JPS59125979A - Treatment of polyurethane-containing fiber sheet - Google Patents

Treatment of polyurethane-containing fiber sheet

Info

Publication number
JPS59125979A
JPS59125979A JP110383A JP110383A JPS59125979A JP S59125979 A JPS59125979 A JP S59125979A JP 110383 A JP110383 A JP 110383A JP 110383 A JP110383 A JP 110383A JP S59125979 A JPS59125979 A JP S59125979A
Authority
JP
Japan
Prior art keywords
polyurethane
fiber sheet
fibers
containing fiber
treatment
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.)
Granted
Application number
JP110383A
Other languages
Japanese (ja)
Other versions
JPS6224552B2 (en
Inventor
雅人 島田
長島 純之助
中村 暉夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP110383A priority Critical patent/JPS59125979A/en
Publication of JPS59125979A publication Critical patent/JPS59125979A/en
Publication of JPS6224552B2 publication Critical patent/JPS6224552B2/ja
Granted legal-status Critical Current

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  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。
(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明はポリウレタン含有繊維シートの製造方法に係り
、さらに詳しくは優れた柔軟性のあるポリウレタン含有
繊維シート製品を得る処理方法に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyurethane-containing fibrous sheet, and more particularly to a processing method for obtaining a polyurethane-containing fibrous sheet product with excellent flexibility.

人工皮革が開発されて以来2種々の製品が上布されてい
る。かかる人工皮革製品は2表面形態やデザインが優れ
ているため市場で人気を博しているが、衣料用途として
はさらにすぐれた風合い。
Since the development of artificial leather, two different types of products have been fabricated. Such artificial leather products are popular in the market because of their excellent two-surface morphology and design, but they have an even better texture when used in clothing.

殊に柔軟性が要求されているのが現状である。このため
、柔軟性改善のために人工皮革の製茶工程で種々検討が
加えられているが、かかる工程改善では、該人工皮革の
強力、摩耗性、形態安定性等の物性低下を招きやすく、
必ずしも満足な結果を得ていない。すなわち1人工皮革
製品として必要な物性を維持し力から、よりすぐれた柔
軟性を得る処理技術の発明が待ち望まれている。
The current situation is that flexibility is particularly required. For this reason, various studies have been conducted in the tea manufacturing process of artificial leather to improve its flexibility, but such process improvements tend to lead to a decrease in the physical properties of the artificial leather, such as strength, abrasion resistance, and shape stability.
The results are not always satisfactory. In other words, the invention of a processing technique that maintains the physical properties necessary for an artificial leather product and obtains superior flexibility from strength is eagerly awaited.

本発明者らは、かかる目的を達成するだめ、鋭意研究し
た結果、繊維シートに含有するポリウレタン同志やポリ
ウレタンと繊維間、繊維シートを構成する繊維同志など
における摩擦抵抗を下げ。
In order to achieve this objective, the present inventors conducted intensive research and found that the frictional resistance between the polyurethanes contained in the fiber sheet, between the polyurethane and the fibers, and between the fibers constituting the fiber sheet was reduced.

揉み工程で夫々移動しやすい状態にすることにより、著
しく柔軟性のすぐれた風合いの人工皮革を得ることを究
明した。すなわち2本発明の骨子は次の通りである。
It was discovered that artificial leather with an extremely flexible texture can be obtained by making it easy to move during the kneading process. That is, the gist of the present invention is as follows.

ポリウレタン含有繊維シートを染色した後、該シートに
含有されるポリウレタン間、および/またはポリウレタ
ンと繊維間、および/または繊維間同志の摩擦抵抗を低
減させる薬剤を付与し、続いて加熱下で揉布処理を施す
ことを特徴とする特リウレタン含有繊維シートの処理方
法である。
After dyeing the polyurethane-containing fiber sheet, an agent is applied to reduce the frictional resistance between the polyurethanes contained in the sheet, between the polyurethane and the fibers, and/or between the fibers, and then the fibers are rubbed under heat. This is a method for treating a fiber sheet containing special urethane, which is characterized by subjecting it to a treatment.

