JPH10102317A - Polyvinyl chloride-based fiber and production thereof - Google Patents
Polyvinyl chloride-based fiber and production thereofInfo
- Publication number
- JPH10102317A JPH10102317A JP25426696A JP25426696A JPH10102317A JP H10102317 A JPH10102317 A JP H10102317A JP 25426696 A JP25426696 A JP 25426696A JP 25426696 A JP25426696 A JP 25426696A JP H10102317 A JPH10102317 A JP H10102317A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl chloride
- resin
- weight
- vinyl
- vinyl acetate
- 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
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリ塩化ビニル系
繊維に関するものである。さらに詳しくは、紡糸に際し
て可塑剤を添加することなく、又、紡糸工程に特殊な手
段を用いることなく、しかも、無可塑ポリ塩化ビニル繊
維の性質を大幅に変えることなく、紡糸（曳糸）性が改
良され、耐熱性に優れ、又、艶や風合いがコントロール
されたポリ塩化ビニル系繊維に関する。The present invention relates to a polyvinyl chloride fiber. More specifically, the spinning (spinning) properties are achieved without adding a plasticizer during spinning, without using any special means in the spinning process, and without significantly changing the properties of the non-plasticized polyvinyl chloride fiber. The present invention relates to a polyvinyl chloride fiber having improved heat resistance, excellent heat resistance, and controlled gloss and texture.
【０００２】[0002]
【従来の技術】従来周知の如く、無可塑ポリ塩化ビニル
樹脂は、繊維として優れた性質を持っているが、紡糸に
際しては、溶融粘度が高く、且つ、高温時において熱分
解することから、高倍率の曳糸延伸は不可能であった。
又、溶融紡糸により製造した一般のポリ塩化ビニル系繊
維は、ガラスの破片が光線を反射した場合のごとき特有
の光沢（艶）があり、繊維用としては不自然なため、塩
素化ポリ塩化ビニル樹脂等、溶融温度の高い、溶解性の
異なる艶消し剤が添加される。このため、曳糸性が更に
低下し、紡糸に際して糸切れが増加する傾向にあった。2. Description of the Related Art As is well known in the art, non-plasticized polyvinyl chloride resin has excellent properties as a fiber, but has a high melt viscosity during spinning and is thermally decomposed at high temperatures. Magnification spinning was not possible.
In addition, general polyvinyl chloride fibers produced by melt spinning have a specific gloss (gloss) when glass fragments reflect light, and are unnatural for fibers. A matting agent having a high melting temperature and different solubility, such as a resin, is added. For this reason, the spinnability tends to further decrease, and yarn breakage tends to increase during spinning.
【０００３】これらの問題を回避するため、一般には溶
剤を用いて乾式、又は湿式紡糸法により製造するか、或
いは特殊な方法、例えばノズルより紡出した溶融糸を直
ちに高温の熱媒中へ導く方法や、特公昭３４−６９０８
号公報に開示されたような繊維軸方向に設けた加熱紡糸
筒を通し瞬間的に加熱溶融し曳糸を行う方法が知られて
いる。又、特公昭４８−４３３８１号公報に開示された
ように塩化ビニルと共重合可能なプロピレン等の単量体
を共重合したポリ塩化ビニル系樹脂が使用されたりもし
ている。又、特公昭５１−２１０９号では、メチルメタ
クリレート系共重合体を配合する方法が開示されてい
る。しかし、これらの方法は、いずれも工程が複雑化し
たり、繊維の艶が増加したり、又、曳糸性改良効果が不
十分であったりして、決して満足の得られるものではな
かった。[0003] In order to avoid these problems, it is generally produced by a dry or wet spinning method using a solvent, or a special method, for example, a molten yarn spun from a nozzle is immediately introduced into a high-temperature heating medium. Method and Japanese Patent Publication No. 34-6908
There is known a method of instantaneously heating and melting through a heated spinning cylinder provided in a fiber axis direction as disclosed in Japanese Patent Application Laid-Open Publication No. H11-15064. Further, as disclosed in JP-B-48-43381, a polyvinyl chloride resin obtained by copolymerizing a monomer such as propylene copolymerizable with vinyl chloride has been used. Japanese Patent Publication No. Sho 51-2109 discloses a method of blending a methyl methacrylate copolymer. However, these methods have never been satisfactory because of complicated processes, increased gloss of fibers, and insufficient spinnability improving effect.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、耐熱
