JPS5851389B2 - Manufacturing method of battery separator - Google Patents
Manufacturing method of battery separatorInfo
- Publication number
- JPS5851389B2 JPS5851389B2 JP52016109A JP1610977A JPS5851389B2 JP S5851389 B2 JPS5851389 B2 JP S5851389B2 JP 52016109 A JP52016109 A JP 52016109A JP 1610977 A JP1610977 A JP 1610977A JP S5851389 B2 JPS5851389 B2 JP S5851389B2
- Authority
- JP
- Japan
- Prior art keywords
- volumes
- porous membrane
- weight
- acid
- organic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【発明の詳細な説明】
本発明は、実質的にポリオレフィン樹脂と無機微粉体と
耐酸性有機物からなり、微細な孔を多数有し、機械的強
度に優れた多孔膜を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a porous membrane that is substantially composed of a polyolefin resin, an inorganic fine powder, and an acid-resistant organic substance, has many fine pores, and has excellent mechanical strength. be.
特に本発明は、水湿潤性と、電解液中での低い電気抵抗
を備え、かつ優れた耐久性(耐酸化性、耐酸性)をもつ
電池隔離板を製造する方法に関するものである。In particular, the present invention relates to a method for producing a battery separator with water wettability, low electrical resistance in an electrolyte, and excellent durability (oxidation resistance, acid resistance).
鉛蓄電池の隔離板は、使用時には温度70〜80℃、濃
度30〜40φの硫酸中に浸漬され、かつ充電時には陽
極から発生する酸素により酸化雰囲気に曝される。During use, the separator of a lead-acid battery is immersed in sulfuric acid at a temperature of 70 to 80° C. and a concentration of 30 to 40 φ, and during charging it is exposed to an oxidizing atmosphere due to oxygen generated from the anode.
このために電池用隔離板は、これに耐えうる慶れた耐酸
化性、耐酸性が要求される。For this reason, battery separators are required to have excellent oxidation and acid resistance to withstand this.
従来より鉛蓄電池用隔離板としては、(1)塩化ビニル
樹脂を焼結したもの、(2)シート状のリンターパルプ
にフェノール樹脂を含浸処理したもの、(3)塩化ビニ
ル樹脂、溶剤、非溶剤からなる溶液を不織布に含浸、乾
燥し、多孔体としたもの等があるが、これらはいずれも
耐久性について満足されるものではない。Conventional separators for lead-acid batteries include (1) sintered vinyl chloride resin, (2) sheet-like linter pulp impregnated with phenolic resin, and (3) vinyl chloride resin, solvent, and non-solvent. There is a method in which a nonwoven fabric is impregnated with a solution of the above-mentioned material and dried to form a porous material, but none of these methods are satisfactory in terms of durability.
また、耐久性を有する隔離板として、(4)ゴムラテッ
クスにデンプン、硫黄、加硫促進剤を混合、加硫後デン
プンを溶出せしめたもの、(5)MI=00ポリオレフ
ィン樹脂、シリカ、プロセスオイルの混合物をシート状
に溶融成形した後、プロセスオイルを抽出せしめたもの
(特公昭45−32097号)がある。In addition, as a durable separator, (4) rubber latex mixed with starch, sulfur, and a vulcanization accelerator, and the starch eluted after vulcanization, (5) MI=00 polyolefin resin, silica, and process oil. There is a method (Japanese Patent Publication No. 45-32097) in which a mixture of the following is melt-molded into a sheet shape and then the process oil is extracted.
しかしながら、(4)、(5)ともに電気抵抗が高いと
いう欠点を持っている。However, both (4) and (5) have the disadvantage of high electrical resistance.
本発明者らは、低い電気抵抗と優れた耐久性の両者を兼
ね備えた電池用隔離板を実現するために鋭意研究を重ね
た結果、従来技術の1/3〜1/10である0、001
Ωdi/枚以下の低い電気抵抗と、従来技術の最高レベ
ルの耐久性を兼ね備えた電池用隔離板の製造方法を発明
するに至つ九
本発明の特徴は、限定された溶解度係数(SP値)の有
機液状体を被抽出剤として用いて、低電気抵抗の多孔膜
を製造し、か〜る多孔膜に耐酸性有機物を付着せしめ、
低電気抵抗を損うことなく。The inventors of the present invention have conducted intensive research to realize a battery separator that has both low electrical resistance and excellent durability.
We have invented a method for manufacturing a battery separator that has a low electrical resistance of less than Ωdi/sheet and the highest level of durability of the conventional technology.The features of the present invention are a limited solubility coefficient (SP value) Producing a porous membrane with low electrical resistance using the organic liquid as an extractant, and adhering an acid-resistant organic substance to the porous membrane,
without compromising low electrical resistance.
優れた耐久性を賦与することにある。The purpose is to provide excellent durability.
本発明の類似技術として特公昭45−32097号があ
る。Japanese Patent Publication No. 45-32097 is a similar technique to the present invention.
これには耐酸性有機物の一つであるプロセスオイルを被
抽出剤として使用し、この被抽出剤を膜中に残存させる
場合があることが開示されている。This document discloses that process oil, which is one of the acid-resistant organic substances, is used as an extractable agent, and that this extractable agent may remain in the membrane.
しかしながら、プロセスオイルのSP値は8.4以下で
、ポリオレフィン樹脂のSP値と接近しており、この結
果、プロセスオイルの大半は樹脂中に溶解し、これを抽
出した際の空孔形成性が悪いため、電気抵抗は高いもの
となってしまう。However, the SP value of the process oil is 8.4 or less, which is close to the SP value of the polyolefin resin. As a result, most of the process oil is dissolved in the resin, and when extracted, the pore-forming property is low. As a result, the electrical resistance becomes high.
ところが、本発明によれば、抽出の際の空孔形成性の高
いSP値8.4〜9.9の有機液状体を被抽出剤として
用いることにより、充分な機械的強度と柔軟性、高い空
孔度と極めて低い電気抵抗を賦与し、さらにかかる多孔
膜に2〜15重量多重量酸性有機物を付着せしめること
により、機械的強度、柔軟性、水湿潤性、低い電気抵抗
を実質的に損うことなく、極めて優れた耐久性が賦与さ
れるものである。However, according to the present invention, by using an organic liquid with a SP value of 8.4 to 9.9, which has a high pore-forming property during extraction, as an extractant, sufficient mechanical strength, flexibility, and high By imparting porosity and extremely low electrical resistance, and further adhering 2 to 15% heavy weight acidic organic material to such porous membranes, mechanical strength, flexibility, water wettability, and low electrical resistance are substantially compromised. It provides extremely excellent durability without any damage.