さらに2本発明は摩擦抵抗を低減させる薬剤を付与した
後に揉布処理することによりツ思わぬ程の柔軟な風合効
果を達成し得だものであって?該薬剤の単独処理や該薬
剤処理と揉布処理の組み合わせ処理順序が逆の場合では
良好な結果は得られない。
Furthermore, according to the present invention, an unexpectedly soft texture effect can be achieved by applying a chemical that reduces frictional resistance and then applying a rubbing treatment. Good results cannot be obtained if the chemical is used alone or if the chemical treatment and rubbing treatment are combined in the reverse order.

次に2本発明の内容について詳細に説明する。Next, two contents of the present invention will be explained in detail.

本発明に係るポリウレタン含有繊維シートとは。What is the polyurethane-containing fiber sheet according to the present invention?

リアクリル等の合成繊維およびこれらの改質繊維からな
るが、特にナイロンから々る繊維シートに対して効果が
犬である。又、かかる繊維シートを構成する繊維の単糸
繊度は1デニール以下で特に良好な効果が発揮され、こ
れら極細繊維とバインダーで構成される人工皮革に適用
された場合に最大の効果が発揮される。さらに該繊維シ
ートはパフ、起毛、剪毛、電植等の手段を経て立毛化さ
れたものも含む。
Although it is made of synthetic fibers such as acrylic fibers and modified fibers thereof, it is particularly effective on fiber sheets made from nylon. In addition, a particularly good effect is exhibited when the single fiber fineness of the fibers constituting such a fiber sheet is 1 denier or less, and the greatest effect is exhibited when applied to artificial leather composed of these ultrafine fibers and a binder. . Furthermore, the fiber sheets include those that have been raised by means such as puffing, raising, shearing, electroplating, and the like.

該繊維シートに含有するポリウレタンは1組成面から特
に限定されるものでは々いが、エマルジョンタイプおよ
びエマルジョンタイプと溶剤タイプの組み合わせだもの
であることが2本発明効果をより一層促進する。本発明
を実施するにあたり有効なポリウレタン組成としては、
各種ポリエーテル系あるいはポリエステル系のものが挙
げられ。
The polyurethane contained in the fiber sheet is not particularly limited in terms of composition, but the effects of the present invention will be further promoted if it is an emulsion type or a combination of an emulsion type and a solvent type. Polyurethane compositions effective in carrying out the present invention include:
Examples include various polyether-based or polyester-based ones.

長鎖ジオール(ポリエステルまたはポリエーテル)。Long chain diol (polyester or polyether).

ジイソシアナートおよび低分子量の鎖伸長剤(グリコー
ル、ジアミンなど)の反応で得られたポリウレタンが一
般的である。かかるポリウレタンを含浸させる方法は、
ポリウレタン溶液中に繊維シートを通過させ、マングル
で絞液して乾燥させるか、ポリウレタン溶液を繊維シー
ト上にコーティングする方法が一般的である。
Polyurethanes obtained by the reaction of diisocyanates and low molecular weight chain extenders (glycols, diamines, etc.) are common. The method for impregnating such polyurethane is as follows:
Common methods include passing a fiber sheet through a polyurethane solution, squeezing the solution with a mangle and drying it, or coating the fiber sheet with a polyurethane solution.

かかるポリウレタンの含有量は、製造されるポリウレタ
ン含有繊維シートの重量に対して3〜90%であるのが
一般である。
The content of such polyurethane is generally 3 to 90% based on the weight of the polyurethane-containing fiber sheet to be produced.

また1本発明における繊維シートは、ポリウレタンを主
体として含有するものであるが、アクリル、シリコン、
フッ素系樹脂など他のバインダーが併用されていてもよ
い。
In addition, the fiber sheet in the present invention mainly contains polyurethane, but it also contains acrylic, silicone,
Other binders such as fluororesin may also be used in combination.