性があり、艶や風合いがコントロールされたポリ塩化ビ
ニル系繊維を、高い曳糸性と工程安定性で得ることにあ
る。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyvinyl chloride fiber having heat resistance and a controlled luster and texture with high spinnability and process stability.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、ポリ塩化ビニル系
樹脂に、押し出し加工性及び熱安定性が劣り単独では加
熱溶融紡糸が全く困難とされている塩素化ポリ塩化ビニ
ル樹脂を併用し、更に、エチレン・酢ビ／塩ビグラフト
重合樹脂を配合することにより、耐熱性があり、艶や風
合いがコントロールされたポリ塩化ビニル系繊維を、高
い曳糸性と工程安定性で得られることを見い出し、本発
明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that polyvinyl chloride resin has poor extrusion processability and thermal stability, so that hot melt spinning alone can be performed. By using chlorinated polyvinyl chloride resin, which is considered to be quite difficult, and blending an ethylene / vinyl acetate / vinyl chloride graft polymer resin, it has heat resistance and its gloss and texture are controlled. Was found to be obtained with high spinnability and process stability, and the present invention was completed.
【０００６】即ち、本発明は、５０〜９５重量％の塩化
ビニル系樹脂と５〜５０重量％の塩素化ポリ塩化ビニル
樹脂の混合物１００重量部に対し、エチレン・酢ビ／塩
ビグラフト重合樹脂を５〜４０重量部配合した樹脂組成
物からなることを特徴とするポリ塩化ビニル系繊維、及
び、前記樹脂組成物を溶融紡糸することからなるポリ塩
化ビニル系繊維の製造法である。このポリ塩化ビニル系
繊維は、人造毛髪用として好適に用いることができる。That is, according to the present invention, an ethylene / vinyl acetate / vinyl chloride graft resin is added to 100 parts by weight of a mixture of 50 to 95% by weight of a vinyl chloride resin and 5 to 50% by weight of a chlorinated polyvinyl chloride resin. A polyvinyl chloride fiber comprising a resin composition blended in an amount of 5 to 40 parts by weight, and a method for producing a polyvinyl chloride fiber comprising melt-spinning the resin composition. This polyvinyl chloride fiber can be suitably used for artificial hair.
【０００７】[0007]
【発明の実施の形態】本発明において用いられる塩化ビ
ニル系樹脂とは、塩化ビニル単独重合体、塩化ビニルと
２０重量％までの他の共重合可能な単量体との共重合
体、或いはこれらの混合物である。前記共重合可能な単
量体の代表的なものとしては、エチレン、プロピレン、
アルキルビニルエーテル、ビニリデンクロライド、酢酸
ビニル、アクリル酸エステル、マレイン酸エステル等が
使用可能である。共重合体中のコモノマーの量が２０重
量％以上の場合、軟質化されて耐熱性が低下するだけで
なく、高価となるため好ましくない。好ましい共重合体
としては、加熱溶融加工時の熱安定性の点で、エチレ
ン、プロピレン、又は酢酸ビニルと、塩化ビニルとの共
重合体である。BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin used in the present invention refers to a vinyl chloride homopolymer, a copolymer of vinyl chloride and up to 20% by weight of another copolymerizable monomer, or a copolymer thereof. Is a mixture of Representative examples of the copolymerizable monomer include ethylene, propylene,
Alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylates, maleates and the like can be used. If the amount of the comonomer in the copolymer is 20% by weight or more, it is not preferred because not only softening is caused and heat resistance is lowered, but also the cost becomes high. Preferred copolymers are copolymers of ethylene, propylene, or vinyl acetate with vinyl chloride from the viewpoint of thermal stability during heat melt processing.