このように本発明は、特公昭45−3209号とは明ら
かに発想を異にした技術に基き、低い電気抵抗と優れた
耐久性の両者を兼備した電池用隔離板の製造方法に関す
るものである。As described above, the present invention is based on a technology clearly different from that of Japanese Patent Publication No. 45-3209, and relates to a method for manufacturing a battery separator that has both low electrical resistance and excellent durability. .
本発明による耐久性Vclilれた電池隔離板とは、J
IS−C−2311に定められた耐酸化試験法において
、少くとも短絡時間100時間以上、かつ耐酸化試験を
48時間行なった後の隔離板の破断伸びが50%以上の
耐久性を保存するものである。The durable Vclil battery separator according to the present invention is J
According to the oxidation resistance test method specified in IS-C-2311, the separator maintains durability with a short circuit time of 100 hours or more and an elongation at break of 50% or more after conducting the oxidation resistance test for 48 hours. It is.
本発明に用いられる耐酸性有機物は、多孔膜に付着し、
かムる多孔膜に耐久性を賦与するものである。The acid-resistant organic substance used in the present invention adheres to the porous membrane,
This imparts durability to the porous membrane.
耐酸性有機物は、本発明実施例1により製造された気孔
率約55%の多孔性膜状物に約10重量多付着せしめ、
80℃、40重量多硫酸液に5日間浸漬して、付着量の
少くとも50%が硫酸に溶解することなく膜中に残存す
るものに限定される。The acid-resistant organic substance was attached to the porous film-like material with a porosity of about 55% produced according to Example 1 of the present invention in an amount of about 10% by weight,
The film is limited to one in which at least 50% of the deposited amount remains in the film without being dissolved in the sulfuric acid after being immersed in a 40 weight polysulfuric acid solution at 80°C for 5 days.
また耐酸性有機物は溶剤に溶解するものであれば、液体
でも固体であってもよい。Further, the acid-resistant organic substance may be either liquid or solid as long as it dissolves in the solvent.
か瓦る耐酸性有機物は、多孔膜に膜状物重量の2〜15
重量φ重量型しくは3〜10重量多付着される。The acid-resistant organic substance that will cause damage should be added to the porous membrane in an amount of 2 to 15% of the weight of the membrane.
Weight φ weight type or 3 to 10 weight more is attached.
2重量φ未満の付着量では、膜状物の耐久性は改善され
ず、耐酸化試験では短絡は100時間以上起らないが、
48時間後の破断伸びは50%以下と脆くなり、実用上
問題となる。If the coating amount is less than 2 weight φ, the durability of the film will not be improved, and short circuits will not occur for more than 100 hours in the oxidation resistance test, but
The elongation at break after 48 hours is less than 50%, which is brittle and causes a practical problem.
また、15重重量上りも多く付着させると、気孔率が低
下し、電気抵抗が高くなるとともに、耐酸性有機物が遊
離しやすく、かつ水湿潤性が悪化するため好ましくない
。Furthermore, if a large amount of 15% weight is deposited, the porosity decreases, the electrical resistance increases, acid-resistant organic substances tend to be liberated, and water wettability deteriorates, which is not preferable.
本発明に用いられる耐酸性有機物としては、ゴム、プラ
スチックの可塑斉]、軟化剤、粘着賦与剤等として用い
られる一般的な有機化合物で充分である。As the acid-resistant organic substance used in the present invention, general organic compounds used as plasticizers for rubber and plastics, softeners, tackifiers, etc. are sufficient.
例としては、大豆油、ナタネ油、鯨油等の油脂類、コー
ルタール、ピッチ、クロマン−インデン樹脂等のタール
製品、パラフィン系、ナフテン系、アロマ系プロセスオ
イル、スピンドル油等の潤滑油、流動パラフィン、石油
アスファルト、石油樹脂等の石油製品が挙げられる。Examples include oils and fats such as soybean oil, rapeseed oil, and whale oil; tar products such as coal tar, pitch, and chroman-indene resin; lubricating oils such as paraffinic, naphthenic, and aromatic process oils; and spindle oil; and liquid paraffin. , petroleum products such as petroleum asphalt and petroleum resin.
しかし、先の耐酸性の条件を満すものであれば、これに
限定されるものではない。However, it is not limited to this as long as it satisfies the acid resistance conditions mentioned above.
ポリオレフィン樹脂は、数平均分子量(Mn)が150
00以上であることが必要であり、好ましくは1700
0以上である。The polyolefin resin has a number average molecular weight (Mn) of 150
00 or more, preferably 1700
It is 0 or more.
屓nが15000未満のポリオレフィン樹脂を用いた場
合、得られる多孔性膜状物は、破断伸びが50%以下と
なり、脆く実用に供することができない。When a polyolefin resin having a thickness n of less than 15,000 is used, the resulting porous film has an elongation at break of 50% or less, and is too brittle to be put to practical use.
また、ポリオレフィン樹脂の重量平均分子量(Mw)は
600000以下であることが必要である。Further, the weight average molecular weight (Mw) of the polyolefin resin needs to be 600,000 or less.
Mvrの下限はMnm15000を満たすものであれば
、特に限定されるものではないが、実質的には7000
0以上であることが好ましい。The lower limit of Mvr is not particularly limited as long as it satisfies Mnm15000, but it is practically 7000.
It is preferable that it is 0 or more.
Mwが600000を超えると、Q、3m/m以下の膜
厚の成形が難しく、かつ単位厚み当りの電気抵抗が上昇
するため、0.001Ωd??Z2/枚以下の低い電気
抵抗のものを得ることは困難である。When Mw exceeds 600,000, it is difficult to form a film with a thickness of 3 m/m or less, and the electrical resistance per unit thickness increases, so 0.001 Ωd? ? It is difficult to obtain a low electrical resistance of Z2/sheet or less.
