JP3380267B2 - Method of manufacturing heat-resistant thin paper - Google Patents
Method of manufacturing heat-resistant thin paperInfo
- Publication number
- JP3380267B2 JP3380267B2 JP13685892A JP13685892A JP3380267B2 JP 3380267 B2 JP3380267 B2 JP 3380267B2 JP 13685892 A JP13685892 A JP 13685892A JP 13685892 A JP13685892 A JP 13685892A JP 3380267 B2 JP3380267 B2 JP 3380267B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- pulp
- thin paper
- paper
- heat
- 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 - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性薄葉紙、特に電
気的負性ガス、不燃性シリコン油、エポキシ樹脂などの
吸収性、含浸性に優れた耐熱性薄葉紙に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant thin paper, and more particularly to a heat-resistant thin paper which is excellent in absorption and impregnation of electrically negative gas, incombustible silicone oil, epoxy resin and the like.
【０００２】[0002]
【従来の技術】通常、変圧器には、絶縁強さや冷却効果
を高めるための媒体として６フッ化イオウガス等の電気
的負性ガス、不燃性のシリコン油等が使用されている。
従って、変圧器の巻線の絶縁に使用される巻線被覆用の
薄葉紙状絶縁材料は、前記のガス体やシリコン油を充分
に吸収、含浸するものでなければならない。即ち、含浸
性の悪い薄葉紙状絶縁材料では、絶縁物内にボイドが残
り、耐コロナ性、絶縁耐力、ｔａｎδ等の電気特性が著
しく劣ることになり、用途上必要な絶縁強さや冷却効果
を発現できなくなって、変圧器に要求される特性を満足
させ得ることができなくなる。また、電動機等の巻線の
絶縁に使用される巻線被覆用の絶縁材料には、エポキシ
等の樹脂を含浸させた薄葉紙状の絶縁材料が使用される
が、前記と同様に、やはり、樹脂含浸性の良好な材料で
なければ、充分な電気特性を発現できなくなって、電動
機の要求特性を満足させることができなくなる。また一
方、電子写真装置等の定着ローラや感光体のようなクリ
ーニングを必要とする非清掃部材の清掃用として使用さ
れるクリーニングウエブにも耐熱性薄葉紙状材料が活用
されているが、この場合にも前記と同様に、シリコン油
等の含浸性の良好な材料でなければ、充分なクリーニン
グ性を発揮できない。また更に、市場では、これら電
気、電子機器に対する小型化の要求が、近年、ますます
高まっており、それに伴い、絶縁材料についても耐熱性
や電気特性の向上がますます重要視されるようになりつ
つあり、含浸性良好で、かつ、薄くて耐熱性良好な薄葉
紙状の絶縁材料の提供が関連市場において望まれてお
り、これに対応すべく、芳香族ポリアミドパルプと芳香
族ポリアミド短繊維の組み合わせによる耐熱性の薄葉紙
状物が種々提案されている。2. Description of the Related Art Normally, in a transformer, an electrically negative gas such as sulfur hexafluoride gas or a nonflammable silicone oil is used as a medium for enhancing the insulation strength and the cooling effect.
Therefore, the thin paper-like insulating material for covering the winding, which is used for insulating the winding of the transformer, must sufficiently absorb and impregnate the above gas body and silicon oil. That is, in a thin paper-like insulating material with poor impregnating property, voids remain in the insulator, and the electrical properties such as corona resistance, dielectric strength, and tan δ are remarkably inferior. It becomes impossible to satisfy the characteristics required for the transformer. In addition, a thin paper-shaped insulating material impregnated with a resin such as epoxy is used as an insulating material for covering the winding used for insulating the winding of an electric motor or the like. Unless the material has a good impregnating property, sufficient electric characteristics cannot be exhibited and the required characteristics of the electric motor cannot be satisfied. On the other hand, a heat-resistant thin paper-like material is also used for a cleaning web used for cleaning a non-cleaning member such as a fixing roller of an electrophotographic device or a photoconductor that needs cleaning. Similarly to the above, sufficient cleaning properties cannot be exhibited unless the material has a good impregnating property such as silicon oil. Furthermore, in the market, demands for miniaturization of these electric and electronic devices have been increasing more and more in recent years, and accordingly, improvement of heat resistance and electric characteristics of insulating materials has become more and more important. At the same time, it is desired in the related market to provide a thin paper-like insulating material that has good impregnation properties, and is thin and has good heat resistance. To meet this demand, a combination of aromatic polyamide pulp and aromatic polyamide short fibers is required. Have proposed various heat-resistant thin paper sheets.
【０００３】例えば、前述のような市場の要求に対応す
べく、芳香族ポリアミドパルプと芳香族ポリアミド短繊
維のみからなる耐熱性薄葉紙状物としては、特開平２―
２３６９０７号公報あるいは特開平２―１０６８４０号
公報、特開平３―６９６９２号公報などが提案されてい
る。For example, in order to meet the demands of the market as described above, as a heat-resistant thin paper-like material composed only of aromatic polyamide pulp and aromatic polyamide short fibers, JP-A-2-
Japanese Patent Laid-Open No. 236907, Japanese Patent Laid-Open No. 2-106840, Japanese Patent Laid-Open No. 3-69692 and the like are proposed.
【０００４】しかし、これらに提案された耐熱性薄葉紙
状物は、何れも、湿紙形成を優先し、芳香族ポリアミド
パルプを少なくとも２０〜２５重量％含有するものであ
り、抄紙時の濾水性をやや犠牲にしたものである。即
ち、薄葉紙状物形成にあたって、芳香族ポリアミド短繊
維同士を接着するための接着剤の役割を芳香族ポリアミ
ドパルプが担っているが、もともと、木材パルプ等の天
然パルプに比べて、芳香族ポリアミドパルプの接着力は
劣っているため、薄葉紙状物中における、その含有量を
低下させると薄葉紙の強力が低下してくるので、含有量
を減少させるにつれ、その後のカレンダー加工工程にお
ける加工時の温度と圧力を増加しなければ、目的とする
特性を有する品質の薄葉紙状物を得ることができず、従
って、その結果、薄葉紙状物の嵩密度が高くなって、ど
うしても、前記のガス体やシリコン油、エポキシ樹脂等
の含浸性を犠牲にせざるを得ないという問題があった。
また更に、芳香族ポリアミドパルプの量を２５重量％以
上含有せしめると湿紙形成時の濾水性が悪化してくると
いう問題もあった。However, all of the heat-resistant thin paper-like materials proposed in these papers prioritize wet paper formation and contain at least 20 to 25% by weight of aromatic polyamide pulp, and have a drainage property at the time of papermaking. It's a little sacrificed. That is, in forming a thin paper material, the aromatic polyamide pulp plays a role of an adhesive for adhering the aromatic polyamide short fibers to each other. However, compared with natural pulp such as wood pulp, the aromatic polyamide pulp is originally used. Since the adhesive strength of the paper is poor, the strength of the paper decreases when the content of the paper is decreased in the thin paper-like material.Therefore, as the content is decreased, the temperature at the time of processing in the subsequent calendering step and If the pressure is not increased, it is not possible to obtain a quality thin paper-like material having the desired properties, and as a result, the bulk density of the thin paper-like material becomes high. However, there is a problem that the impregnating property of epoxy resin or the like must be sacrificed.