【０００８】又、前記塩化ビニル系樹脂の重合度につい
ては、重合度が高い方が、得られる繊維の強度が大きい
傾向にあるが、反面、曳糸性の点では重合度が低い方が
有利である。これらの関係から、塩化ビニル系樹脂の重
合度は、５００〜１５００程度、より好ましくは７００
〜１３００程度が良い。As for the degree of polymerization of the vinyl chloride resin, the higher the degree of polymerization, the higher the strength of the obtained fiber tends to be. On the other hand, the lower the degree of polymerization, the better in terms of spinnability. It is. From these relations, the polymerization degree of the vinyl chloride resin is about 500 to 1500, more preferably 700.
About 1300 is good.
【０００９】塩化ビニル系樹脂と併用する塩素化ポリ塩
化ビニル樹脂とは、塩素含有量が５６．７重量％以上に
後塩素化されたポリ塩化ビニル樹脂を意味するが、加熱
溶融加工時の熱安定性、加工性の点から、塩素含有量が
５８〜７０重量％のものが好ましい。塩素化の方法は、
気相、液相いずれでも良く、又、塩素化原料ポリ塩化ビ
ニル樹脂は、塊状、懸濁、或いは、その他の特に塩素化
に有利な方法により重合されたもので良く、又、この塩
素化原料ポリ塩化ビニル樹脂の重合度は、加工性の点で
４００〜１０００程度が好ましい。The chlorinated polyvinyl chloride resin used in combination with the vinyl chloride resin refers to a polyvinyl chloride resin having a chlorine content of 56.7% by weight or more and is chlorinated. From the viewpoints of stability and processability, those having a chlorine content of 58 to 70% by weight are preferred. The chlorination method is
The gaseous phase or the liquid phase may be used, and the chlorinated raw material polyvinyl chloride resin may be a lump, a suspension, or a polymer which is polymerized by any other method particularly advantageous for chlorination. The degree of polymerization of the polyvinyl chloride resin is preferably about 400 to 1,000 from the viewpoint of processability.
【００１０】前記塩化ビニル系樹脂と塩素化ポリ塩化ビ
ニル樹脂とを併用することで得られるポリ塩化ビニル系
繊維の耐熱性が向上し、又、艶、風合いがコントロール
される。この場合の両者の混合割合は、塩化ビニル系樹
脂が５０〜９５重量％、塩素化ポリ塩化ビニル樹脂が５
〜５０重量％である。前記塩素化ポリ塩化ビニル樹脂の
割合が５重量％未満の場合には、艶消し性や耐熱性向上
に効果的でなく、又、５０重量％以上の場合には、高温
加工時の熱安定性が大幅に低下するため、長時間の連続
紡糸が困難となる。これらの点より、塩素化ポリ塩化ビ
ニル樹脂の割合は、１０〜４５重量％がより好ましい。[0010] The combined use of the vinyl chloride resin and the chlorinated polyvinyl chloride resin improves the heat resistance of the polyvinyl chloride fiber obtained and controls the luster and texture. In this case, the mixing ratio of the both is 50 to 95% by weight of the vinyl chloride resin and 5 to 95% by weight of the chlorinated polyvinyl chloride resin.
５０50% by weight. When the proportion of the chlorinated polyvinyl chloride resin is less than 5% by weight, it is not effective in improving the matting property and heat resistance, and when it is 50% by weight or more, the thermal stability at the time of high temperature processing. , The continuous spinning for a long time becomes difficult. From these points, the ratio of the chlorinated polyvinyl chloride resin is more preferably from 10 to 45% by weight.