特に0.0006Ωd??Z2/枚以下の極めて低い電
気抵抗の隔離板を得るためには、Mwが300000未
満であることが好ましい。Especially 0.0006Ωd? ? In order to obtain a separator with extremely low electrical resistance of Z2/sheet or less, it is preferable that Mw is less than 300,000.
本発明におけるポリオレフィン樹脂としとは、Mw46
00000、MnTh15000の範囲のものであれば
、ポリエチレン、ポリプロピレン、ポリブテンおよびこ
れらの混合物、またはエチレン、プロピレン、ブテン、
ヘキサンの二種以上の共重合物であってもよい。The polyolefin resin in the present invention is Mw46
00000, MnTh15000, polyethylene, polypropylene, polybutene and mixtures thereof, or ethylene, propylene, butene,
It may also be a copolymer of two or more types of hexane.
これらの樹脂のうち、ポリエチレンまたはエチレンが主
なる共重合体が特に好ましい。Among these resins, polyethylene or a copolymer mainly composed of ethylene is particularly preferred.
無機微粉体は有機液状体を保持し、担体としての機能を
持つものである。The inorganic fine powder holds the organic liquid and functions as a carrier.
即ち、溶融成形時に有機液状体の遊離を防止し、成形を
容易にするものである。That is, it prevents the release of organic liquid during melt molding and facilitates molding.
さらに無機微粉体は多孔膜に水湿潤性を賦与するもので
ある。Furthermore, the inorganic fine powder imparts water wettability to the porous membrane.
無機微粉体は平均ね径0.005〜0.5μ、比表面積
50〜500??Z2/rの範囲にある微小粒子または
多孔性粒子であることが好ましい。The inorganic fine powder has an average diameter of 0.005 to 0.5μ and a specific surface area of 50 to 500? ? Preferably, the particles are microparticles or porous particles in the range of Z2/r.
さらに無機微粉体は有機液状体を少くとも273倍容量
、好ましくは3倍容量以上を吸収し、粉末または顆粒状
態を保つことが好ましい。Further, it is preferable that the inorganic fine powder absorbs at least 273 times the volume of the organic liquid, preferably 3 times the volume or more, and maintains a powder or granule state.
また無機微粉体は一種で用いる場合は必ず親水性であり
、二種以上を混合して用いる場合は少くとも一種が親水
性である。Further, when one type of inorganic fine powder is used, it is always hydrophilic, and when two or more types are used in combination, at least one type is hydrophilic.
本発明に用いられる無機微粉体の例としては、微粉珪酸
、珪酸カルシウム、珪酸アルミニウム、アルミナ、炭酸
カルシウム、炭酸マグネシウム、カオリンクレー、微粉
タルク、酸化チタン、珪藻土、カーボンブラック等が挙
げられる。Examples of the inorganic fine powder used in the present invention include finely divided silicic acid, calcium silicate, aluminum silicate, alumina, calcium carbonate, magnesium carbonate, kaolin clay, finely divided talc, titanium oxide, diatomaceous earth, and carbon black.
鉛蓄電池用隔離板の用途には微粉珪酸が特に有効である
。Finely divided silicic acid is particularly effective for use as separators for lead-acid batteries.
しかしながら、これに限定されるものではない。However, it is not limited to this.
本発明に用いられる有機液状体は成形物中より抽出され
、成形物に多孔性を賦与するものである。The organic liquid used in the present invention is extracted from the molded product and imparts porosity to the molded product.
有機液状体は溶融成形時に液体であり、かつ不活性であ
ることが要求される。The organic liquid is required to be liquid and inert during melt molding.
さらに有機液状体はSP値が8.4〜9.9の範囲のも
のでなくてはならない。Furthermore, the organic liquid must have an SP value in the range of 8.4 to 9.9.
この範囲のものを用いることにより溶融成形時、有機液
状体は適度にポリオレフィン樹脂中に溶解し、かつ大半
が無機微粉体表面に吸着した状態を形成する。By using a material within this range, during melt molding, the organic liquid is appropriately dissolved in the polyolefin resin, and most of the organic liquid is adsorbed on the surface of the inorganic fine powder.
この結果、良好な成形性、抽出性、機械的強度、低電気
抵抗の多孔膜が得られる。As a result, a porous membrane with good moldability, extractability, mechanical strength, and low electrical resistance can be obtained.
有機液状体のSP値が9.9を超えると、樹脂への溶解
性が低下し、成形時に遊離する。When the SP value of the organic liquid exceeds 9.9, the solubility in the resin decreases and the organic liquid becomes liberated during molding.
このため樹脂同志の溶着が妨げられ、成形性が悪化し、
かつポリオレフィン樹脂の網状構造の平均開孔径が0.
5μ以上に粗大となり、強伸度が低下する。This prevents welding of resins together, resulting in poor moldability.
and the average pore diameter of the network structure of the polyolefin resin is 0.
It becomes coarse when it is 5μ or more, and its strength and elongation decrease.
またSP値が8.4未満であると、ポリオレフィン樹脂
への溶解量が増加し、無機微粉体への吸着量が小さくな
る。Moreover, when the SP value is less than 8.4, the amount dissolved in the polyolefin resin increases and the amount adsorbed to the inorganic fine powder becomes small.
この結果、溶融物の溶着は充分に行なわれ、成形性、機
械的強度は向上する反面、有機液状体の空孔形成のため
の寄与率が低下し、多孔膜の気孔率が低下する。As a result, the melt is sufficiently welded and the moldability and mechanical strength are improved, but the contribution rate of the organic liquid to the formation of pores is reduced, and the porosity of the porous membrane is reduced.
さらに抽出性が悪化し、抽出時間も増加する。Furthermore, the extractability deteriorates and the extraction time also increases.
本発明に用いられるSP値が8.4〜9.9の有機液状
体の例として(九フタル酸ジエチル(DEP)、フタル
酸ジプチル(DBP)、フタル酸ジオクチル(DOP)
等のフタル酸エステル、セバシン酸ジオクチル(DO8
)等のセバシン酸エステル、アジピン酸ジオクチル等の
アジピン酸エステル、トリメリット酸トリオクチル(T
OTM)等のトリメット酸エステル、リン酸トリブチル
(TBP)、リン酸オクチルジフェニル等のリン酸エス
テル、ポリエチレングリコール等のグリコール類が挙げ
られる。Examples of organic liquids with SP values of 8.4 to 9.9 used in the present invention include diethyl nine phthalate (DEP), diptyl phthalate (DBP), and dioctyl phthalate (DOP).