本発明法では、かかるポリウレタン含有繊維シートを染
色するものであるが、必要により、染色前に立毛化、熱
セット、極細化などの処理工程を付与し得る。染色手段
としては、基本的には従来繊維シートに適用されるよう
な手段2例えば、液流染色機やウィンス染色機を使用す
ればよく2本発明法で何ら制限を受けるものでない。
In the method of the present invention, such a polyurethane-containing fiber sheet is dyed, but if necessary, processing steps such as napping, heat setting, and ultra-fineness may be applied before dyeing. As a dyeing means, basically any means conventionally applied to fiber sheets, such as a jet dyeing machine or a wince dyeing machine, may be used, and the method of the present invention is not limited in any way.

本発明法では、上記染色後、ポリウレタン含有繊維シー
トに含有するポリウレタン同志、ポリウレタンと繊維間
、シートを構成する繊維同志の摩擦抵抗を低減させる薬
剤を付与し、揉布処理する手段を適用する点に特徴を有
する。上述の摩擦抵抗を低減させる薬剤としては、カチ
オン活性剤。
In the method of the present invention, after the above-mentioned dyeing, an agent is applied to reduce the frictional resistance between the polyurethanes contained in the polyurethane-containing fiber sheet, between the polyurethane and the fibers, and between the fibers constituting the sheet, and a means of rubbing is applied. It has the following characteristics. As the agent for reducing the frictional resistance mentioned above, a cationic activator is used.

性剤、牛脂油、オリーブ油等の天然動植物油脂が効果的
である。これらのうち1合成界面活性剤では、ソルビタ
ンモノオレートの如き多価アルコール型非イオン活性剤
、ポリオールポリウレタン系非イオン活性剤などは、特
に効果的である。さらに、最終製品品位や後の加工工程
での取扱い性を考慮して、公知の静電防止薬剤を加えて
もよい。
Natural animal and vegetable oils such as sexual agents, tallow oil, and olive oil are effective. Among these synthetic surfactants, polyhydric alcohol type nonionic surfactants such as sorbitan monooleate, polyol polyurethane type nonionic surfactants, etc. are particularly effective. Furthermore, a known antistatic agent may be added in consideration of the quality of the final product and ease of handling in subsequent processing steps.

かかる薬剤の付与方法は含浸法、パッディング法、スプ
レー法、コーティング法などいずれの方法でもよい。ま
だ、薬剤の使用濃度は上述の付与方法、繊維シートの種
類、形状、所望する風合いにより決定すればよい。
The method for applying such a drug may be any method such as an impregnation method, a padding method, a spray method, or a coating method. However, the concentration of the drug to be used may be determined depending on the above-mentioned application method, the type and shape of the fiber sheet, and the desired texture.

続いて、かかる薬剤を付与した後、乾燥し、あるいは未
乾燥のまま揉布処理を行なう。かかる揉布処理の効果は
、ポリウレタン含有繊維シートを構成するポリウレタン
間、ポリウレタンと繊維間。
Subsequently, after applying such a chemical, the material is dried or subjected to a rubbing treatment without being dried. The effect of such a rubbing treatment is between the polyurethanes constituting the polyurethane-containing fiber sheet and between the polyurethane and the fibers.

および構成する繊維間に該薬剤を浸透促進させ。and promote penetration of the drug between the constituent fibers.

均一に拡散させ、この結果、該ポリウレタン同志。This results in uniform dispersion of the polyurethane.

該ポリウレタンと該繊維間、該繊維同志の平滑性を高め
ることにより完全な柔軟性が付与される。
Complete flexibility is imparted by increasing the smoothness between the polyurethane and the fibers and between the fibers.

さらに、かかる揉布処理は、ポリウレタン含有繊維シー
トを外力により伸張、収縮、圧縮、屈曲。
Furthermore, in this rubbing process, the polyurethane-containing fiber sheet is stretched, contracted, compressed, and bent by external force.

衝突などの作用が交絡して与えられるから、上述の作用
効果が発揮されるのである。
The effects described above are achieved because effects such as collisions are intertwined with each other.