Furthermore, if the content of the aromatic polyamide pulp is 25% by weight or more, the drainage property at the time of wet paper web formation is deteriorated.
【０００５】本発明者らは、上記のかかる問題を克服す
べく、鋭意研究の結果、特殊な芳香族ポリアミドパルプ
を使用すれば、耐熱性薄葉紙状物中における芳香族ポリ
アミドパルプの含有量を２０重量％以下におさえても抄
紙が充分可能で、濾水性も改善され、従って、得られた
薄葉紙状物の嵩密度も比較的低く、即ち、前記のガス体
やシリコン油、樹脂等の含浸性も良好な薄葉紙を得るこ
とができることを見出し、本発明を完成するに至った。
以下本発明について詳説する。The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems, and as a result, if a special aromatic polyamide pulp is used, the content of the aromatic polyamide pulp in the heat-resistant thin paper sheet is 20%. Papermaking is sufficiently possible even if the content is less than 10% by weight, and drainage is also improved. Therefore, the bulk density of the obtained thin paper-like material is relatively low, that is, impregnating property of the gas body, silicone oil, resin, etc. The inventors have found that a good thin paper can be obtained, and have completed the present invention.
The present invention will be described in detail below.
【０００６】[0006]
【発明の目的】本発明の目的は、電気的負性ガス体やシ
リコン油、エポキシ樹脂等の含浸性に優れ、かつ、耐熱
性、耐コロナ性、絶縁耐力、ｔａｎδ等の電気特性の良
好な薄葉紙を提供することにある。It is an object of the present invention to have excellent impregnability with an electrically negative gas body, silicone oil, epoxy resin, etc., and to have good electrical properties such as heat resistance, corona resistance, dielectric strength and tan δ. To provide thin paper.
【０００７】[0007]
【発明の構成】即ち本発明は、「（請求項１）芳香族ポ
リアミドパルプ１〜２０重量％と、芳香族ポリアミド短
繊維９９〜８０重量％との混合物からなる水性スラリー
から湿式抄造法によって形成された湿紙を加熱加圧加工
して得られる耐熱性薄葉紙の製造方法において、加熱加
圧加工前の薄葉紙中の芳香族ポリアミドパルプに含まれ
る極性溶媒の量が、０．０２〜４．５０％であり、か
つ、加熱加圧加工後の薄葉紙の坪量が８〜４５ｇ／
ｍ2、嵩密度が０．２０〜０．９０ｇ／ｃｍ3であること
を特徴とする耐熱性薄葉紙の製造方法。（請求項２）約
１５０トールの真空下で３日間含浸させた場合におけ
る、１２００センチストローク以下の粘度であるシリコ
ン油の含浸率が１５重量％以上である請求項１に記載の
耐熱性薄葉紙の製造方法。」である。That is, the present invention relates to "(Claim 1) A wet slurry is formed from an aqueous slurry comprising a mixture of 1 to 20% by weight of aromatic polyamide pulp and 99 to 80% by weight of aromatic polyamide short fibers. In the method for producing a heat-resistant thin paper obtained by heating and pressing the wet paper, the amount of the polar solvent contained in the aromatic polyamide pulp in the thin paper before the heating and pressing is 0.02 to 4.50. %, And the basis weight of the thin paper after heat and pressure processing is 8 to 45 g /
method for producing a heat-resistant tissue paper, wherein m 2, a bulk density of 0.20~0.90g / cm 3. (Claim 2) Silicone having a viscosity of 1200 cm stroke or less when impregnated under a vacuum of about 150 Torr for 3 days.
The method for producing a heat-resistant thin paper according to claim 1, wherein the impregnation rate of the oil is 15% by weight or more. It is.
【０００８】ここでいう芳香族ポリアミドとは芳香族ポ
リアミド、及び芳香族ポリアミドイミドである。芳香族
ポリアミドは従来公知の（Ａ）芳香族環を有するジカル
ボン酸と芳香族環を有するジアミンとの縮合ポリアミ
ド、（Ｂ）芳香族環を有するアミノカルボン酸を縮合し
てなる縮合ポリアミド、（Ｃ）前記の（Ａ）と（Ｂ）と
を共重合したポリアミド、などがあげられる。The aromatic polyamide referred to here is an aromatic polyamide and an aromatic polyamideimide. The aromatic polyamide is a conventionally known condensed polyamide of (A) a dicarboxylic acid having an aromatic ring and a diamine having an aromatic ring, (B) a condensed polyamide obtained by condensing an aminocarboxylic acid having an aromatic ring, (C ) Polyamide obtained by copolymerizing the above (A) and (B).
【０００９】また、芳香族ポリアミドイミドは、下記の
一般式で示される単位を有するポリアミドイミドであ
る。The aromatic polyamideimide is a polyamideimide having a unit represented by the following general formula.
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】但し、ＲはHowever, R is
【００１２】[0012]
【化２】 [Chemical 2]
【００１３】また、ＸはAlso, X is
【００１４】[0014]
【化３】 [Chemical 3]
【００１５】Ｒ′は低級アルキレン基である。R'is a lower alkylene group.