Phthalate esters such as dioctyl sebacate (DO8
), adipate esters such as dioctyl adipate, trioctyl trimellitate (T
Examples include trimethic acid esters such as OTM), phosphoric acid esters such as tributyl phosphate (TBP) and octyldiphenyl phosphate, and glycols such as polyethylene glycol.
本発明の製造方法をさらに詳しく説明する。The manufacturing method of the present invention will be explained in more detail.
無機微粉体、有機液状体およびポリオレフィン樹脂の合
計容量に対して、7〜42容量優、好ましくは10〜2
0容量優の無機微粉体、30〜75容量多、好ましくは
50〜70容量φの有機液状体、10〜60容量宏好ま
しくは15〜40容量多のポリオレフィン樹脂の三者を
混合する。7 to 42 volumes, preferably 10 to 2 volumes, based on the total volume of the inorganic fine powder, organic liquid, and polyolefin resin.
The following three materials are mixed: an inorganic fine powder with a volume of more than 0, an organic liquid with a volume of 30 to 75, preferably 50 to 70, and a polyolefin resin with a volume of 10 to 60, preferably 15 to 40.
この時、無機微粉体量が7容量φ未満では、有効な多孔
膜を作るのに必要な有機液状体を吸着することができず
、混合物は粉末または顆粒状態を保つことができず、成
形が困難となる。At this time, if the amount of inorganic fine powder is less than 7 volumes φ, it will not be possible to adsorb the organic liquid necessary to make an effective porous membrane, the mixture will not be able to maintain a powder or granule state, and molding will be difficult. It becomes difficult.
一方、42容量多を超えると溶融時の流動性が悪く、か
つ得られる成形品は脆く実用に供することができない。On the other hand, if the volume exceeds 42, the fluidity during melting will be poor and the resulting molded product will be brittle and cannot be put to practical use.
また有機液状体の量は30容量多未満では、有機液状体
の空孔形成に対する寄与率が低下し、得られる多孔膜の
空孔度は30条を下まわり、実質的に多孔膜として有効
なものが得られない。Furthermore, if the amount of the organic liquid is less than 30 by volume, the contribution rate of the organic liquid to the formation of pores decreases, and the porosity of the obtained porous membrane is less than 30, making it substantially ineffective as a porous membrane. I can't get anything.
一方、75容量条な超えると成形が困難となり、機械的
強度の高い多孔膜は得られない。On the other hand, if it exceeds 75 volumes, molding becomes difficult and a porous membrane with high mechanical strength cannot be obtained.
ポリオレフィン樹脂が10容量多未満では、樹脂が少な
すぎて強度が小さく、成形性も悪い。If the polyolefin resin is less than 10 volumes, the resin is too small, resulting in low strength and poor moldability.
60容量優を超えると、空孔度の大きい多孔膜が得られ
ず好ましくない。If the volume exceeds 60, a porous membrane with high porosity cannot be obtained, which is not preferable.
本発明に供せられる配合物は、主にポリオレフィン樹脂
、無機微粉体、有機液状体の三者により構成される。The composition used in the present invention is mainly composed of three components: a polyolefin resin, an inorganic fine powder, and an organic liquid.
しかしながら、他に本発明の効果を大きく阻害しない範
囲で、滑剤、酸化防止剤、紫外線吸収剤、可塑剤、成形
助剤等を必要に応じて添加することは何ら差支えない。However, there is no problem in adding other lubricants, antioxidants, ultraviolet absorbers, plasticizers, molding aids, etc. as necessary, as long as they do not significantly impair the effects of the present invention.
これら三成分の混合には、ヘンシェルミキサーソーブレ
ンダ−、リボンブレンダー等の配合機を用いた通常の混
合法で充分である。For mixing these three components, a conventional mixing method using a blender such as a Henschel mixer saw blender or ribbon blender is sufficient.
この混合物は、押出機、バンバリーミキサ−1二本ロー
ル、ニーダ−等の溶融混線装置により混練される。This mixture is kneaded using a melt mixing device such as an extruder, a Banbury mixer with 1 and 2 rolls, or a kneader.
得られる混線物は、溶融成形方法により膜状に成形され
るが、本発明方法に用いられる溶融成形方法としては、
Tダイ法やインフレーション法等の押出成形、カレンダ
ー成形、圧扁成形、射出成形等がある。The obtained mixed wire is formed into a film shape by a melt molding method, and the melt molding method used in the method of the present invention is as follows.
Examples include extrusion molding such as the T-die method and inflation method, calendar molding, compression molding, and injection molding.
また混合物を押出機、ニーダ−ルーダ−等の混線押出両
機能を有する装置により、直接成形することも可能であ
る。It is also possible to directly mold the mixture using an extruder, kneader-ruder, or other device having both cross-wire extrusion and extrusion functions.
これらの成形法により三成分混合物は0.05〜1%の
膜状物に成形される。These molding methods mold the ternary mixture into a 0.05-1% film.
特に0.10〜0.30%の薄膜成形にはTダイ法押出
成形が特に有効である。In particular, T-die extrusion molding is particularly effective for forming thin films of 0.10 to 0.30%.
得られた膜状成形物からポリオレフィン樹脂の融点以下
の温度にて、用いられた有機液状体の溶剤を用いて有機
液状体の抽出を行なう。The organic liquid is extracted from the obtained film-like molded product at a temperature below the melting point of the polyolefin resin using a solvent for the organic liquid used.
但し、該溶剤はポリオレフィン樹脂を実質的に溶解する
ものであってはならない。However, the solvent must not substantially dissolve the polyolefin resin.
抽出は回分法や向流多段法等の膜状物の一般的な抽出方
法により容易に行なわれる。Extraction is easily carried out using common extraction methods for membrane-like materials, such as a batch method or a countercurrent multi-stage method.
抽出に用いられる溶剤としては、メタノール、エタノー
ル、イソプロピルアルコール等のアルコール類、アセト
ン等のケトン類、Ll。Solvents used for extraction include alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone, and Ll.
