発明の効果が発現しづらい。本発明の特徴は、坪量／厚みで定義される密度が０．５５ｇ／ｃｍ３以下であり、かつ引張強度が８００Ｎ／ｍ以上であることにある。 The nonwoven fabric substrate of the present invention has a thickness of 30 μm or less, a density defined by basis weight / thickness of 0.55 g / cm 3 or less, and a tensile strength of 800 N / m or more. A thick nonwoven fabric substrate having a thickness of more than 30 μm is less likely to cause the coating liquid to penetrate even if it is not according to the present invention, and the effects of the present invention are difficult to be exhibited. The feature of the present invention is that the density defined by basis weight / thickness is 0.55 g / cm 3 or less and the tensile strength is 800 N / m or more.
本発明の不織布基材は、密度が０．５５ｇ／ｃｍ３以下であることによって、塗液を内部に保持する能力が高く、裏抜けが生じにくい。また、引張強度が８００Ｎ／ｍ以上であることによって、塗工操作における破断等が生じにくく、生産性を高くすることができる。 When the density of the nonwoven fabric substrate of the present invention is 0.55 g / cm 3 or less, the ability to hold the coating liquid inside is high, and back-through is unlikely to occur. Moreover, when the tensile strength is 800 N / m or more, breakage or the like in the coating operation hardly occurs, and productivity can be increased.
本発明の不織布基材の厚みは１５〜３０μｍが好ましく、１５〜２７μｍがより好ましく、１５〜２５μｍがさらに好ましい。１５μｍ未満では、十分な不織布基材の強度が得られない場合があり、３０μｍより厚いと、セパレータの薄膜化が難しくなる。 15-30 micrometers is preferable, as for the thickness of the nonwoven fabric base material of this invention, 15-27 micrometers is more preferable, and 15-25 micrometers is further more preferable. If it is less than 15 μm, sufficient strength of the nonwoven fabric substrate may not be obtained. If it is thicker than 30 μm, it is difficult to make the separator thin.
本発明の不織布基材の密度は０．４０〜０．５５ｇ／ｃｍ３が好ましく、０．４１〜０．５４ｇ／ｃｍ３がより好ましく、０．４２〜０．５３ｇ／ｃｍ３がさらに好ましい。０．４０ｇ／ｃｍ３未満では、十分な不織布基材の強度が得られない場合があり、０．５５ｇ／ｃｍ３より高いと、塗液を不織布基材内部に保持する能力が不十分で、裏抜けが生じやすい。 The density of the nonwoven fabric substrate of the present invention is preferably 0.40~0.55g / cm 3, more preferably 0.41~0.54g / cm 3, more preferably 0.42~0.53g / cm 3. If it is less than 0.40 g / cm 3 , sufficient strength of the nonwoven fabric substrate may not be obtained, and if it is higher than 0.55 g / cm 3 , the ability to hold the coating liquid inside the nonwoven fabric substrate is insufficient, There is a tendency to break through.
本発明の不織布基材の引張強度は８００〜３０００Ｎ／ｍが好ましく、８２０〜２７００Ｎ／ｍがより好ましく、８５０〜２５００Ｎ／ｍがさらに好ましい。引張強度が８００Ｎ／ｍ未満では、塗工操作における破断等が生じやすく、生産性が落ちる。引張強度が３０００Ｎ／ｍよりも強い場合、厚み３０μｍ以下とすることが難しい場合がある。 800-3000 N / m is preferable, the tensile strength of the nonwoven fabric base material of this invention has more preferable 820-2700 N / m, and 850-2500 N / m is further more preferable. When the tensile strength is less than 800 N / m, breakage or the like in the coating operation is likely to occur, and productivity is lowered. When the tensile strength is stronger than 3000 N / m, it may be difficult to make the thickness 30 μm or less.
本発明の不織布基材は、次のようにして製造することができる。すなわち、湿式法により抄造された原反を、加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０以下のロールとの間を通過させ処理することで、厚み３０μｍ以下、密度が０．５５ｇ／ｃｍ３以下、引張強度が８００Ｎ／ｍ以上の不織布基材とすることができる。 The nonwoven fabric substrate of the present invention can be produced as follows. That is, the raw material made by the wet method is processed by passing between a heated metal roll and a roll having a hardness measured by a durometer A defined by JIS K6253 of 80 or less, thereby obtaining a thickness of 30 μm. Hereinafter, a nonwoven fabric substrate having a density of 0.55 g / cm 3 or less and a tensile strength of 800 N / m or more can be obtained.