【００１１】前記塩化ビニル系樹脂と塩素化ポリ塩化ビ
ニル樹脂の混合物に配合するエチレン・酢ビ／塩ビグラ
フト重合樹脂とは、エチレン−酢酸ビニル共重合体に塩
化ビニルをグラフト重合した樹脂である。前記エチレン
−酢酸ビニルの共重合体としては、酢酸ビニル含量が５
〜６０重量％で分子量が１００００〜６００００のもの
であれば特に製法は問わないが、曳糸性と耐熱性の点
で、酢酸ビニル含量は１０〜５０重量％で分子量が１４
０００〜４００００のものがより好ましい。酢酸ビニル
含量が５重量％未満であったり、分子量が６００００を
超えるのものは、溶融時の粘度が高くなり曳糸性改良効
果が充分でない。又、酢酸ビニル含量が６０重重％以上
であったり分子量が１００００以下の場合、得られる繊
維の耐熱性が低下し、艶も増すので好ましくない。エチ
レン−酢酸ビニル共重合体への塩化ビニルのグラフト重
合は、配合される塩化ビニル系樹脂と塩素化塩化ビニル
樹脂の混合物に対する均一混練性が改良されるので実施
される。グラフトする塩化ビニルの重合度としては５０
０〜１５００の範囲にあれば良いが、繊維の曳糸性と強
度、耐熱性の点で７００〜１３００程度がより好まし
い。グラフト重合は水中懸濁法が一般的だが、方法は特
に問わない。The ethylene / vinyl acetate / vinyl chloride graft polymer resin blended in the mixture of the vinyl chloride resin and the chlorinated polyvinyl chloride resin is a resin obtained by graft polymerization of vinyl chloride to an ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer has a vinyl acetate content of 5
The production method is not particularly limited as long as the molecular weight is 10,000 to 60,000 and the molecular weight is 10,000 to 60,000. From the viewpoint of spinnability and heat resistance, the vinyl acetate content is 10 to 50% by weight and the molecular weight is 14%.
000 to 40,000 is more preferable. If the vinyl acetate content is less than 5% by weight or the molecular weight exceeds 60,000, the viscosity at the time of melting is high, and the spinnability improving effect is not sufficient. On the other hand, when the vinyl acetate content is 60% by weight or more or the molecular weight is 10,000 or less, the heat resistance of the obtained fiber is decreased, and the gloss is undesirably increased. The graft polymerization of vinyl chloride onto the ethylene-vinyl acetate copolymer is carried out because the uniform kneading property of the mixture of the vinyl chloride resin and the chlorinated vinyl chloride resin to be blended is improved. The degree of polymerization of vinyl chloride to be grafted is 50
It is good if it is in the range of 0 to 1500, but it is more preferably about 700 to 1300 in view of the spinnability, strength and heat resistance of the fiber. The graft polymerization is generally performed by a suspension method in water, but the method is not particularly limited.
【００１２】前記塩化ビニル系樹脂と塩素化ポリ塩化ビ
ニル樹脂の混合物に前記るエチレン・酢ビ／塩ビグラフ
ト重合樹脂を配合することで紡糸（曳糸）性が向上す
る。この場合の配合割合は、塩化ビニル系樹脂と塩素化
ポリ塩化ビニル樹脂の混合物１００重量部に対し、エチ
レン・酢ビ／塩ビグラフト重合樹脂が５〜４０重量部で
ある。前記エチレン・酢ビ／塩ビグラフト重合樹脂の配
合量が塩化ビニル系樹脂と塩素化ポリ塩化ビニル樹脂の
混合物１００重量部に対して５重量部未満では曳糸性が
低下し糸切れが多くなる。又、４０重量部を超えて配合
すると繊維の耐熱性低下が大きく、繊維としての目的を
減ずる。これらの点から、塩化ビニル系樹脂と塩素化ポ
リ塩化ビニル樹脂の混合物に対するエチレン・酢ビ／塩
ビグラフト重合樹脂の配合割合は１０〜３５重量部がよ
り好ましい。By blending the ethylene / vinyl acetate / vinyl chloride graft resin with the mixture of the vinyl chloride resin and the chlorinated polyvinyl chloride resin, the spinning (spinning) property is improved. In this case, the blending ratio is 5 to 40 parts by weight of the ethylene / vinyl acetate / vinyl chloride graft resin with respect to 100 parts by weight of the mixture of the vinyl chloride resin and the chlorinated polyvinyl chloride resin. If the blending amount of the ethylene / vinyl acetate / vinyl chloride graft resin is less than 5 parts by weight with respect to 100 parts by weight of the mixture of the vinyl chloride resin and the chlorinated polyvinyl chloride resin, the spinnability will decrease and the thread breakage will increase. Further, when the amount is more than 40 parts by weight, the heat resistance of the fiber is greatly reduced, and the purpose of the fiber is reduced. From these points, the blending ratio of the ethylene / vinyl acetate / vinyl chloride graft polymer to the mixture of the vinyl chloride resin and the chlorinated polyvinyl chloride resin is more preferably 10 to 35 parts by weight.