【００１６】更に、本発明において使用する芳香族ポリ
アミドパルプ（以下、パルプ状微粒子という）とは、従
来公知の通常の構造の微粒子形状で湿紙形性能を有する
ものであって、例えば、特公昭３５―１１８５１号公
報、特公昭３７―５７３２号公報等に記載された形状を
有するものであるが、従来公知のパルプ状粒子と異なる
ところは、このパルプ状粒子を混合し、湿式抄造法によ
って形成された湿紙を乾燥して得られる加熱加圧加工前
（カレンダー加工前）の乾燥紙中に存在するパルプ状粒
子中に残存する極性溶媒量が０．０２〜４．５０重量％
の範囲内になるように予め設定、調整されているパルプ
状粒子を用いる点である。なお、このパルプ状粒子と混
合する短繊維には芳香族ポリアミドからなる短繊維が用
いられる。なお、芳香族ポリアミドパルプ及び芳香族ポ
リアミド短繊維としては、特にポリメタフェニレンイソ
フタラミド系が好ましく、芳香族ポリアミド短繊維はパ
ルプ状微粒子と同一の化学構造のものが最も好ましい
が、限定されるものではなく、異なる化学構造のもので
もよい。Further, the aromatic polyamide pulp (hereinafter referred to as pulp-like fine particles) used in the present invention is a conventionally known fine particle having a normal structure and having wet paper web-like performance. Although it has a shape described in Japanese Patent Publication No. 35-11851, Japanese Patent Publication No. 37-5732, etc., the difference from the conventionally known pulp-like particles is that the pulp-like particles are mixed and formed by a wet papermaking method. The amount of the polar solvent remaining in the pulp-like particles present in the dried paper before heat and pressure processing (before calendering) obtained by drying the wet paper obtained is 0.02 to 4.50 % by weight.
The point is to use pulp-like particles that are preset and adjusted to fall within the range. As the short fibers mixed with the pulp-like particles, short fibers made of aromatic polyamide are used. Incidentally, as the aromatic polyamide pulp and the aromatic polyamide short fibers, a polymetaphenylene isophthalamide type is particularly preferable, and the aromatic polyamide short fibers are most preferably those having the same chemical structure as the pulp-like fine particles, but are not limited thereto. However, it may have a different chemical structure.
【００１７】また更に、ガス体やシリコン油等の吸収
性、樹脂類の含浸性、耐熱性などをより向上させるため
に、必要ならば、雲母微粒子、水酸化アルミニウム、酸
化アルミニウム等の無機粉体を混合してもよい。If necessary, in order to further improve the absorption of gas and silicon oil, the impregnation of resins, and the heat resistance, inorganic powder such as mica fine particles, aluminum hydroxide, aluminum oxide, etc. May be mixed.
【００１８】また、短繊維は芳香族ポリアミドからなる
短繊維のみでもよいし、必要に応じて、これに少量の無
機質の短繊維を混合したものでもよい。なお短繊維の単
糸繊度は芳香族ポリアミド短繊維の場合、２０．０デニ
ール以下、更に好ましくは０．５〜１０．０デニールで
あり、無機質繊維の場合は３０．０μｍ以下がよく、好
ましくは０．３〜２０μｍである。The short fibers may be only short fibers made of aromatic polyamide, or may be a mixture of a small amount of inorganic short fibers if necessary. The single-filament fineness of the short fibers is 20.0 denier or less in the case of aromatic polyamide short fibers, more preferably 0.5 to 10.0 denier, and 30.0 μm or less in the case of inorganic fibers, preferably It is 0.3 to 20 μm.
【００１９】本発明においては、極性溶剤を比較的多量
に含むパルプ状微粒子と短繊維、更に、必要に応じて無
機質粒子や無機質短繊維を混合し、固形分濃度が約０．
２５〜０．４５重量％になるように調整した水性スラリ
ーから、従来公知の湿式抄造法、例えば長網式、丸網式
等の抄紙機を用いて湿紙を形成し、この湿紙を脱水、乾
燥して得た乾燥紙を加熱加圧カレンダー加工して、特定
の乾燥紙の厚さ、嵩密度を有する耐熱性薄葉紙状物を得
ることができる。In the present invention, pulp-like fine particles containing a relatively large amount of polar solvent and short fibers, and if necessary, inorganic particles or inorganic short fibers are mixed to give a solid content of about 0.
A wet paper is formed from an aqueous slurry adjusted to have a content of 25 to 0.45% by weight using a conventionally known wet paper making method, for example, a Fourdrinier type or a round net type paper machine, and the wet paper is dehydrated. Then, the dried paper obtained by drying can be subjected to heat and pressure calendering to obtain a heat-resistant thin paper sheet having a specific dry paper thickness and bulk density.
【００２０】この場合、極性溶剤を含むパルプ状微粒子
の比率は１〜２０重量％であり、好ましくは８〜１５重
量％である。かつ、このパルプ状微粒子が含んでいる極
性溶剤の含有量は、０．０２〜４．５０重量％が望まし
い。本発明の目的はガス体やシリコン油等の吸収性、樹
脂類の含浸性に優れ、かつ、最低限必要な諸物性値を有
する耐熱性薄葉紙状物を提供することにあるため、カレ
ンダー加工後の薄葉紙状物中における短繊維同士の接着
点、融着点を極力減少せしめ、かつ、該接着点や融着点
の接着強力、融着強力を従来以上に高めて、必要な諸物
性値を発現させることにある。そのためには、使用する
パルプ状微粒子の量を極力少なくし、かつ、パルプ状微
粒子の接着剤としての性能を従来以上に充分に高く発現
させるようにしなければならない。In this case, the proportion of the pulp-like fine particles containing the polar solvent is 1 to 20% by weight, preferably 8 to 15% by weight. Further, the content of the polar solvent contained in the pulp-like fine particles is preferably 0.02 to 4.50 % by weight. Since the object of the present invention is to provide a heat-resistant thin paper sheet having excellent absorbability of gas and silicon oil and the like, impregnability with resins, and having the minimum required physical property values, after calendering Adhesion points between short fibers in the thin paper-like material, the fusion points are reduced as much as possible, and the adhesion strength at the adhesion points and the fusion points, and the fusion strength are increased more than ever before to obtain the required physical property values. To express it. For that purpose, it is necessary to reduce the amount of the pulp-like fine particles to be used as much as possible and to make the performance of the pulp-like fine particles as an adhesive sufficiently higher than ever before.