本発明に係る揉布処理手段としては、タンブラ−、カム
フィツト、縮絨などの方法があるが、前記した伸張、収
縮、圧縮、屈曲、衝突などの作用を個々に有する装置を
組み合わせる方法でもよい。
The rubbing treatment means according to the present invention includes methods such as a tumbler, a cam fit, and a carpet, but it is also possible to use a combination of devices each having the above-mentioned stretching, shrinking, compressing, bending, and colliding functions.

まだ、かかる揉布処理に際しては1通常50〜120°
Cで、20〜60分間の条件が適用されるが。
However, during such rubbing treatment, the temperature is usually 50 to 120°.
At C, conditions of 20 to 60 minutes are applied.

必要に応じて、他の条件を採用してもよいし、また水分
を付与して処理してもよい。かかる水分付与方法として
は、揉処理機内の水分率を少なくとも5%−好ましくは
10〜50係の雰囲気に保てばよく、具体的には、たと
えば揉処理機内に生蒸気を噴出させる方法、揉処理機人
口で繊維シート上に水を噴霧させる方法などの手段を採
用することができる。
If necessary, other conditions may be adopted, or moisture may be added for treatment. As such a method of adding moisture, it is sufficient to maintain the moisture content in the rubbing machine at an atmosphere of at least 5% - preferably 10 to 50%.Specifically, for example, a method of spouting live steam into the rubbing machine, Means such as a method of spraying water onto the fiber sheet using a processing machine can be adopted.

かかる水分の付与と加熱は、ポリウレタン含有繊維シー
トを構成するポリウレタン間、ポリウレタンと繊維間、
該構成繊維間に、水分子の空隙を与え、摩擦抵抗を低減
させるに効果のある前記合成界面活性剤や天然動植物油
脂の浸透拡散、および該薬剤の該繊維シート内層部での
定着に一層効果的である。
This application of moisture and heating is performed between the polyurethanes constituting the polyurethane-containing fiber sheet, between the polyurethane and the fibers, and between the polyurethane and the fibers.
Providing voids for water molecules between the constituent fibers, which is more effective in permeating and diffusing the synthetic surfactant and natural animal and vegetable oils and fats that are effective in reducing frictional resistance, and fixing the drug in the inner layer of the fiber sheet. It is true.

かくて9本発明法を適用したポリウレタン含有繊維シー
トは1表面触感のみ々らず、完全な柔軟風合いの染色製
品となる。
Thus, the polyurethane-containing fiber sheet to which the method of the present invention is applied becomes a dyed product with not only a surface texture but also a perfect soft texture.

以下、実施例を挙げて本発明を具体的に説明するが、何
らこれに限定されるものではない。
Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto in any way.

実施例1 島成分にポリアミド57受、海成分にポリスチレン46
係を用いた16島の海島型高分子相互配列体繊維(3,
8eL 、  51 mm 、  ケン縮付与)ステー
プルをクロスラップウェッブとして十分ニードルパン*
 Ll  フェルトを得た。これを乾熱収縮させり後、
エマルジョンタイプウレタンとポリビニールアルコール
の混合液を含浸させ、乾燥後140°0のキユアリング
を行なった。次いでトリクレン中で海成分ポリスチレン
を除去し、そして溶剤タイプポリウレタンである12%
ポリウレタンジメチルホルムアミド液にさらに含浸し、
絞った後水系液中で凝固し、温水で充分洗浄した。その
後2枚にスライスおよびパフィングして表面に毛羽を有
し、単糸デニール0.16デニールのポリアミド繊維6
0%、  トータルポリウレタン量が4Q%からなるス
ェード調人工皮革の非染色生機を得た。これをサーキュ
ラ染色機にて酸性染料を用いて100℃x40分染色し
・ ブラウン色に染め上げた。この着色物をバキューム
脱水した後、ポリエチレンポリアミン高級脂肪酸アマイ
ド誘導体(有効成分13%)30g/7と脂肪酸アミン
のアミド化合物(有効成分10%) 10 g7’lか
らなるパッド浴を通して、乾燥した。
Example 1 Polyamide 57 for the island component and polystyrene 46 for the sea component
16-island sea-island type polymer mutual array fiber (3,
8eL, 51 mm, crimped) Needle pan enough to cross-wrap the staples*
Ll felt was obtained. After dry heat shrinking this,
It was impregnated with a mixture of emulsion type urethane and polyvinyl alcohol, dried and then cured at 140°0. The sea-component polystyrene was then removed in triclene and the 12% solvent-type polyurethane
Further impregnated with polyurethane dimethylformamide solution,
After squeezing, it solidified in an aqueous solution and was thoroughly washed with warm water. Thereafter, it is sliced into two pieces and puffed to form a polyamide fiber 6 with fluff on the surface and a single yarn denier of 0.16 denier.
A non-dyed gray material of suede-like artificial leather was obtained with a total polyurethane content of 0% and 4Q%. This was dyed in a circular dyeing machine using an acid dye at 100°C for 40 minutes to give it a brown color. After vacuum dehydration of this colored material, it was dried through a pad bath consisting of 30 g/7'l of a polyethylene polyamine higher fatty acid amide derivative (active ingredient 13%) and 10 g/7'l of a fatty acid amine amide compound (active ingredient 10%).