【００１３】本発明で得られる繊維は、塩化ビニル系樹
脂に混合される塩素化ポリ塩化ビニルの量や、ノズルか
らの紡出速度に対する引き取り速度の比である曳糸（ド
ラフト）倍率により表面凹凸の程度をコントロールでき
る。即ち、塩素化ポリ塩化ビニルの混合量を多くし、曳
糸（ドラフト）倍率を小さくすると表面凹凸が多くな
り、艶が高度に消えた繊維となる。従って、このような
繊維は、特に自然な艶を要求されるかつらなどの頭飾用
製品に使用する人造毛髪用に好適である。ドールヘアー
やお祭り用かつら等には艶のあるものが要望されること
もあるが、混合する塩素化ポリ塩化ビニルの量や曳糸
（ドラフト）倍率により任意に対応可能である。又、塩
素化ポリ塩化ビニル樹脂の量を多くすると、得られる繊
維の耐熱性が向上し、カール保持性を要求されるかつら
等の人造毛髪用繊維としてさらに好適である。The fiber obtained in the present invention has surface irregularities depending on the amount of chlorinated polyvinyl chloride mixed with the vinyl chloride resin and the draw ratio, which is the ratio of the drawing speed to the spinning speed from the nozzle. Control the degree of That is, when the mixing amount of the chlorinated polyvinyl chloride is increased and the spinning (draft) magnification is reduced, the surface unevenness increases, and the fiber becomes highly glossy. Accordingly, such fibers are particularly suitable for artificial hair used in head decoration products such as wigs that require natural luster. Although doll hair and festive wigs are sometimes required to be glossy, they can be arbitrarily adjusted depending on the amount of chlorinated polyvinyl chloride to be mixed and the draft ratio. In addition, when the amount of the chlorinated polyvinyl chloride resin is increased, the heat resistance of the obtained fiber is improved, and it is more suitable as a fiber for artificial hair such as a wig that requires curl retention.
【００１４】本発明で得られる繊維は、人造毛髪用途だ
けでなく、防虫網やブラシ、カーペット類等の産業資材
分野にも使用可能である。この分野では、低価格が要望
される場合が多く、繊維の生産性が高い必要があるが、
本発明では、塩化ビニル系樹脂と塩素化ポリ塩化ビニル
樹脂の混合物に対し、エチレン・酢ビ／塩ビグラフト重
合樹脂を配合することにより、高い曳糸性が得られ、生
産性に優れるので好適である。The fiber obtained by the present invention can be used not only for artificial hair but also for industrial materials such as insect nets, brushes, carpets and the like. In this field, low prices are often required, and high fiber productivity is required.
In the present invention, by blending an ethylene / vinyl acetate / vinyl chloride graft resin with a mixture of a vinyl chloride resin and a chlorinated polyvinyl chloride resin, high spinnability is obtained and productivity is excellent. is there.
【００１５】本発明のポリ塩化ビニル系繊維は、湿式、
乾式、半乾半湿式、溶融紡糸いずれの方法によっても製
造可能である。湿式、乾式、半乾半湿式の製造法は、ジ
メチルホルムアミド、ジメチルアセトアミド、ジメチル
スルホキシド、又はテトラヒドロフランの単独、もしく
は混合溶媒に上記樹脂組成物を溶解し、通常の紡糸方法
で可能である。好ましい製造方法は、工程が比較的簡単
で曳糸性向上効果も顕著に発揮される溶融紡糸である。[0015] The polyvinyl chloride fiber of the present invention is a wet type,
It can be produced by any of dry, semi-dry, semi-wet and melt spinning methods. The wet, dry, or semi-dry semi-wet production method can be performed by a conventional spinning method by dissolving the above resin composition in dimethylformamide, dimethylacetamide, dimethylsulfoxide, or tetrahydrofuran alone or in a mixed solvent. A preferred production method is melt spinning, in which the steps are relatively simple and the effect of improving spinnability is remarkably exhibited.