【００２１】本研究者らは鋭意研究の結果、カレンダー
加工前の薄葉紙状物中のパルプ状微粒子中に含まれる極
性溶剤の量が多いほど、カレンダー加工工程でパルプ状
微粒子が溶融し易くなって、融着力、接着力が高まるこ
とを発見した。但し、パルプ状微粒子中の極性溶剤の量
が多すぎるとカレンダー加工後の耐熱性薄葉紙状物中に
残存する極性溶剤量も多くなりすぎて、電気特性、特に
絶縁強さや耐熱性を悪化せしめて、用途上好ましくなく
なるため、カレンダー加工前の薄葉紙状物中のパルプ状
微粒子中に含まれる極性溶剤の量を０．０２〜４．５０
重量％とする必要がある。パルプ状微粒子中に含まれる
極性溶剤の量が０．０２重量％未満では、カレンダー加
工後の薄葉紙状物の引張強力が不充分である。また、極
性溶剤の量が４．５０重量％を越えると、前述の如く、
電気特性や耐熱性が低下し、目的とする用途の要求特性
を満足し得なくなる。なお、ここでいう極性溶剤とは、
当該パルプ状微粒子を少なくとも３．０重量％以上溶解
する溶剤であり、例えば、Ｎ―メチル―２―ピロリド
ン、Ｎ，Ｎ―ジメチルホルムアミド、Ｎ，Ｎ―ジメチル
アセトアミド等のアミド系溶剤、及び、ジメチルスルホ
キシド、Ｎ―メチルカプロラクタム、Ｎ―メチルピペリ
ジン等である。As a result of earnest research by the present inventors, the larger the amount of polar solvent contained in the pulp-like fine particles in the thin paper sheet before calendering, the more easily the pulp-like fine particles are melted in the calendering process. , And found that the fusion strength and adhesive strength are increased. However, when the amount of the polar solvent in the pulp-like fine particles is too large, the amount of the polar solvent remaining in the heat-resistant thin paper sheet after calendering also becomes too large, and the electrical properties, particularly the insulation strength and heat resistance are deteriorated. However, the amount of the polar solvent contained in the fine pulp particles in the thin paper sheet before calendaring is 0.02 to 4.50 because it becomes unfavorable for use.
It is necessary to set it to the weight percent. When the amount of the polar solvent contained in the pulp-like fine particles is less than 0.02 % by weight, the tensile strength of the thin paper sheet after calendering is insufficient. Further, when the amount of the polar solvent exceeds 4.50 % by weight, as described above,
The electrical characteristics and heat resistance are reduced, and it becomes impossible to satisfy the required characteristics for the intended use. Incidentally, the polar solvent referred to here,
A solvent that dissolves at least 3.0% by weight of the pulp-like fine particles, and examples thereof include amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide, and dimethyl. Examples thereof include sulfoxide, N-methylcaprolactam, N-methylpiperidine and the like.
【００２２】極性溶剤を含有するパルプ状微粒子のカレ
ンダー加工前の乾燥紙中に占める比率が１重量％未満で
は、水性スラリーから抄紙機で抄造する場合、湿紙形成
能力が著しく悪化して抄造が不可能となり好ましくな
い。また、パルプ状微粒子の比率が１０重量％を越えた
場合、濾水性が低下し、かつ、カレンダー加工後に得ら
れる薄葉紙状物のシリコン油や樹脂等の吸収性、含浸性
が低下するので、極性溶剤を含有するパルプ状微粒子の
カレンダー加工前の乾燥紙中に占める比率は１〜２０重
量％とすることが必要である。従って、カレンダー加工
前の乾燥紙中に占める芳香族ポリアミド繊維、又は、芳
香族ポリアミド短繊維と無機質の短繊維とを加えたもの
の比率は、９９〜８０重量％である。When the ratio of pulp-like fine particles containing a polar solvent in the dry paper before calendering is less than 1% by weight, the wet paper forming ability is remarkably deteriorated when papermaking is performed from an aqueous slurry by a paper machine, and papermaking is performed. It is impossible and not preferable. Further, when the ratio of the pulp-like fine particles exceeds 10% by weight, the drainage is lowered, and the absorbability and impregnability of silicon oil or resin of the thin paper-like material obtained after calendering is lowered. The proportion of the pulp-like fine particles containing the solvent in the dry paper before calendering needs to be 1 to 20% by weight. Therefore, the ratio of the aromatic polyamide fiber or the aromatic polyamide short fiber and the inorganic short fiber added in the dry paper before calendering is 99 to 80% by weight.
【００２３】更に、本発明においては、加熱加圧加工後
の薄葉紙の坪量が８〜４５ｇ／ｍ2、嵩密度が０．２０
〜０．９０ｇ／cm3 になるようにカレンダー加工する。
このカレンダー加工は、通常、直径が約１５〜８０cmか
らなる１つの硬質表面ロールと直径が約３０〜１００cm
からなる１つの変形可能な弾性ロールとの間、又は直径
が約２０〜８０cmからなる２ケの硬質表面ロール同士の
間で行われるが、硬質表面ロールと変形可能な弾性ロー
ルとの間で加熱加圧して行うのが望ましい。この時の硬
質表面ロールの表面温度は、約３１０℃以下、好ましく
は１８０〜２９０℃であり、加圧力は約４００kg／cm以
下、好ましくは１５０〜３５０kg／cmである。カレンダ
ーロールの表面温度、及び圧力が上記の範囲を外れると
得られる薄葉紙状物の嵩密度が０．２５〜０．９０ｇ／
cm3 の範囲内に入らなくなるばかりでなく、薄葉紙状物
の強力の低下や、シリコン油、樹脂の吸収性、含浸性の
低下を招く等の問題を生じる。Further, in the present invention, the basis weight of the thin paper after heat and pressure processing is 8 to 45 g / m 2 , and the bulk density is 0.20.
Calendar processing to ~ 0.90 g / cm 3 .
This calendering is usually one hard surface roll with a diameter of about 15-80 cm and a diameter of about 30-100 cm.
Heating between a hard elastic roll and a deformable elastic roll, but between two hard elastic rolls each having a diameter of about 20 to 80 cm. It is desirable to pressurize. At this time, the surface temperature of the hard surface roll is about 310 ° C. or lower, preferably 180 to 290 ° C., and the pressing force is about 400 kg / cm or lower, preferably 150 to 350 kg / cm. When the surface temperature and pressure of the calender roll are out of the above ranges, the bulk density of the thin paper sheet obtained is 0.25 to 0.90 g /
Not only will it not fall within the cm 3 range, but the strength of the thin paper-like material will be reduced, and the absorption and impregnation of silicon oil and resin will be reduced.