次いで次の条件でタンブラ加工機で揉布処理した後、仕
上セットした。
Next, it was rubbed in a tumbler processing machine under the following conditions, and then finished and set.

タンブラ加工機二東洗(株)製 予 熱二80°cx5分 湿 熱:98℃×4分(湿度30%RH)乾 燥:50
〜b 回転数:30r、plm タンブラ加工時の試料形態二袋詰め 得られた製品は非常に柔軟性のあるソフトタッチのもの
であった。
Tumbler processing machine manufactured by Nitoarai Co., Ltd. Preheat at 280°C x 5 minutes Humidity Heat: 98°C x 4 minutes (humidity 30% RH) Dry: 50
-b Rotation speed: 30 r, plm Sample form during tumble processing: Two bags of the obtained product were very flexible and soft to the touch.

比較例1 実施例1の染色、薬剤付与後乾燥し、続いてタンブラ−
加工を実施せずに仕上セットを行なった。
Comparative Example 1 After dyeing and applying chemicals in Example 1, drying, followed by tumbler
Finishing was performed without any processing.

得られた製品は2表面の触感はソフトであるが。The resulting product has a soft texture on the surface.

芯のある硬さを有するものとなった。It has a certain hardness.

比較例2 実施例1の染色後、薬剤を付与せずにタンブラ−加工を
実施した。その後、仕上セットを行なった。タンブラ−
加工条件は実施例1と同条件を適用したにかかわらず、
得られた製品は風合いががさつき2表面触感の悪いもの
であった。
Comparative Example 2 After dyeing in Example 1, tumble processing was carried out without applying any chemicals. After that, I did the finishing set. tumbler
Although the processing conditions were the same as in Example 1,
The resulting product had a rough texture and a poor surface feel.

比較例3 実施例1の染色後乾燥し、実施例1と同条件でタンブラ
−加工を実施した後に薬剤を付与した。
Comparative Example 3 After dyeing in Example 1, it was dried and tumbled under the same conditions as in Example 1, and then a chemical was applied.

続いて乾燥し、仕上セットを実施した。得られた製品品
位は、比較例1の場合と大差ない風合の悪いものであっ
た。
Subsequently, it was dried and a finishing set was performed. The quality of the obtained product was not much different from that of Comparative Example 1, and had a poor texture.

実施例2 実施例1に記述するスェード調人工皮革をサーキュラー
染色機により、錯塩酸性染料を用いて赤色に染色した。
Example 2 The suede-like artificial leather described in Example 1 was dyed red using a complex acid dye using a circular dyeing machine.