【００１６】尚、本発明の繊維に対しては、製造方法や
品質の必要に応じて、他の成分も適宜混合可能である。
例えば、溶融紡糸においては、塩化ビニル系樹脂及び塩
素化ポリ塩化ビニル樹脂の溶融押し出し加工上必須の熱
安定剤及び滑材を任意に適当量配合でき、更に必要なら
ば、帯電防止剤、酸化防止剤、紫外線吸収剤、或いは顔
料等を配合することが可能である。The fiber of the present invention can be mixed with other components as required according to the production method and quality.
For example, in the melt spinning, a heat stabilizer and a lubricant which are essential for melt extrusion of a vinyl chloride resin and a chlorinated polyvinyl chloride resin can be arbitrarily added in appropriate amounts. , An ultraviolet absorber, a pigment, or the like.
【００１７】又、本発明の繊維を溶融紡糸する場合の樹
脂組成物は、リボンブレンダーやヘンシェルミキサー等
の通常の粉末混合機を用い、常温或いは加熱混合して得
ることができる。得られた樹脂組成物は、粉末状のまま
直接押し出し機へ投入して加熱溶融紡糸が可能である
が、混練ロール、又は押し出し機、ニーダー等で造粒化
して紡糸原料とすることが望ましい。The resin composition for melt-spinning the fiber of the present invention can be obtained by mixing at ordinary temperature or by heating using a conventional powder mixer such as a ribbon blender or a Henschel mixer. The obtained resin composition can be directly poured into an extruder in the form of a powder and subjected to heat-melt spinning. However, it is preferable that the obtained resin composition is granulated by a kneading roll, an extruder, a kneader, or the like to obtain a spinning raw material.
【００１８】上記のようにして得られた紡糸原料は、加
工性に優れているので、通常の１軸或いは２軸の押し出
し機等を用い、１５０〜２００℃程度の温度設定で加熱
溶融して細孔ノズルより紡出することができる。本発明
の繊維に関わる紡糸原料は、このままでも優れた曳系性
を発揮するが、ノズル直下に繊維軸方向に加熱紡糸筒を
設け、紡出された溶融糸を瞬間的に加熱して高度に曳糸
することも可能である。特に熱分解を起こしやすい塩素
化ポリ塩化ビニル等を多量に混合使用する場合は、押し
出し機を比較的低い温度で運転し、ノズルを出た直後の
加熱筒で瞬間的に加熱溶融して高度に曳糸する方が、樹
脂の熱劣化を少なくでき、長時間の連続運転が可能とな
るので好ましい。この方法によれば、ノズルからの紡出
速度に対する引き取り速度の比である曳糸（ドラフト）
倍率を３００程度までとることも可能となる。Since the spinning raw material obtained as described above is excellent in processability, it is heated and melted at a temperature of about 150 to 200 ° C. using a usual single-screw or twin-screw extruder. It can be spun from a fine nozzle. The spinning raw material relating to the fiber of the present invention exhibits excellent spinning properties as it is, but a heated spinning cylinder is provided in the fiber axis direction immediately below the nozzle, and the spun molten yarn is instantaneously heated to a high degree. It is also possible to spin. In particular, when using a large amount of chlorinated polyvinyl chloride or the like, which tends to cause thermal decomposition, operate the extruder at a relatively low temperature and instantaneously heat and melt it in a heating cylinder immediately after it comes out of the nozzle. Stringing is preferred because thermal degradation of the resin can be reduced and continuous operation can be performed for a long time. According to this method, the draft is a ratio of the take-up speed to the spinning speed from the nozzle.
The magnification can be set to about 300.