【００２４】[0024]
【発明の効果】本発明によって得られる薄葉紙は上述の
とおり、ガス体やシリコン油、樹脂等の吸収性、含浸性
が必要とされる変圧器、電動機等の巻線用の耐熱性薄葉
紙状絶縁材料として有用であるばかりでなく、電子写真
装置等の定着ロールや感光体のようなクリーニングを必
要とする非清掃部材の清掃用に使用されるクリーニング
ウエブとしても非常に有用な耐熱性薄葉紙状材料であ
る。As described above, the thin paper obtained according to the present invention is a heat-resistant thin paper-like insulation for windings of transformers, electric motors, etc., which require absorption and impregnation of gas, silicon oil, resin, etc. Not only useful as a material, but also very useful as a cleaning web used for cleaning non-cleaning members such as fixing rolls and photoconductors for electrophotographic devices, etc. Is.
【００２５】以下実施例により本発明の耐熱性薄葉紙状
物の製造方法について、更に具体的に説明する。なお、
実施例に示した各特性値は以下の方法により評価した値
である。
１）坪量：ＪＩＳ Ｐ８１２４に準じて測定した。
２）厚さ：マイクロメーターを用いて、ＪＩＳ Ｃ２１
１１，５．２により測定した。
３）嵩密度：ＪＩＳ Ｃ２１１１，６．１により測定し
た。
４）引張強力：定速伸長型引張試験機を用いて、ＪＩＳ
Ｃ２１１１の７に準じて測定した。
５）シリコン含浸率：薄葉紙状物から採取した試料を常
温下で１２００センチストロークス以下の粘度であるシ
リコン油中にいれ、約１５０トールの真空下で、シリコ
ン油を３日間含浸させた後に試料をとりだし、下記式に
より算出した。
シリコン含浸率（％）＝１００×｛（シリコン含浸後の
試料の重量―シリコン含浸前の試料の重量）／シリコン
含浸前の試料の重量｝
６）パルプ状微粒子中の極性溶剤量測定：熱分解（抽
出）法により測定した。The method for producing the heat-resistant thin paper sheet of the present invention will be described in more detail with reference to the following examples. In addition,
Each characteristic value shown in the examples is a value evaluated by the following method. 1) Basis weight: Measured according to JIS P8124. 2) Thickness: JIS C21 using a micrometer
It was measured according to 11, 5.2. 3) Bulk density: Measured according to JIS C211, 6.1. 4) Tensile strength: Using a constant speed extension type tensile tester, JIS
It measured according to 7 of C2111. 5) Silicon impregnation rate: A sample taken from a thin paper-like material is put in silicon oil having a viscosity of 1200 cm strokes or less at room temperature and impregnated with silicon oil for 3 days under a vacuum of about 150 Torr, and then the sample is Then, it was calculated by the following formula. Silicon impregnation rate (%) = 100 × {(weight of sample after silicon impregnation-weight of sample before silicon impregnation) / weight of sample before silicon impregnation} 6) Measurement of polar solvent amount in pulp fine particles: thermal decomposition It was measured by the (extraction) method.
【００２６】[0026]
【実施例１】特公昭４７―１０８６３号公報に記載の界
面重合法によりポリメタフェニレンイソフタレミドを製
造した。このポリマーをＮ―メチル―２―ピロリドンに
溶解して測定した固有粘度（ＩＶ）は、１．３５であ
り、ポリマー中に無機塩を含んでいない。次に、このポ
リマーをＮ―メチル―２―ピロリドンにポリマー濃度１
２．５重量％となるように溶解し、沈澱用のポリマー溶
液とした。Example 1 Polymetaphenylene isophthalemide was produced by the interfacial polymerization method described in JP-B-47-10863. The intrinsic viscosity (IV) measured by dissolving this polymer in N-methyl-2-pyrrolidone was 1.35, and the polymer did not contain an inorganic salt. Next, this polymer was added to N-methyl-2-pyrrolidone at a polymer concentration of 1
It was dissolved so as to be 2.5% by weight to obtain a polymer solution for precipitation.
【００２７】一方、Ｎ―メチル―２―ピロリドンの濃度
が通常より多めの４０重量％となるように水を加えて水
溶液を作り、沈澱剤とした。このポリマー溶液及び、沈
澱剤を用いて、特開昭５２―１５１６２号公報に記載さ
れた沈澱装置により、同公報に記載されている方法でパ
ルプ状微粒子を製造した。なお、このパルプ状微粒子中
に含まれているＮ―メチル―２―ピロリドンの量は、約
８．５０重量％であった。次に、このパルプ状微粒子を
パルパー、高速解離機、ディスクリファイナーを用いて
スラリー濃度０．４％でカナディアン標準濾水度１１０
mlの水性スラリーを作成した。なお、これらの工程で
は、パルプ状微粒子中に含まれているＮ―メチル―２―
ピロリドンが溶出せずに、できるだけ多く残存するよう
に注意して手早く作業を実施した。On the other hand, water was added so that the concentration of N-methyl-2-pyrrolidone was 40% by weight, which is higher than usual, to prepare an aqueous solution, which was used as a precipitant. Using this polymer solution and the precipitating agent, pulp-like fine particles were produced by the method described in JP-A-52-15162 by the method described therein. The amount of N-methyl-2-pyrrolidone contained in the pulp fine particles was about 8.50% by weight. Next, using a pulper, a high-speed dissociator, and a disc refiner, the pulp-like fine particles were added to a Canadian standard freeness of 110% at a slurry concentration of 0.4%.
A ml aqueous slurry was made. In addition, in these steps, N-methyl-2-
The work was carried out quickly, taking care that pyrrolidone did not elute and remained as much as possible.