1−トリクロルエタン、トリクロルエチレン等の塩素化
炭化水素類のような一般的な溶剤で充分である。Common solvents such as chlorinated hydrocarbons such as 1-trichloroethane, trichlorethylene, etc. are sufficient.
また抽出を終了した多孔膜には、有機液状体が膜の性能
をそこなわない範囲で残存することが許される。Further, the organic liquid is allowed to remain in the porous membrane after extraction to the extent that it does not impair the performance of the membrane.
しかし、残存量が大きいと膜の気孔率が低下するために
好ましくない。However, if the residual amount is large, the porosity of the membrane decreases, which is not preferable.
有機液状体の多孔膜中での残存量は5容量多以下、好ま
しくは2%以下である。The amount of organic liquid remaining in the porous membrane is 5 volumes or less, preferably 2% or less.
抽出が終了した多孔膜は、抽出に用いられた溶剤を含ん
だま〜か、あるいは乾燥除去した後、耐酸性有機物の含
浸付着工程へ供される。After the extraction has been completed, the porous membrane contains the solvent used for the extraction, or after drying and removing it, it is subjected to an impregnating and adhering step with an acid-resistant organic substance.
多孔膜への耐酸性有機物の付着は、浸漬法、噴霧法、コ
ーティング法等一般的な含浸方法により容易に行なわれ
る。The acid-resistant organic substance can be easily attached to the porous membrane by a general impregnation method such as a dipping method, a spraying method, or a coating method.
含浸液は、耐酸性有機物100%あるいはその溶剤との
混合溶液である。The impregnating liquid is a 100% acid-resistant organic substance or a mixed solution thereof with a solvent.
また耐酸性有機物の溶剤は、ポリオレフィン樹脂を実質
的に溶解するものであってはならない。Further, the acid-resistant organic solvent must not substantially dissolve the polyolefin resin.
溶剤の例としては、メタノール、イソプロピルアルコー
ル等のアルコール類、アセトン、MEK等のケトン類、
1,1,1−トリクロルエタン、トリクロルエチレン等
の塩素系炭化水素類、n −ヘプタン、n−ヘキサン等
の炭化水素類のような一般的な溶剤である。Examples of solvents include alcohols such as methanol and isopropyl alcohol, ketones such as acetone and MEK,
These are common solvents such as chlorinated hydrocarbons such as 1,1,1-trichloroethane and trichlorethylene, and hydrocarbons such as n-heptane and n-hexane.
含浸が完了した多孔膜は、必要があればポリオレフィン
樹脂の融点以下の温度にて溶剤を乾燥除去する。Once impregnated, the porous membrane is dried to remove the solvent at a temperature below the melting point of the polyolefin resin, if necessary.
乾燥は常圧または減圧下、熱風または加熱ロール等の一
般的な方法によって行なわれる。Drying is carried out under normal pressure or reduced pressure by a common method such as hot air or heated rolls.
本発明によって製造された多孔膜は、実質的にポリオレ
フィン樹脂、無機微粉体、耐酸性有機物の混合物と30
〜75%の空孔によって形成される。The porous membrane produced according to the present invention consists of a mixture of polyolefin resin, inorganic fine powder, and acid-resistant organic material.
Formed by ~75% vacancies.
本発明の多孔膜の組成は、ポリオレフィン樹脂40〜9
0容量優、無機微粉体10〜60容量φ、有機液状体O
〜5容量容量上び耐酸性有機物2〜15重量多重量材着
前の多孔性膜状物重量)からなる。The composition of the porous membrane of the present invention is a polyolefin resin of 40 to 9
0 capacity excellent, inorganic fine powder 10-60 capacity φ, organic liquid O
~5 volume capacity and acid-resistant organic material 2 to 15 weight (weight of porous membrane material before deposition).
電池隔離板等の柔軟性と水湿潤性および耐久性が要求さ
れる用途には、ポリオレフイン樹脂50〜80容量宏無
機微粉体20〜50容量宏有機液状体O〜2容量俤、耐
酸性有機物3〜10重量%(対付着前の多孔性膜状物重
量)の組成範囲のものが好ましい。For applications that require flexibility, water wettability, and durability, such as battery separators, polyolefin resins 50 to 80 volumes, inorganic fine powders 20 to 50 volumes, organic liquids O to 2 volumes, acid-resistant organic substances 3 A composition range of 10% by weight (based on the weight of the porous membrane material before adhesion) is preferred.
また本発明による多孔膜の気孔率は少くとも30〜75
宏蓄電池隔離板等の用途には50〜70%であることが
好ましい。Moreover, the porosity of the porous membrane according to the present invention is at least 30 to 75.
It is preferably 50 to 70% for applications such as Hiroshi storage battery separators.
本発明による多孔膜は0.05〜1%の膜厚を有する。The porous membrane according to the invention has a thickness of 0.05-1%.
充分な膜強度および電気抵抗から、蓄電池隔離板等の用
途にはo、io〜0.30%の膜厚のものが特に好まし
い。In view of sufficient film strength and electrical resistance, a film thickness of o, io to 0.30% is particularly preferred for applications such as storage battery separators.
このように、本発明による多孔膜は微細な網状構造をも
つ高気孔率の薄膜で、良好な機械的強度と優れた柔軟性
を備え、従来になく抜群に低い電気抵抗と、極めて優れ
た耐久性を実現するものであり、本発明の多孔膜を隔離
板として用いることにより、鉛蓄電池は同容量のものに
対し、大巾に性能向上をはかることが可能となった。As described above, the porous film according to the present invention is a thin film with a high porosity and a fine network structure, and has good mechanical strength and excellent flexibility.It also has an extremely low electrical resistance and extremely high durability. By using the porous membrane of the present invention as a separator, it has become possible to significantly improve the performance of lead-acid batteries compared to those of the same capacity.
さらに耐久性と高性能が必要とされる電気自動車用蓄電
池の隔離板としても充分使用できるものである。Furthermore, it can be used satisfactorily as a separator for storage batteries for electric vehicles, which require durability and high performance.
次に本発明の効果を明らかにするために実施例および比
較例を示す。Next, Examples and Comparative Examples will be shown to clarify the effects of the present invention.
しかし、本発明は、これらの実施例によって限定される
ものではない。However, the present invention is not limited to these examples.