【００１９】細孔ノズルより紡出され、引き取りロール
で曳糸された繊維の強度は比較的小さいが、伸度に富む
ため、更に公知の後延伸、及び緩和熱処理を実施し、強
度、伸度のバランスをとると共に熱収縮を小さくして製
品とすることができる。公知の後延伸とは、繊維束を９
０〜１００℃程度の熱水浴、或いは１０５〜１３０℃程
度の熱風循環箱を通すか、１０５〜１３０℃程度の熱板
に接触させて走行させ、その間に２〜５倍に引き延ばす
操作である。又、緩和熱処理としては、１０５〜１６０
℃程度の熱風を循環させた１個以上の箱の中に各複数個
のロールを設置し、ロールの回転速度を段階的に減速す
ることにより、その間を走行する繊維を段階的に合計で
１０〜２５％程度収縮させる方法が一般的である。この
緩和熱処理に際し、先端径を細くした円錐形ロールを対
にして熱風循環箱の中に設置し、繊維を前記対になった
ロール間を引き回すことにより、ロールの回転につれて
その表面に巻かれた繊維に緊張状態で徐々に収縮を与え
ながらロールの先端に向けて送ることができる。この方
法によれば、連続的に緩和熱処理ができるので、一対以
上のロールを設置すれば、１０５〜１２０℃の比較的低
い温度で３０％程度の緩和熱処理ができ、高い耐熱性
（低い熱収縮率）が得られる。ロールの円錐形の傾斜・
長さや対の数等は、熱処理温度・時間と共に、必要とさ
れる耐熱性により決定されるが、この方法は装置が小さ
くなり実用的で好ましい。The strength of the fiber spun from the nozzle and drawn by the take-off roll is relatively small, but the fiber is rich in elongation. And heat shrinkage is reduced to obtain a product. Known post-stretching means that the fiber bundle is
It is an operation of passing through a hot water bath of about 0 to 100 ° C. or a hot air circulation box of about 105 to 130 ° C. or running in contact with a hot plate of about 105 to 130 ° C., and extending it 2 to 5 times during that time. . Further, as the relaxation heat treatment, 105 to 160
A plurality of rolls are installed in one or more boxes in which hot air of about 10 ° C. is circulated, and the rotation speed of the rolls is gradually reduced so that the fibers traveling between the rolls are gradually reduced by a total of 10 °. A method of shrinking about 25% is common. At the time of this relaxation heat treatment, the conical rolls having a reduced tip diameter were set in pairs in a hot air circulation box, and the fibers were wound around the surface as the rolls were rotated by drawing the fibers between the paired rolls. The fibers can be fed toward the tip of the roll while gradually shrinking under tension. According to this method, the relaxation heat treatment can be performed continuously. Therefore, if at least one pair of rolls is installed, the relaxation heat treatment of about 30% can be performed at a relatively low temperature of 105 to 120 ° C., and high heat resistance (low heat shrinkage) can be obtained. Rate) is obtained. Roll conical slope
The length, the number of pairs and the like are determined by the required heat resistance together with the heat treatment temperature and time, but this method is practical and preferable because the apparatus becomes small.
【００２０】通常、延伸後の繊維には油剤が付与され
る。この油剤の付与は、櫛を通したり金属との接触時に
滑りが良いように、また静電気が発生して取扱に支障を
来さないように、繊維に制電性を持たせることを目的と
したものである。Usually, an oil agent is applied to the drawn fiber. The purpose of applying this oil agent was to make the fibers have antistatic properties so that they would slide well when passing through a comb or contact with metal, and so that they would not interfere with handling due to the generation of static electricity. Things.
【００２１】この様にして得られる繊維の単糸繊度は、
人造毛髪用繊維としては１０〜１００デニールが一般的
であるが、その他の用途に応じて細くも太くも紡糸する
事が可能である。The single yarn fineness of the fiber thus obtained is
As a fiber for artificial hair, 10 to 100 denier is generally used. However, it is possible to spin fine or thick depending on other uses.
【００２２】又、繊維の製品形状としては、加工機械に
かけるため高速で引き出し使用される場合はボビン巻き
が、又、多数本同時に使用される場合は繊維束の状態で
巻き取られたり箱に振り込まれたりと、使用目的により
任意に選択できる。As the product shape of the fiber, a bobbin winding is used when the fiber is drawn out at a high speed to be applied to a processing machine, and when a plurality of fibers are used at the same time, the fiber is wound in a bundle or wound into a box. It can be arbitrarily selected depending on the purpose of use, such as being transferred.