【００２８】また一方、ポリメタフェニレンイソフタラ
ミド延伸糸として、単糸繊度が２．０デニール、繊維長
６．０mmの短繊維を１％濃度でパルパーにより水中に解
離分散させた。このオリメタフェニレンイソフタラミド
短繊維分散液と、パルプ状微粒子分散スラリーとを短繊
維対パルプ状微粒子の比率が８２重量％対１８重量％と
なるように混合、撹拌して、均一な抄紙用スラリーを作
成した。この工程でも、極力、パルプ状微粒子中に含ま
れているＮ―メチル―２―ピロリドンが、前記同様、溶
出しないように手早く注意して作業を実施した。次に、
タッピー式角型手抄機を用いて、該抄紙用スラリーを使
用して抄紙し、重量が約３００ｇ／ｍ2の水分を多量に
含んだ湿紙を得た。なお、この湿紙は乾燥した後の坪量
が２４．４ｇ／ｍ2 であった。またこの乾燥紙を分解し
てパルプ状微粒子を取り出し、Ｎ―メチル―２―ピロリ
ドンの含有量を測定したところ、約１．１２重量％含ま
れていることが判った。得られた乾燥紙を、直径が約２
５cmの硬質表面ロールと直径が約５０cmの変形可能な弾
性ロールにより、表１に示す条件でカレンダー加工を実
施し、目的とする薄葉紙状物を得た。得られた薄葉紙状
物について諸特性を測定し、その結果を表１に示した。On the other hand, as the polymetaphenylene isophthalamide drawn yarn, a short fiber having a single yarn fineness of 2.0 denier and a fiber length of 6.0 mm was dissociated and dispersed in water with a pulper at a concentration of 1%. This orimetaphenylene isophthalamide short fiber dispersion liquid and pulp-like fine particle dispersion slurry are mixed and stirred so that the ratio of short fibers to pulp-like fine particles is 82% by weight to 18% by weight, and uniform for papermaking. A slurry was created. In this step as well, the work was carried out with careful attention so as not to elute N-methyl-2-pyrrolidone contained in the pulp-like fine particles as much as possible, as described above. next,
Using a tappy type square hand machine, papermaking was performed using the slurry for papermaking to obtain a wet paper containing a large amount of water having a weight of about 300 g / m 2 . The basis weight of this wet paper after drying was 24.4 g / m 2 . Further, the dried paper was decomposed to take out pulp-like fine particles, and the content of N-methyl-2-pyrrolidone was measured. As a result, it was found that the content was about 1.12% by weight. The dry paper obtained has a diameter of about 2
Calendering was carried out under the conditions shown in Table 1 using a hard surface roll of 5 cm and a deformable elastic roll having a diameter of about 50 cm to obtain the target thin paper sheet. Various properties of the obtained thin paper sheet were measured, and the results are shown in Table 1.
【００２９】[0029]
【実施例２】実施例１の場合と同様にして作成したポリ
メタフェニレンイソフタラミド短繊維分散液と、パルプ
状微粒子分散スラリーとを短繊維対パルプ状微粒子の比
率が９７重量％対３重量％となるように混合、撹拌し
て、均一な抄紙用スラリーを作成した。但し、パルプ状
微粒子中に含まれているＮ―メチル―２―ピロリドン
が、実施例１の場合と同様にスラリー作成工程でできる
だけ溶出しないように、残存させるべく、手早く注意し
て作業を実施した。次に、タッピー式角型手抄機を用い
て、該抄紙用スラリーを使用して抄紙し、重量が約３５
０ｇ／ｍ2 の水分を多量に含んだ湿紙を得た。なお、こ
の湿紙は乾燥した後の坪量が３３．５ｇ／ｍ 2 であっ
た。またこの乾燥紙を分解してパルプ状微粒子を取り出
し、Ｎ―メチル―２―ピロリドンの含有量を測定したと
ころ、約１．１５重量％含まれていることが判ったの
で、さらに、パルプ状微粒子にＮ―メチル―２―ピロリ
ドンを含浸させるべく、噴霧器を用いＮ―メチルピロリ
ドンを乾燥紙に噴霧して、パルプ状微粒子に含まれるＮ
―メチル―２―ピロリドンの量が４．５重量％になるよ
うに調整した乾燥紙を得た。得られた乾燥紙を、実施例
１で用いたものと同一のカレンダー機により、表１に示
す条件でカレンダー加工を実施し、目的とする薄葉紙状
物を得た。得られた薄葉紙状物について諸特性を測定
し、その結果を表１に示した。Example 2 Polyresin prepared in the same manner as in Example 1
Metaphenylene isophthalamide short fiber dispersion and pulp
Ratio of short fiber to pulp-like fine particles dispersed slurry
Mix and stir so that the ratio is 97% by weight to 3% by weight.
To prepare a uniform papermaking slurry. However, pulpy
N-methyl-2-pyrrolidone contained in fine particles
However, as in the case of Example 1, it can be performed in the slurry forming step
Just be careful not to elute, so that it will remain.
And carried out the work. Next, using a tappy type square hand machine
Papermaking using the papermaking slurry, the weight is about 35
0 g / m2A wet paper web containing a large amount of water was obtained. In addition, this
Wet paper has a basis weight of 33.5 g / m after drying. 2And
It was In addition, the dry paper is decomposed to take out pulp-like fine particles.
Then, the content of N-methyl-2-pyrrolidone was measured.
Around that time, I found out that it contained about 1.15% by weight.
In addition, N-methyl-2-pyrroli
N-methylpyrroli
N is contained in the pulp-like fine particles by spraying dong on dry paper.
-The amount of methyl-2-pyrrolidone will be 4.5% by weight.
A dry paper adjusted in this way was obtained. The obtained dry paper was used as an example.
Shown in Table 1 with the same calender machine used in 1.
Calendar paper is processed under the following conditions to obtain the desired thin paper
I got a thing. Measure various properties of the obtained thin paper
The results are shown in Table 1.