なお、本発明の明細書および実施例に示されている諸物
性は次の測定方法によった。In addition, the various physical properties shown in the specification and examples of the present invention were measured by the following measurement method.
重量平均分子量(Mw)
数平均分子量 (Mn)
GPC測定装置−Waters社製Mode1200カ
ラム−東洋ソーダ製G70008〜G3000 S溶剤
〜トリクロルベンゼン
測定温度−135℃
粘度平均分子量(Mv )(Mv v:Mw)溶剤−デ
カリン
測定温度−135℃
[η、l= 6.20X10 Mv””(Chian
gO式)SLMI−00ポリエチレンの重量平均牙子量
は本法により算出しtら
組成比(容量%)
各組成の添加重量を真比重にて除した値から算出d
気孔率(Q
気孔率=空孔容積/多孔膜容積×100
空孔容積=含水重量−絶乾重量
ポリオレフィン網状構造体表面平均開孔径(4)多孔膜
より無機微粉体を抽出除去したポリオレフィン網状構造
体表面の走査型電子顕微鏡写真で観察される開孔部20
0ケの長径と短径の平均を加重平均して算出。Weight average molecular weight (Mw) Number average molecular weight (Mn) GPC measuring device - Waters Model 1200 column - Toyo Soda G70008~G3000 S solvent - Trichlorobenzene measurement temperature - 135°C Viscosity average molecular weight (Mv) (Mv v: Mw) Solvent - Decalin measurement temperature - 135°C [η, l = 6.20X10 Mv"" (Chian
gO formula) The weight average tusk weight of SLMI-00 polyethylene is calculated using this method. t Composition ratio (volume %) Calculated from the value obtained by dividing the added weight of each composition by the true specific gravity d Porosity (Q Porosity = Void Pore volume/Porous membrane volume x 100 Pore volume = Water content - Bone dry weight Polyolefin network structure surface average pore diameter (4) Scanning electron micrograph of the surface of the polyolefin network structure after inorganic fine powder was extracted and removed from the porous membrane Opening 20 observed in
Calculated by weighted average of the long axis and short axis of 0 pieces.
比表面積Crr?/1)
BET吸着法により測定
多孔膜平均孔径(ホ)
次式により算出
2■
d=−d:直径(4)、S=比表面積(yf/7)V:
細孔容積Cml/fl)
破断強さく kV/lt? )、破断伸び(資)インス
トロン型引張試験機によりASTM D−882に準
じて測定。Specific surface area Crr? /1) Porous membrane average pore diameter (e) measured by BET adsorption method Calculated by the following formula 2■ d=-d: diameter (4), S=specific surface area (yf/7) V:
Pore volume Cml/fl) Breaking strength kV/lt? ), elongation at break (capital) measured using an Instron tensile tester in accordance with ASTM D-882.
(歪速度2.0 min/mm ・min )電気抵抗
(Ωdi/枚、Ωdtr?/ 0.1 van )JI
S−C−2313にしたがい測定。(Strain rate 2.0 min/mm ・min) Electrical resistance (Ωdi/sheet, Ωdtr?/0.1 van) JI
Measured according to S-C-2313.
透気度(秒/1007flA)
A S TM D−726Method A により
測定。Air permeability (sec/1007flA) Measured by ASTM D-726Method A.
耐折強さく回)
JIS−P−8115により側床
MIT型試験機 張力0.3hy/15’簡巾SLMI
:
ASTM−D−1238−56T条件Eにより測定
溶解パラメーターC8P値)
次式により算出
dΣG
SP値=□ d:比重
G:モル牽引定数
耐酸化試験
JIS−C−2311にしたがい測定。Folding strength: JIS-P-8115, side floor MIT type testing machine, tension: 0.3hy/15' width, SLMI
: Solubility parameter C8P value measured according to ASTM-D-1238-56T condition E) Calculated using the following formula dΣG SP value=□ d: Specific gravity G: Molar traction constant Oxidation resistance test Measured according to JIS-C-2311.
短絡時間:電圧が0.2■以上低下するか、2.6V以
下になるまでの通電時間。Short-circuit time: The time it takes for the voltage to drop by 0.2■ or more or to become 2.6V or less.
48時間後の破断伸び148時間耐酸化試験を行った後
乾燥し、破断伸びを測定。Elongation at break after 48 hours After conducting an oxidation resistance test for 148 hours, it was dried and the elongation at break was measured.
実施例 1
微粉珪酸〔ニブシルVN−3(商品名)、比表面積28
0rr?/S’、平均ね径16mμ:113.6容量優
と、ジオクチルフタレート(DOP SP値8.9 )
60.8容量優をヘンシェルミキサーで混合し、これ
lcMw=85000、Mn=21000、SLMI=
1のポリエチレン樹脂パウダー(5untec S−3
60P C商品名):125.6容量多を添加、再度ヘ
ンシェルミキサーで混合した。Example 1 Finely divided silicic acid [Nibsil VN-3 (trade name), specific surface area 28
0rr? /S', average diameter 16 mμ: 113.6 capacity, dioctyl phthalate (DOP SP value 8.9)
60.8 volumes were mixed in a Henschel mixer, lcMw = 85000, Mn = 21000, SLMI =
1 polyethylene resin powder (5untec S-3
60PC (trade name): 125.6 volumes was added and mixed again using a Henschel mixer.
当該混合物を30%/二軸押出機で混練しペレットにし
た。The mixture was kneaded at a rate of 30% using a twin-screw extruder to form pellets.
このペレットを30%/二軸押出機に420%巾Tダイ
を取付けたフィルム製造装置に成形した。The pellets were molded into a film manufacturing apparatus equipped with a 30%/twin screw extruder and a 420% width T-die.
この時の押出量は12.5 kV/Hr 。引取速度は
277277n 、樹脂圧は65驚であった。The extrusion rate at this time was 12.5 kV/Hr. The take-up speed was 277,277 nm, and the resin pressure was 65 mm.
成形された膜状物は1,1.1−)リクロルエタン〔ク
ロロ七ン(商品名)〕中で5分間浸漬し、DOPの抽出
を行なった。The formed membrane was immersed in 1,1.1-)lichloroethane (Chloro7ane (trade name)) for 5 minutes to extract DOP.