本発明における湿式法は、繊維を水中に分散して均一な抄紙スラリーとし、この抄紙スラリーを円網、長網、傾斜式等のワイヤーの少なくとも１つを有する抄紙機を用いて、繊維ウェブを得る方法である。 In the wet method of the present invention, the fibers are dispersed in water to form a uniform papermaking slurry. The papermaking slurry is made into a fiber web by using a papermaking machine having at least one of a wire such as a circular net, a long net, and an inclined type. How to get.
繊維ウェブから不織布を製造する方法としては、水流交絡法、ニードルパンチ法、バインダー接着法等を使用することができる。特に、均一性を重視して湿式法を用いる場合、熱融着性繊維を含有させて、バインダー接着法によって該熱融着性短繊維を接着させることが好ましい。バインダー接着法により、均一なウェブから均一な不織布基材原反が形成される。 As a method for producing a nonwoven fabric from a fibrous web, a hydroentanglement method, a needle punch method, a binder adhesion method, or the like can be used. In particular, when the wet method is used with emphasis on uniformity, it is preferable to include a heat-fusible fiber and bond the heat-fusible short fiber by a binder bonding method. A uniform nonwoven fabric base material is formed from a uniform web by the binder bonding method.
本発明の不織布基材の原反を、加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０以下のロールとの間を通過させ処理する際のニップ圧は５０〜２５０ｋＮ／ｍが好ましく、７０〜２３０ｋＮ／ｍがより好ましく、１００〜２００ｋＮ／ｍがさらに好ましい。５０ｋＮ／ｍ未満では、十分な不織布基材の強度が得られない場合があり、２５０ｋＮ／ｍより高いと、不織布基材の密度が高くなり過ぎる場合がある。 The nip pressure when the raw fabric of the nonwoven fabric substrate of the present invention is processed by passing between a heated metal roll and a roll having a hardness of 80 or less as measured by durometer A defined in JIS K6253 is 50. -250 kN / m is preferable, 70-230 kN / m is more preferable, and 100-200 kN / m is further more preferable. If it is less than 50 kN / m, sufficient strength of the nonwoven fabric substrate may not be obtained, and if it is higher than 250 kN / m, the density of the nonwoven fabric substrate may be too high.
本発明の不織布基材の原反を、加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０以下のロールとの間を通過させ処理する際の処理速度は５〜８０ｍ／ｍｉｎが好ましく、７〜７０ｍ／ｍｉｎがより好ましく、１０〜６０ｍ／ｍｉｎがさらに好ましい。５ｍ／ｍｉｎ未満では、不織布基材の密度が高くなり過ぎる場合があり、８０ｍ／ｍｉｎより速いと、十分な不織布基材の強度が得られない場合がある。 The processing speed at the time of processing the raw fabric of the nonwoven fabric base material of the present invention by passing between a heated metal roll and a roll having a hardness measured by durometer A defined by JIS K6253 of 80 or less is 5 -80 m / min is preferable, 7-70 m / min is more preferable, and 10-60 m / min is more preferable. If it is less than 5 m / min, the density of the nonwoven fabric substrate may be too high, and if it is faster than 80 m / min, sufficient strength of the nonwoven fabric substrate may not be obtained.
本発明の不織布基材の原反を処理する際の金属ロールの温度は１７５〜２１０℃が好ましく、１８０〜２０５℃がより好ましく、１８５〜２００℃がさらに好ましい。１７５℃未満では、十分な不織布基材の強度が得られない場合があり、２１０℃より高いと、不織布基材の密度が高くなり過ぎる場合がある。 175-210 degreeC is preferable, as for the temperature of the metal roll at the time of processing the raw material of the nonwoven fabric base material of this invention, 180-205 degreeC is more preferable, and 185-200 degreeC is further more preferable. If it is less than 175 degreeC, the intensity | strength of sufficient nonwoven fabric base material may not be acquired, and if it exceeds 210 degreeC, the density of a nonwoven fabric base material may become high too much.