【００３０】[0030]
【実施例３】実施例１の場合と同様にして作成したポリ
メタフェニレンイソフタラミド短繊維分散液と、パルプ
状微粒子分散スラリーとを短繊維対パルプ状微粒子の比
率が８７重量％対１３重量％となるように混合、撹拌し
て、均一な抄紙用スラリーを作成した。但し、パルプ状
微粒子中に含まれているＮ―メチル―２―ピロリドン
が、実施例１の場合よりも少なくなるようにするため
に、抄紙用スラリー液の固形分濃度が０．２５重量％に
なるように調整した。次に、タッピー式角型手抄機を用
いて、該抄紙用スラリーを使用して抄紙し、重量が約２
５０ｇ／ｍ2 の水分を多量に含んだ湿紙を得た。なお、
この湿紙は乾燥した後の坪量が１８．５ｇ／ｍ2 であっ
た。またこの乾燥紙を分解してパルプ状微粒子を取り出
し、Ｎ―メチル―２―ピロリドンの含有量を測定したと
ころ、約０．０３重量％含まれていることが判った。得
られた乾燥紙を、実施例１で用いたものと同一のカレン
ダー機により、表１に示す条件でカレンダー加工を実施
し、目的とする薄葉紙状物を得た。得られた薄葉紙状物
について諸特性を測定し、その結果を表１に示した。Example 3 Polymetaphenylene isophthalamide short fiber dispersion prepared in the same manner as in Example 1 and pulp-like fine particle dispersion slurry were mixed at a ratio of short fibers to pulp fine particles of 87% by weight to 13% by weight. % And mixed and stirred to prepare a uniform papermaking slurry. However, in order to reduce the amount of N-methyl-2-pyrrolidone contained in the pulp-like fine particles as compared with that in Example 1, the solid concentration of the papermaking slurry liquid was set to 0.25% by weight. I adjusted it so that. Next, a tappy type square hand machine was used to make paper using the slurry for paper making, and the weight was about 2
A wet paper web containing a large amount of water of 50 g / m 2 was obtained. In addition,
The wet paper had a basis weight after drying of 18.5 g / m 2 . The dried paper was decomposed to take out pulp-like fine particles, and the content of N-methyl-2-pyrrolidone was measured. As a result, it was found that the content was about 0.03% by weight. The obtained dried paper was calendered under the conditions shown in Table 1 by the same calender machine as that used in Example 1 to obtain the target thin paper sheet. Various properties of the obtained thin paper sheet were measured, and the results are shown in Table 1.
【００３１】[0031]
【比較例１】実施例１と比較するために、実施例１と同
様の方法で、短繊維対パルプ状微粒子の比率が８２重量
％対１８重量％となるように混合、撹拌して均一な抄紙
用スラリーを作成した。但し、パルプ状微粒子中に含ま
れているＮ―メチル―２―ピロリドンが、実施例１の場
合よりも少なくなるようにするために、抄紙用スラリー
液の固形分濃度が０．２５重量％になるように調整し
た。次に、タッピー式角型手抄機を用いて、該抄紙用ス
ラリーを使用して抄紙し、かつ水洗して、重量が約２３
２ｇ／ｍ2 の水分を多量に含んだ湿紙を得た。なお、こ
の湿紙は乾燥した後の坪量が２５．５ｇ／ｍ2 であっ
た。またこの乾燥紙を分解してパルプ状微粒子を取り出
し、Ｎ―メチル―２―ピロリドンの含有量を測定したと
ころ、約０．０１重量％含まれていることが判った。得
られた乾燥紙を、実施例１で用いたものと同一のカレン
ダー機により、表１に示す条件でカレンダー加工を実施
し、目的とする薄葉紙状物を得た。得られた薄葉紙状物
について諸特性を測定し、その結果を表１にまとめ比較
例１として示した。Comparative Example 1 For comparison with Example 1, mixing and stirring were performed in the same manner as in Example 1 so that the ratio of short fibers to pulp-like fine particles was 82% by weight to 18% by weight. A papermaking slurry was prepared. However, in order to reduce the amount of N-methyl-2-pyrrolidone contained in the pulp-like fine particles as compared with that in Example 1, the solid concentration of the papermaking slurry liquid was set to 0.25% by weight. I adjusted it so that. Next, using a tappy type square hand machine, papermaking was performed using the slurry for papermaking and washed with water, and the weight was about 23.
A wet paper web containing a large amount of 2 g / m 2 of water was obtained. The wet paper had a basis weight after drying of 25.5 g / m 2 . Further, when the dried paper was decomposed to take out pulp-like fine particles and the content of N-methyl-2-pyrrolidone was measured, it was found that the content was about 0.01% by weight. The obtained dried paper was calendered under the conditions shown in Table 1 by the same calender machine as that used in Example 1 to obtain the target thin paper sheet. Various properties of the obtained thin paper sheet were measured, and the results are summarized in Table 1 and shown as Comparative Example 1.
【００３２】[0032]
【比較例２】比較のため、パルプ状微粒子にＮ―メチル
―２―ピロリドンを含浸させるべく、噴霧器を用いＮ―
メチル―２―ピロリドンを乾燥紙に噴霧して、パルプ状
微粒子に含まれるＮ―メチル―２―ピロリドンの量が
６．５０重量％になるように調整した以外は実施例２と
同様に行って乾燥紙を得、得られ他乾燥紙を、実施例１
で用いたものと同一のカレンダー機により、表１に示す
条件でカレンダー加工を実施し、得た薄葉紙状物の諸特
性を測定し、その結果について表１に示した。[Comparative Example 2] For comparison, N-methyl-2-pyrrolidone was impregnated into pulp-like fine particles by using a sprayer N-.
The same procedure as in Example 2 was performed except that methyl-2-pyrrolidone was sprayed onto dry paper so that the amount of N-methyl-2-pyrrolidone contained in the pulp-like fine particles was adjusted to 6.50% by weight. A dry paper was obtained and the other dry paper obtained was used in
Calendering was performed under the conditions shown in Table 1 using the same calendering machine as used in 1., and various characteristics of the obtained thin paper sheet were measured. The results are shown in Table 1.
【００３３】[0033]
【比較例３】比較のため、実施例１の場合と同様にして
作成したポリメタフェニレンイソフタラミドの短繊維分
散液と、パルプ状微粒子分散スラリーとを、短繊維対パ
ルプ状微粒子の比率が９９．５重量％対０．５重量％に
なるように混合、撹拌して、均一な抄紙用スラリーを作
成した以外は実施例２と同様にして乾燥紙を得、その乾
燥紙について実施例２と同様にカレンダー加工を実施
し、得られた薄葉紙状物について諸特性を測定して、そ
の結果を表１に比較例３として示した。COMPARATIVE EXAMPLE 3 For comparison, a short fiber dispersion of polymetaphenylene isophthalamide prepared in the same manner as in Example 1 and a pulp-like fine particle dispersion slurry were mixed at a ratio of short fibers to pulp-like fine particles. Dry paper was obtained in the same manner as in Example 2 except that a uniform papermaking slurry was prepared by mixing and stirring so that the content was 99.5% by weight to 0.5% by weight. Calendering was carried out in the same manner as above, and various properties of the obtained thin paper sheet were measured, and the results are shown in Table 1 as Comparative Example 3.