染色後、染色機中で薬剤としてンルビタンモノオレエー
ト:8%OWfとPOEモノオレエート:2%OWfを
該皮革に付着せしめ、その後、乾燥した。続いて次の条
件で実施例1と同様にタンブラ−加工した。
After dyeing, Nrubitan monooleate: 8% OWf and POE monooleate: 2% OWf were applied to the leather as chemicals in a dyeing machine, and then dried. Subsequently, tumble processing was performed in the same manner as in Example 1 under the following conditions.

乾 燥:60〜b 回転数:45r、p6m 最後に仕上セットを実施した。Drying: 60~b Rotation speed: 45r, p6m Finally, a finishing set was performed.

得られた製品は、芯のないこなれた柔軟焦合いのものと
なった。
The resulting product had a smooth, flexible focus with no core.

Claims (1)

【特許請求の範囲】[Claims] ポリウレタン含有繊維シートを染色した後、該シートに
含有されるポリウレタン間、および/またはポリウレタ
ンと繊維間、および/または繊維間同志の摩擦抵抗を低
減させる薬剤を付与し、続いて加熱下で揉布処理を施す
ことを特徴とするポリウレタン含有繊維シートの処理方
法。
After dyeing the polyurethane-containing fiber sheet, an agent is applied to reduce the frictional resistance between the polyurethanes contained in the sheet, between the polyurethane and the fibers, and/or between the fibers, and then the fibers are rubbed under heat. A method for treating a polyurethane-containing fiber sheet, which comprises subjecting it to a treatment.
JP110383A 1983-01-10 1983-01-10 Treatment of polyurethane-containing fiber sheet Granted JPS59125979A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP110383A JPS59125979A (en) 1983-01-10 1983-01-10 Treatment of polyurethane-containing fiber sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP110383A JPS59125979A (en) 1983-01-10 1983-01-10 Treatment of polyurethane-containing fiber sheet

Publications (2)

Publication Number Publication Date
JPS59125979A true JPS59125979A (en) 1984-07-20
JPS6224552B2 JPS6224552B2 (en) 1987-05-28

Family

ID=11492142

Family Applications (1)

Application Number Title Priority Date Filing Date
JP110383A Granted JPS59125979A (en) 1983-01-10 1983-01-10 Treatment of polyurethane-containing fiber sheet

Country Status (1)

Country Link
JP (1) JPS59125979A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6183378A (en) * 1984-10-01 1986-04-26 Toray Ind Inc Suede-like artificial leather
JPS63303185A (en) * 1987-05-30 1988-12-09 Yoshimitsu Saito Flexibilizing processing and wrinkling processing for artificial leathers and machine device therefor
JPS6485378A (en) * 1987-06-19 1989-03-30 Rorika Etsuse Pi A Production of synthetic same leather
WO2007099951A1 (en) * 2006-02-28 2007-09-07 Kuraray Co., Ltd. Artificial leather and method for producing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4996041A (en) * 1972-12-12 1974-09-11
JPS52102344A (en) * 1976-02-24 1977-08-27 Dai Ichi Kogyo Seiyaku Co Ltd Modifier for surface-coating material of synthetic leather
JPS5324006A (en) * 1976-08-17 1978-03-06 Kuraray Co Production of soft leather like sheet article

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4996041A (en) * 1972-12-12 1974-09-11
JPS52102344A (en) * 1976-02-24 1977-08-27 Dai Ichi Kogyo Seiyaku Co Ltd Modifier for surface-coating material of synthetic leather
JPS5324006A (en) * 1976-08-17 1978-03-06 Kuraray Co Production of soft leather like sheet article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6183378A (en) * 1984-10-01 1986-04-26 Toray Ind Inc Suede-like artificial leather
JPS63303185A (en) * 1987-05-30 1988-12-09 Yoshimitsu Saito Flexibilizing processing and wrinkling processing for artificial leathers and machine device therefor
JPS6485378A (en) * 1987-06-19 1989-03-30 Rorika Etsuse Pi A Production of synthetic same leather
WO2007099951A1 (en) * 2006-02-28 2007-09-07 Kuraray Co., Ltd. Artificial leather and method for producing the same

Also Published As

Publication number Publication date
JPS6224552B2 (en) 1987-05-28

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