本発明の不織布基材の原反を処理する際のゴムロールのＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度は５０〜８０が好ましく、５５〜７７がより好ましく、６０〜７５がさらに好ましい。５０未満では、十分な不織布基材の強度が得られない場合があり、８０より高いと、不織布基材の密度が高くなり過ぎたり、引張強度が弱くなり過ぎたりすることがあり、密度が０．５５ｇ／ｃｍ３以下かつ引張強度が８００Ｎ／ｍ以上とすることが難しい場合がある。 The hardness measured by the durometer A defined in JIS K6253 of the rubber roll when processing the raw fabric of the nonwoven fabric substrate of the present invention is preferably 50 to 80, more preferably 55 to 77, and still more preferably 60 to 75. If it is less than 50, sufficient strength of the nonwoven fabric substrate may not be obtained. If it is higher than 80, the density of the nonwoven fabric substrate may be too high or the tensile strength may be too weak, and the density is 0. .55 g / cm 3 or less and tensile strength of 800 N / m or more may be difficult.
以下、実施例により本発明をさらに詳しく説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example.
表１に示した原料と配合量に従って、抄紙用スラリーを調製した。ここで、表１中の「ＰＥＴ１」は、繊度０．０６ｄｔｅｘ、繊維長３ｍｍのポリエチレンテレフタレート繊維、「ＰＥＴ２」は、繊度０．１０ｄｔｅｘ、繊維長３ｍｍのポリエチレンテレフタレート繊維、「ＰＥＴ３」は、繊度０．２０ｄｔｅｘ、繊維長３ｍｍの未延伸ポリエチレンテレフタレート繊維、「ＰＡ１」は、繊度０．７５ｄｔｅｘ、繊維長３ｍｍの全芳香族ポリアミド繊維（コポリ（パラ−フェニレン−３，４′−オキシジフェニレンテレフタルアミド））、「ＰＡ２」は、繊度０．０８ｄｔｅｘ、繊維長３ｍｍの半芳香族ポリアミド繊維、「Ａ１」は、繊度０．１０ｄｔｅｘ、繊維長３ｍｍのアクリル系繊維（アクリロニトリル、アクリル酸メチル、メタクリル酸誘導体の３成分からなるアクリロニトリル系共重合体）を意味する。 A papermaking slurry was prepared according to the raw materials and blending amounts shown in Table 1. Here, “PET1” in Table 1 is a polyethylene terephthalate fiber having a fineness of 0.06 dtex and a fiber length of 3 mm, “PET2” is a polyethylene terephthalate fiber having a fineness of 0.10 dtex and a fiber length of 3 mm, and “PET3” is a fineness of 0 .20 dtex, unstretched polyethylene terephthalate fiber having a fiber length of 3 mm, “PA1” is a wholly aromatic polyamide fiber having a fineness of 0.75 dtex and a fiber length of 3 mm (copoly (para-phenylene-3,4′-oxydiphenylene terephthalamide) ), “PA2” is a semi-aromatic polyamide fiber having a fineness of 0.08 dtex and a fiber length of 3 mm, and “A1” is an acrylic fiber (acrylonitrile, methyl acrylate, methacrylic acid derivative having a fineness of 0.10 dtex and a fiber length of 3 mm) Meaning acrylonitrile copolymer consisting of 3 components) That.
＜不織布基材用原反＞
スラリー１〜４を円網・傾斜コンビネーション抄紙機を用いて湿式抄紙し、表２に示す不織布基材用原反１〜７を作製した。
<Original fabric for nonwoven fabric substrate>
Slurries 1 to 4 were subjected to wet paper making using a circular mesh / tilted combination paper machine, and raw materials 1 to 7 for nonwoven fabric substrates shown in Table 2 were produced.
＜不織布基材＞
（実施例１）
不織布基材用原反１を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が６０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例１の不織布基材を作製した。
<Nonwoven fabric substrate>
Example 1
A nip pressure of 100 kN / m and a processing speed of 10 m / g between a metal roll heated to 195 ° C. and a roll having a hardness of 60 measured by durometer A defined in JIS K6253 The nonwoven fabric substrate of Example 1 shown in Table 3 was produced by passing it through min.
（実施例２）
不織布基材用原反１を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例２の不織布基材を作製した。
(Example 2)
A nip pressure of 100 kN / m and a processing speed of 10 m / g between a metal roll heated to 195 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric substrate of Example 2 shown in Table 3 was produced by passing it through min.
（実施例３）
不織布基材用原反２を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧１５０ｋＮ／ｍ、処理速度２０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例３の不織布基材を作製した。
(Example 3)
A nip pressure of 150 kN / m and a processing speed of 20 m / g between a metal roll heated to 195 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric substrate of Example 3 shown in Table 3 was produced by passing it through min.