得られた膜の厚みは0.195%、気孔率55転電気抵
抗は0.00042Ωdm”/枚であった。The thickness of the obtained film was 0.195%, the porosity was 55%, and the electrical resistance was 0.00042 Ωdm''/sheet.
また多厚膜基材の組成は、ポリエチレン樹脂64.8容
量優、微粉珪酸34.4容量多、DOPo、8容量φで
あった。The composition of the multi-thick film base material was 64.8 volumes of polyethylene resin, 34.4 volumes of fine silicic acid, DOPo, and 8 volumes φ.
この多孔膜の耐酸化試験の短絡時間は162時間であっ
たが、耐酸化試験を48時間行なった後の破断伸びは2
優であった。The short circuit time of this porous membrane in the oxidation resistance test was 162 hours, but the elongation at break after 48 hours of the oxidation resistance test was 2.
It was excellent.
この多孔膜をナンテン系プロセスオイル
(5onic R−200(商品名)〕4重量多クロ
りセン溶液に10分間浸漬した後、70℃で熱風乾燥し
た。This porous membrane was immersed in a 4-weight chlorocene solution of nandene-based process oil (5onic R-200 (trade name)) for 10 minutes, and then dried with hot air at 70°C.
プロセスオイルの付着量は5.2重量条であった。The amount of process oil deposited was 5.2 weight strips.
この含浸処理膜の気孔率は54%、電気抵抗は0.00
045Ωdrr?/枚とほとんど変化がなかった。The porosity of this impregnated membrane is 54% and the electrical resistance is 0.00.
045Ωdrr? / sheet and there was almost no change.
耐酸化試験の短絡時間は200時間以上、耐酸化試験4
8時間後の破断伸びは330条と優れた耐久性を保持し
ていた。Oxidation resistance test short circuit time is over 200 hours, oxidation resistance test 4
The elongation at break after 8 hours was 330, indicating excellent durability.
また膜表面に水滴を落すと瞬間的に吸収された。Also, when a drop of water was dropped on the membrane surface, it was instantly absorbed.
実施例 2
実施例1で製造した未処理多孔膜をβ−ピネン重合体(
P 1ccolyte A−115(商品名)〕3.5
重量多クロロセり溶液に5分間浸漬し、乾燥した。Example 2 The untreated porous membrane produced in Example 1 was treated with β-pinene polymer (
P 1ccolyte A-115 (product name)] 3.5
It was immersed in a heavy weight chlorine solution for 5 minutes and dried.
β−ピネン重合体の付着量は4.2重量φであった。The amount of β-pinene polymer deposited was 4.2 weight φ.
この膜の電気抵抗は0.00046Ωdrr?/枚と低
くかった。The electrical resistance of this film is 0.00046Ωdrr? / piece was low.
耐酸化試験短絡時間は200時間以上、耐酸化試験48
時間後の破断伸びは200%と優れた柔軟性と耐久性を
示した。Oxidation resistance test short circuit time is over 200 hours, oxidation resistance test 48
The elongation at break after hours was 200%, indicating excellent flexibility and durability.
実施例 3〜7
実施例1にしたがって製造した未処理多孔膜を用い、各
種含浸処理を行なった結果を表1に示しtうともに極め
て低い電気抵抗と優れた耐久性を示した。Examples 3 to 7 The untreated porous membranes produced according to Example 1 were subjected to various impregnation treatments. The results are shown in Table 1, and the membranes exhibited extremely low electrical resistance and excellent durability.
実施例 8
Mw= 330000、Mn=20000、SLMI=
0のポリエチレンを用いた以外は、実施例1にしたがっ
て製造した。Example 8 Mw=330000, Mn=20000, SLMI=
It was manufactured according to Example 1 except that No. 0 polyethylene was used.
膜厚は0.22m、ナフテン系プロセスオイルの付着量
は4.9重量気気孔率は51%、電気抵抗は0.000
72Ωamシ′枚であった。The film thickness is 0.22m, the amount of naphthenic process oil attached is 4.9, the weight porosity is 51%, and the electrical resistance is 0.000.
It was a 72Ωam sheet.
耐酸化試験短絡時間200時間以上、耐酸化試験48時
間後の破断伸びは240φであった。The elongation at break after 200 hours or more of oxidation resistance test short circuit time and 48 hours of oxidation resistance test was 240φ.
実施例 9
Mw=600000のポリエチレン樹脂15容量多、微
粉珪酸15容量多、DOP70容量多を用いた以外は、
実施例1にしたがって製造した。Example 9 Except for using 15 volumes of polyethylene resin with Mw = 600,000, 15 volumes of fine silicic acid, and 70 volumes of DOP,
Manufactured according to Example 1.
プロセスオイルの付着量は5.7重量気気孔率は58優
、電気抵抗は0.00089Ωdr/?/枚(膜厚0.
28Y、)であった。The amount of process oil attached is 5.7, the weight porosity is 58, and the electrical resistance is 0.00089Ωdr/? / sheet (film thickness 0.
28Y, ).
耐酸化試験短絡時間は2200時間以上、耐酸化試験4
8時間後の破断伸びは96優であった。Oxidation resistance test short circuit time is over 2200 hours, oxidation resistance test 4
The elongation at break after 8 hours was 96.
比較例 1
有機液状体としてナフテン系プロセスオイルを用い、実
施例1にしたがい多孔膜を製造した。Comparative Example 1 A porous membrane was produced according to Example 1 using naphthenic process oil as the organic liquid.
また抽出溶剤として石油エーテルを用いた。Petroleum ether was also used as an extraction solvent.
得られた多孔膜中にはプロセスオイルが8.1%残存し
ていた。8.1% of process oil remained in the obtained porous membrane.
この多孔膜の破断伸びは143%であった。耐酸化試験
短絡時間は200時間以上、耐酸化試験48時間後の破
断伸びは68%と一応伸びを保持シティタカ、ra低抵
抗0.00148Ωdrr?/枚(膜厚0.21%)と
高かった。The elongation at break of this porous membrane was 143%. The oxidation resistance test short circuit time is over 200 hours, and the elongation at break after 48 hours of the oxidation resistance test is 68%, which maintains the elongation. City Taka, RA low resistance 0.00148Ωdrr? /sheet (film thickness 0.21%).