【００３４】[0034]
【比較例４】比較のため、従来公知の技術にもとずき作
成したポリメタフェニレンイソフタラミドの短繊維分散
液と、スラリー濃度を低下せしめて、極性溶剤が極力水
中に溶出するようにして作成したパルプ状微粒子分散ス
ラリーとを短繊維対パルプ状微粒子の比率が７５重量％
対２５重量％になるように混合、撹拌して、均一な抄紙
用スラリーを試作した。続いて、タッピー式角型手抄機
を用いて、該抄紙用スラリーを使用して抄紙し、約２６
０ｇ／ｍ2 の重量からなる水分を多量に含んだ湿紙を作
成した。なお、この湿紙は、乾燥した後の坪量が２０．
５ｇ／ｍ2 であった。またこの乾燥紙を分解してパルプ
状微粒子を取り出し、Ｎ―メチル―２―ピロリドンの含
有量を測定したところ、約０．０１重量％含まれてい
た。濾紙を乾燥して得た乾燥紙を実施例１で用いたもの
と同一のカレンダー機により、表１に示す条件でカレン
ダー加工を実施し、目的とする薄葉紙状物を得、その薄
葉紙状物について諸特性を測定し、結果を表１に比較例
４として示した。[Comparative Example 4] For comparison, a short fiber dispersion liquid of polymetaphenylene isophthalamide prepared based on a conventionally known technique and a slurry concentration were reduced so that a polar solvent was dissolved in water as much as possible. The pulp-like fine particle-dispersed slurry prepared by the above method has a short fiber to pulp-like fine particle ratio of 75% by weight.
A uniform slurry for papermaking was made as a trial by mixing and agitating so as to be 25% by weight. Then, using a tappy type square hand machine, papermaking was performed using the slurry for papermaking to about 26
A wet paper containing a large amount of water having a weight of 0 g / m 2 was prepared. The wet paper has a basis weight of 20.
It was 5 g / m 2 . Further, the dry paper was decomposed to take out pulp-like fine particles, and the content of N-methyl-2-pyrrolidone was measured, and it was found to be about 0.01% by weight. The dried paper obtained by drying the filter paper was calendered under the conditions shown in Table 1 using the same calender as that used in Example 1 to obtain the target thin paper-like material. Various properties were measured, and the results are shown in Table 1 as Comparative Example 4.
【００３５】[0035]
【表１】 [Table 1]
【００３６】表１から明らかなように、本発明の耐熱性
薄葉紙状物は実用的強力を有し、かつ、シリコン油等の
吸収性、含浸性に優れているため、変圧器、電動機等の
巻線用絶縁材料として、また電子写真装置の定着ロール
や感光体等に使用されるクリーニングウエブとして有用
である。As is clear from Table 1, the heat-resistant thin paper-like material of the present invention has practical strength and is excellent in absorption and impregnation of silicon oil and the like. It is useful as an insulating material for windings and as a cleaning web used for fixing rolls and photoconductors of electrophotographic apparatuses.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｇ０３Ｇ 15/20 １０５ Ｇ０３Ｇ 15/20 １０５ Ｈ０１Ｆ 41/12 Ｈ０１Ｆ 41/12 Ｅ ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification code FI // G03G 15/20 105 G03G 15/20 105 H01F 41/12 H01F 41/12 E
Claims (2)
と、芳香族ポリアミド短繊維９９〜８０重量％との混合
物からなる水性スラリーから湿式抄造法によって形成さ
れた湿紙を加熱加圧加工して得られる耐熱性薄葉紙の製
造方法において、加熱加圧加工前の薄葉紙中の芳香族ポ
リアミドパルプに含まれる極性溶媒の量が、０．０２〜
４．５０％であり、かつ、加熱加圧加工後の薄葉紙の坪
量が８〜４５ｇ／ｍ2、嵩密度が０．２０〜０．９０ｇ
／ｃｍ3であることを特徴とする耐熱性薄葉紙の製造方
法。1. Aromatic polyamide pulp 1 to 20% by weight
And a heat-resistant thin paper obtained by heat-pressing a wet paper formed by a wet papermaking method from an aqueous slurry comprising a mixture of 99-80% by weight of aromatic polyamide short fibers. The amount of the polar solvent contained in the aromatic polyamide pulp in the thin paper before is 0.02 to
4.50 %, and the basis weight of the thin paper after heat and pressure processing is 8 to 45 g / m 2 , and the bulk density is 0.20 to 0.90 g.
/ Cm 3 is a method for producing a heat-resistant thin paper.
せた場合における、１２００センチストローク以下の粘
度であるシリコン油の含浸率が１５重量％以上である請
求項１に記載の耐熱性薄葉紙の製造方法。2. Viscosity of 1200 cm stroke or less when impregnated under a vacuum of about 150 Torr for 3 days.
The method for producing a heat-resistant thin paper according to claim 1, wherein the degree of impregnation of the silicone oil is 15% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13685892A JP3380267B2 (en) | 1992-05-28 | 1992-05-28 | Method of manufacturing heat-resistant thin paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13685892A JP3380267B2 (en) | 1992-05-28 | 1992-05-28 | Method of manufacturing heat-resistant thin paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05325693A JPH05325693A (en) | 1993-12-10 |
| JP3380267B2 true JP3380267B2 (en) | 2003-02-24 |
Family
ID=15185162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13685892A Expired - Lifetime JP3380267B2 (en) | 1992-05-28 | 1992-05-28 | Method of manufacturing heat-resistant thin paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3380267B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007109671A (en) * | 2006-12-22 | 2007-04-26 | Du Pont Teijin Advanced Paper Kk | Aramid thin-leaf material and manufacturing method of the same |
| CN102930978B (en) * | 2012-11-15 | 2014-09-10 | 常州市英中电气有限公司 | Wet forming process of super-high voltage transformer insulator |
-
1992
- 1992-05-28 JP JP13685892A patent/JP3380267B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05325693A (en) | 1993-12-10 |
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