（実施例４）
不織布基材用原反３を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧１５０ｋＮ／ｍ、処理速度２０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例４の不織布基材を作製した。
Example 4
A nip pressure of 150 kN / m between a metal roll heated to 195 ° C. and a roll having a hardness measured by durometer A defined in JIS K6253 of 70 kN / m and a processing speed of 20 m / m. The nonwoven fabric substrate of Example 4 shown in Table 3 was produced by passing it through min.
（実施例５）
不織布基材用原反４を、２１０℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧２５０ｋＮ／ｍ、処理速度８０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例５の不織布基材を作製した。
(Example 5)
A nip pressure of 250 kN / m and a processing speed of 80 m / g between a metal roll heated to 210 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Example 5 shown in Table 3 was produced by passing it through min.
（実施例６）
不織布基材用原反２を、１７５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が５０のロールとの間をニップ圧５０ｋＮ／ｍ、処理速度５ｍ／ｍｉｎで通過させ処理し、表３に示す実施例６の不織布基材を作製した。
(Example 6)
A nip pressure of 50 kN / m between a metal roll heated to 175 ° C. and a roll having a hardness measured by durometer A defined in JIS K6253 is 50 kN / m, and a processing speed is 5 m / min. The nonwoven fabric base material of Example 6 shown in Table 3 was produced by passing it through min.
（実施例７）
不織布基材用原反１を、１８５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例７の不織布基材を作製した。
(Example 7)
A nip pressure of 100 kN / m and a processing speed of 10 m / g between a metal roll heated to 185 ° C. and a roll having a hardness of 80 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Example 7 shown in Table 3 was produced by passing it through min.
（実施例８）
不織布基材用原反１を、１８５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が４５のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例８の不織布基材を作製した。
(Example 8)
A nip pressure of 100 kN / m and a processing speed of 10 m / g between a metal roll heated to 185 ° C. and a roll having a hardness measured by a durometer A specified by JIS K6253 of 45 are used for the nonwoven fabric base material 1. The nonwoven fabric base material of Example 8 shown in Table 3 was produced by passing it through min.
（実施例９）
不織布基材用原反１を、１７５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧５０ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例９の不織布基材を作製した。
Example 9
A nip pressure of 50 kN / m, a processing speed of 10 m / m between a metal roll heated to 175 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Example 9 shown in Table 3 was produced by passing it through min.
（実施例１０）
不織布基材用原反５を、２００℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例１０の不織布基材を作製した。
(Example 10)
A nip pressure of 100 kN / m, a processing speed of 10 m / m between a metal roll heated to 200 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Example 10 shown in Table 3 was produced by passing it through min.
（実施例１１）
不織布基材用原反６を、２００℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す実施例１１の不織布基材を作製した。
(Example 11)
A nip pressure of 100 kN / m, a processing speed of 10 m / m between a metal roll heated to 200 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Example 11 shown in Table 3 was produced by passing it through min.
（比較例１）
不織布基材用原反１を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す比較例１の不織布基材を作製した。
(Comparative Example 1)
A nip pressure of 100 kN / m and a processing speed of 10 m / m between a metal roll heated to 195 ° C. and a roll having a hardness of 80 measured by durometer A defined in JIS K6253. The nonwoven fabric substrate of Comparative Example 1 shown in Table 3 was produced by passing it through min.
（比較例２）
不織布基材用原反１を、１７５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧４０ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す比較例２の不織布基材を作製した。
(Comparative Example 2)
A nip pressure of 40 kN / m, a processing speed of 10 m / m between a metal roll heated to 175 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Comparative Example 2 shown in Table 3 was produced by passing it through min.
（比較例３）
不織布基材用原反７を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が７０のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す比較例３の不織布基材を作製した。
(Comparative Example 3)
A nip pressure of 100 kN / m and a processing speed of 10 m / g between a metal roll heated to 195 ° C. and a roll having a hardness of 70 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Comparative Example 3 shown in Table 3 was produced by passing it through min.
（比較例４）
不織布基材用原反１を、１９５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８５のロールとの間をニップ圧１００ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す比較例４の不織布基材を作製した。
(Comparative Example 4)
A nip pressure of 100 kN / m and a processing speed of 10 m / g between a metal roll heated to 195 ° C. and a roll having a hardness of 85 measured by durometer A defined in JIS K6253. The nonwoven fabric substrate of Comparative Example 4 shown in Table 3 was produced by passing it through min.