また膜上に水滴を落したが、水滴のまへ残った。Also, water droplets were dropped on the membrane, but the water remained in the water droplets.
比較例 2
Mw=330000、Mn=20000、SLMI=0
0ポリエチレン15容量優、微粉珪酸15容量多、ナフ
テン系プロセスオイル70容量多を用いた以外は、比較
例1にしたがって製造した。Comparative example 2 Mw=330000, Mn=20000, SLMI=0
Comparative Example 1 was performed except that 15 volumes of polyethylene, 15 volumes of finely divided silicic acid, and 70 volumes of naphthenic process oil were used.
得られた膜中にはプロセスオイルがio、。多残ってい
た。Process oil is present in the resulting film. There was a lot left.
この膜の気孔率は56%、電気抵抗は0.00070Ω
dy&/枚(0,22X)、破断伸びは52%と小さか
った。The porosity of this membrane is 56% and the electrical resistance is 0.00070Ω
dy&/sheet (0,22X), the elongation at break was as small as 52%.
耐酸化試験短絡時間は200時間以上であったが、耐酸
化試験48時間後の破断伸びは28饅と脆くなっていた
。Although the short-circuit time in the oxidation resistance test was 200 hours or more, the elongation at break after 48 hours in the oxidation resistance test was 28 hours, which was brittle.
比較例 3
Mw=600000のポリエチレンを用いた以外は、実
施例2にしたがって製造した。Comparative Example 3 Produced according to Example 2 except that polyethylene with Mw=600,000 was used.
この多孔膜は耐久性は優れていたが、電気抵抗が0.0
0106Ωdd/枚と高かった。Although this porous membrane had excellent durability, its electrical resistance was 0.0.
It was as high as 0106Ωdd/piece.
その他の性能を表1に示した。Other performances are shown in Table 1.
比較例 4
実施例1にしたがって製造した多孔膜に、ナフテン系プ
ロセスオイルを1.7重量多含浸付着させた。Comparative Example 4 A porous membrane produced according to Example 1 was impregnated with naphthenic process oil at a concentration of 1.7% by weight.
この膜の気孔率は55先電気抵抗は0.00042Ωd
tr?/枚(膜厚0.195%)と低かった。The porosity of this membrane is 55, and the electrical resistance is 0.00042Ωd.
tr? /sheet (film thickness 0.195%).
耐酸化試験短絡時間は186時間であったが、耐酸化試
験48時間後の破断伸びは15%と小さく、含浸処理の
効果はほとんどなかった。The short circuit time in the oxidation resistance test was 186 hours, but the elongation at break after 48 hours in the oxidation resistance test was as small as 15%, and the impregnation treatment had almost no effect.
比較例 5
ナフテン系プロセスオイルを20.8重量上付着させた
以外は、比較例4にしたがって製造した。Comparative Example 5 Comparative Example 4 was produced except that 20.8 weight of naphthenic process oil was deposited.
得られた多孔膜の気孔率は47.3%、電気抵抗は0.
00066ΩdW?/枚であったが、硫酸に浸漬すると
、プロセスオイルの一部が遊離してきた。The resulting porous membrane had a porosity of 47.3% and an electrical resistance of 0.
00066ΩdW? / sheet, but when immersed in sulfuric acid, some of the process oil was liberated.
−8後には付着量は15.8%に減少していた。After -8, the adhesion amount had decreased to 15.8%.
また、水濡れ性が悪かった。In addition, the water wettability was poor.
Claims (1)
600000以下のポリオレフィン樹脂10〜60容量
優、無機微粉体7〜42容量条、溶解度係数8.4〜9
.9の有機液状体30〜75容量俤を混合した後シート
状に溶融成形し、次いでかかる成形物より有機液状体を
抽出して得られるポリオレフィン樹脂40〜90容量俤
、無機微粉体10〜60容量多、有機液状体O〜5容量
多からなる多孔膜に、耐酸性有機物を当該膜状物重量の
2〜15重量多重量蓋せしめることを特徴とする電池隔
離板の製造方法。1 Polyolefin resin with a number average molecular weight of 15,000 or more and a weight average molecular weight of 600,000 or less, 10 to 60 volumes, inorganic fine powder 7 to 42 volumes, solubility coefficient 8.4 to 9
.. After mixing 30 to 75 volumes of the organic liquid of No. 9, they are melt-molded into a sheet, and then the organic liquid is extracted from the molded product, resulting in a polyolefin resin of 40 to 90 volumes and an inorganic fine powder of 10 to 60 volumes. 1. A method for manufacturing a battery separator, which comprises capping a porous film containing an organic liquid with a volume of 0 to 5 with an acid-resistant organic substance in an amount of 2 to 15 times the weight of the film.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52016109A JPS5851389B2 (en) | 1977-02-18 | 1977-02-18 | Manufacturing method of battery separator |
MX77100850U MX5279E (en) | 1977-02-18 | 1977-10-06 | IMPROVED MICROPOROUS FILM AND METHOD FOR OBTAINING IT |
BR7706720A BR7706720A (en) | 1977-02-18 | 1977-10-07 | MICRO-POROUS FILM PROCESSING THE SAME AND BATTERY SEPARATOR |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52016109A JPS5851389B2 (en) | 1977-02-18 | 1977-02-18 | Manufacturing method of battery separator |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS53101633A JPS53101633A (en) | 1978-09-05 |
JPS5851389B2 true JPS5851389B2 (en) | 1983-11-16 |
Family
ID=11907338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP52016109A Expired JPS5851389B2 (en) | 1977-02-18 | 1977-02-18 | Manufacturing method of battery separator |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS5851389B2 (en) |
BR (1) | BR7706720A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5173807A (en) * | 1974-12-24 | 1976-06-26 | Hitachi Ltd | RAINSHING OSOSHUTSUKAIRO |
-
1977
- 1977-02-18 JP JP52016109A patent/JPS5851389B2/en not_active Expired
- 1977-10-07 BR BR7706720A patent/BR7706720A/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5173807A (en) * | 1974-12-24 | 1976-06-26 | Hitachi Ltd | RAINSHING OSOSHUTSUKAIRO |
Also Published As
Publication number | Publication date |
---|---|
BR7706720A (en) | 1978-08-22 |
JPS53101633A (en) | 1978-09-05 |
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