（比較例５）
不織布基材用原反１を、１７５℃に加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８５のロールとの間をニップ圧５０ｋＮ／ｍ、処理速度１０ｍ／ｍｉｎで通過させ処理し、表３に示す比較例５の不織布基材を作製した。
(Comparative Example 5)
A nip pressure of 50 kN / m, a processing speed of 10 m / m between a metal roll heated to 175 ° C. and a roll having a hardness of 85 measured by durometer A defined in JIS K6253. The nonwoven fabric base material of Comparative Example 5 shown in Table 3 was produced by passing it through min.
実施例及び比較例の不織布基材について、下記の評価を行い、その結果を表３に示した。 The following evaluation was performed about the nonwoven fabric base material of the Example and the comparative example, and the result was shown in Table 3.
［不織布基材の厚み］
ＪＩＳ Ｃ２１１１に準拠して１試料について５ヶ所以上基材の厚みを測定し、その平均値を算出した。
[Thickness of nonwoven fabric substrate]
In accordance with JIS C2111, the thickness of the substrate was measured at five or more locations for one sample, and the average value was calculated.
［不織布基材の密度］
ＪＩＳ Ｐ８１２４に準拠して基材の坪量を測定し、坪量を厚みで除した値を密度とした。
[Nonwoven fabric substrate density]
The basis weight of the substrate was measured according to JIS P8124, and the value obtained by dividing the basis weight by the thickness was defined as the density.
［引張強度］
実施例及び比較例の不織布基材を流れ方向に長辺がくるように５０ｍｍ巾、２００ｍｍ長に切り取り、試験片を卓上型材料試験機（商品名：ＳＴＡ−１１５０、（株）オリエンテック製）を用いて、つかみ間隔１００ｍｍ、引張速度３００ｍｍ／分の条件で伸長し、切断時の荷重値を引張強度とした。１試料について５ヶ所以上引張強度を測定し、全測定値の平均値を表に示した。
[Tensile strength]
The nonwoven fabric substrates of Examples and Comparative Examples were cut to a width of 50 mm and a length of 200 mm so that the long side was in the flow direction, and the test piece was a desktop material testing machine (trade name: STA-1150, manufactured by Orientec Co., Ltd.) Was used under the conditions of a grip interval of 100 mm and a tensile speed of 300 mm / min, and the load value at the time of cutting was taken as the tensile strength. Ten or more tensile strengths were measured for one sample, and the average value of all measured values was shown in the table.
［塗液の裏抜け評価］
体積平均粒子径０．９μｍ、ＢＥＴ比表面積５．５ｍ２／ｇのベーマイト１００質量部を、水１５０質量部に分散したものに、その１質量％水溶液の２５℃における粘度が２００ｍＰａ・ｓのカルボキシメチルセルロースナトリウム塩２質量％水溶液７５質量部を添加・攪拌混合し、ガラス転移点−１８℃、体積平均粒子径０．２μｍのカルボキシ変性スチレン−ブタジエン共重合樹脂エマルション（固形分濃度５０質量％）１０部を添加・攪拌混合し、最後に調整水を加えて固形分濃度を２５質量％に調整し、塗液Ａを作製した。実施例及び比較例の不織布基材のゴムロール面に、塗工装置としてリバースグラビアコーターを用い、３０ｍ／ｍｉｎのライン速度にて、塗液Ａを、液としての付着量が４７ｇ／ｍ２となるように片面塗工した。塗工された基材は、リバースグラビアコーターに直結されたフローティングエアドライヤーで、９０℃の熱風を吹き付けて乾燥させ、セパレータを得た。「塗液の裏抜け」の評価として、塗工装置のガイドロール及びフローティングエアドライヤー内部への塗工液の付着状態により、次の３段階に分類した。
[Evaluation of strikethrough of coating liquid]
A 100% part by weight boehmite having a volume average particle size of 0.9 μm and a BET specific surface area of 5.5 m 2 / g is dispersed in 150 parts by weight of water. 75 parts by mass of a 2% by weight aqueous solution of methylcellulose sodium salt was added and stirred and mixed, and a carboxy-modified styrene-butadiene copolymer resin emulsion having a glass transition point of -18 ° C. and a volume average particle size of 0.2 μm (solid content concentration: 50% by mass) 10 Part was added and stirred and mixed, and finally adjusted water was added to adjust the solid content concentration to 25% by mass to prepare a coating liquid A. Using a reverse gravure coater as a coating apparatus on the rubber roll surface of the nonwoven fabric base material of the example and the comparative example, the coating liquid A becomes a deposition amount of 47 g / m 2 at a line speed of 30 m / min. So that one side was coated. The coated substrate was dried by blowing hot air at 90 ° C. with a floating air dryer directly connected to a reverse gravure coater to obtain a separator. As the evaluation of “through-through of coating liquid”, the coating liquid was classified into the following three stages depending on the state of adhesion of the coating liquid to the inside of the guide roll and floating air dryer of the coating apparatus.
○：ガイドロールまたはフローティングエアドライヤー内部への塗工液の付着がほとんど無い。
△：ガイドロールまたはフローティングエアドライヤー内部に塗工液が付着しているが、セパレータに再転写はしない。
×：裏抜けした塗工液がガイドロールまたはフローティングエアドライヤー内部に付着しており、得られたセパレータに再転写による面の不均一性が生じている。
○: Almost no coating liquid adheres to the inside of the guide roll or floating air dryer.
Δ: The coating liquid adheres inside the guide roll or floating air dryer, but is not retransferred to the separator.
X: The coating liquid which penetrated has adhered to the inside of a guide roll or a floating air dryer, and the nonuniformity of the surface by retransfer has arisen in the obtained separator.
［塗工時の破断評価］
前記の塗液の裏抜け評価の際に、「塗工時の破断」の評価として、不織布基材の破断状況により、次の３段階に分類した。
[Evaluation of fracture during coating]
In the evaluation of the strike through of the coating liquid, the evaluation of “breakage during coating” was classified into the following three stages according to the breakage of the nonwoven fabric substrate.
○：不織布基材１０００ｍに塗工した際に、不織布基材が破断し、不良が生じた回数が０回の場合。
△：不織布基材１０００ｍに塗工した際に、不織布基材が破断し、不良が生じた回数が１〜２回の場合。
×：不織布基材１０００ｍに塗工した際に、不織布基材が破断し、不良が生じた回数が３回以上の場合。
◯: When the nonwoven fabric base material is broken when the nonwoven fabric base material 1000m is coated, and the number of times of failure is zero.
(Triangle | delta): When the nonwoven fabric base material 1000m is coated, when a nonwoven fabric base material fractures | ruptures and the frequency | count that the defect arose is 1-2 times.
X: When the number of times that the nonwoven fabric substrate broke and a defect occurred when applied to the nonwoven fabric substrate 1000 m was 3 times or more.
表３に示した通り、実施例１〜１１で作製した不織布基材は、ポリエチレンテレフタレートを主体としてなり、厚み３０μｍ以下、坪量／厚みで定義される密度が０．５５ｇ／ｃｍ３以下、引張強度が８００Ｎ／ｍ以上であることから、無機顔料の塗液を塗工した際の裏抜けが少なく、塗工操作における破断等が生じにくいことから、高い生産性で不織布基材に無機顔料を塗工したリチウムイオン二次電池セパレータを製造することができ、優れていた。 As shown in Table 3, the nonwoven fabric base materials produced in Examples 1 to 11 are mainly composed of polyethylene terephthalate, the thickness is 30 μm or less, and the density defined by basis weight / thickness is 0.55 g / cm 3 or less. Since the strength is 800 N / m or more, there are few see-throughs when an inorganic pigment coating solution is applied, and breakage in the coating operation is less likely to occur. The coated lithium ion secondary battery separator could be manufactured and was excellent.
すなわち、ポリエチレンテレフタレート繊維を主体としてなる不織布基材の密度が０．５５ｇ／ｃｍ３以下であることによって、塗液を不織布基材内部に保持する能力が高くなり、塗液の裏抜けを生じにくくすることができる。また、引張強度が８００Ｎ／ｍ以上であることによって、塗工操作における破断等が生じにくく、生産性を高くすることができる。 That is, when the density of the nonwoven fabric substrate mainly composed of polyethylene terephthalate fiber is 0.55 g / cm 3 or less, the ability to hold the coating liquid inside the nonwoven fabric substrate is increased, and the back-through of the coating liquid is unlikely to occur. can do. Moreover, when the tensile strength is 800 N / m or more, breakage or the like in the coating operation hardly occurs, and productivity can be increased.
一方、比較例１、４で作製した不織布基材は、密度が０．５５ｇ／ｃｍ３より高いことから、塗液を不織布基材内部に保持する能力が不十分となり、塗液の裏抜けが見られた。比較例２、５で作製した不織布基材は、引張強度が８００Ｎ／ｍよりも弱いため、塗工操作における破断等が生じやすく、生産性に劣っていた。比較例３で作製した不織布基材は、厚みが３０μｍよりも厚いため、セパレータの厚みを薄くすることが困難となる。 On the other hand, since the non-woven fabric base material produced in Comparative Examples 1 and 4 has a density higher than 0.55 g / cm 3 , the ability to hold the coating liquid inside the non-woven fabric base becomes insufficient, and the back-through of the coating liquid occurs. It was seen. Since the nonwoven fabric base materials produced in Comparative Examples 2 and 5 had a tensile strength weaker than 800 N / m, breakage and the like in the coating operation were likely to occur, and the productivity was poor. Since the nonwoven fabric base material produced in Comparative Example 3 is thicker than 30 μm, it is difficult to reduce the thickness of the separator.
比較例４、５で作製した不織布基材は、加熱された金属ロールと、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が８０よりも高いロールを用いて処理しているが、不織布基材の密度が高くなり過ぎたり、引張強度が弱くなり過ぎたりし、密度が０．５５ｇ／ｃｍ３以下、かつ引張強度が８００Ｎ／ｍ以上とすることが難しかった。 Although the nonwoven fabric base material produced by the comparative examples 4 and 5 is processed using the heated metal roll and the roll whose hardness measured by durometer A prescribed | regulated to JISK6253 is higher than 80, The density of the material became too high or the tensile strength became too weak, and it was difficult to make the density 0.55 g / cm 3 or less and the tensile strength 800 N / m or more.
実施例６で作製した不織布基材は、密度がやや低いことから、引張強度がやや弱く、実施例１〜５、７、１０の不織布基材に比べ、塗工時における破断がやや生じやすかった。 Since the non-woven fabric substrate produced in Example 6 has a slightly lower density, the tensile strength is slightly weaker, and the breakage during coating is slightly more likely to occur than in the non-woven fabric substrates of Examples 1 to 5, 7, and 10. .
実施例７で作製した不織布基材は、密度が０．５５ｇ／ｃｍ３とやや高いことから、実施例１〜６、８〜１１の不織布基材に比べ、塗液の裏抜けがやや多く見られた。 Since the non-woven fabric base material produced in Example 7 has a density as high as 0.55 g / cm 3 , the see-through of the coating liquid is slightly larger than those of the non-woven fabric base materials of Examples 1 to 6 and 8 to 11. It was.
実施例８で作製した不織布基材は、ＪＩＳ Ｋ６２５３に規定されるデュロメータＡにより測定される硬度が４５のロールを用いて処理しているが、引張強度がやや弱く、実施例１〜５、７、１０の不織布基材に比べ、塗工時における破断がやや生じやすかった。 Although the nonwoven fabric base material produced in Example 8 is processed using the roll whose hardness measured by durometer A prescribed | regulated to JISK6253 is 45, tensile strength is a little weak, Examples 1-5, 7 Compared to 10 nonwoven fabric substrates, breakage during coating was slightly more likely to occur.
実施例９で作製した不織布基材は、引張強度が８００Ｎ／ｍとやや弱いため、実施例１〜５、７、１０の不織布基材に比べ、塗工時における破断がやや生じやすかった。 Since the nonwoven fabric base material produced in Example 9 had a slightly weak tensile strength of 800 N / m, it was slightly easier to break during coating than the nonwoven fabric base materials of Examples 1 to 5, 7 and 10.
実施例１１で作製した不織布基材は、厚みがやや薄いことから、引張強度がやや弱く、実施例１〜５、７、１０の不織布基材に比べ、塗工時における破断がやや生じやすかった。 Since the nonwoven fabric base material produced in Example 11 was somewhat thin, the tensile strength was slightly weak, and the breakage during coating was slightly more likely to occur than the nonwoven fabric base materials of Examples 1-5, 7, and 10. .
本発明の活用例としては、リチウムイオン二次電池セパレータ用不織布基材が好適である。 As an application example of the present invention, a nonwoven fabric base material for a lithium ion secondary battery separator is suitable.
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