【００２３】[0023]
【実施例】次に、本発明を溶融紡糸の実施例により更に
詳細に説明するが、これによって本発明の範囲を限定す
るものではない。Next, the present invention will be described in more detail by way of examples of melt spinning, but this does not limit the scope of the present invention.
【００２４】［実施例１〜３、比較例１〜２］塩化ビニ
ル系樹脂、塩素化ポリ塩化ビニル樹脂、及びエチレン・
酢ビ／塩ビグラフト重合樹脂を、下記の表１に示す所定
の割合で混合し、更にジブチル錫マレートを３重量部、
ジブチル錫ラウレートを１重量部、合成ワックスを０．
５重量部、及びステアリン酸を０．５重量部配合した。
この配合物を、リボンブレンダーを用いて１１０℃で４
０分攪拌混合した後、押し出し機を用い、シリンダー温
度１４０℃、ダイス温度１４５℃でペレット化した。こ
の樹脂ペレットを、Ｌ／Ｄ＝２０の３０ｍｍφ押し出し
機に孔径０．７ｍｍφ孔数６０のノズルを取り付け、シ
リンダー温度１５０〜１８０℃、ノズル温度１８０℃前
後の範囲で各例で曳糸性の良い条件で押し出し、第１の
引き取りロールによって曳糸した。次に第２の延伸ロー
ルとの間で１１０℃の熱風循環箱を通して２．５倍に延
伸した。さらに１１５℃に温度調節した箱の中に設置し
た２対の円錐形ロール間を引き回し、連続的に２５％の
緩和熱処理を実施し、単糸繊度６０デニールのマルチフ
ィラメントを巻き取った。このときの加工性（紡糸
性）、及び各例で得られたマルチフィラメントの物性に
ついて、下記の方法で判定した。結果を表１に示した。Examples 1-3 and Comparative Examples 1-2 Vinyl chloride resin, chlorinated polyvinyl chloride resin, ethylene
A vinyl acetate / vinyl chloride graft polymer resin was mixed at a predetermined ratio shown in Table 1 below, and further 3 parts by weight of dibutyltin malate was added.
1 part by weight of dibutyltin laurate and 0.1 part of synthetic wax.
5 parts by weight and 0.5 parts by weight of stearic acid were blended.
This formulation is heated at 110 ° C. for 4 hours using a ribbon blender.
After stirring and mixing for 0 minutes, the mixture was pelletized at a cylinder temperature of 140 ° C. and a die temperature of 145 ° C. using an extruder. This resin pellet is attached to a 30 mmφ extruder with L / D = 20, equipped with a nozzle having a hole diameter of 0.7 mmφ and 60 holes, and has good spinnability in each case at a cylinder temperature of 150 to 180 ° C and a nozzle temperature of around 180 ° C. It was extruded under the conditions and drawn by a first take-up roll. Next, it was stretched 2.5 times with a second stretching roll through a 110 ° C. hot air circulation box. Furthermore, the wire was drawn between two pairs of conical rolls installed in a box adjusted to a temperature of 115 ° C., subjected to a continuous relaxation heat treatment of 25%, and wound up a multifilament having a single yarn fineness of 60 denier. At this time, the processability (spinning property) and the physical properties of the multifilament obtained in each example were determined by the following methods. The results are shown in Table 1.
【００２５】〔物性等判定法〕 （１）紡糸性 引き取りロールの速度を糸切れが始まるまで上げた時の
ロール速度／紡出速度＝最大曳糸倍率とし、最大曳糸倍
率が５０以上を「良」、５０〜１０を「やや良」、１０
以下を「悪」と判定した。 （２）艶の程度 ポリ塩化ビニルの艶の程度を１、人毛髪の艶の程度を
５、その間を２、３、４と５ランクに表示した。人毛髪
より艶消しになったものを６、７と表示した。 （３）熱収縮率 ２０ｃｍ長のマルチフィラメント１２本を９０℃のギア
オーブン中に吊り下げ、１５分後の各サンプルの収縮率
の内、中間値１０個を平均して熱収縮率とした。熱収縮
率は４％以下が好ましい。[Methods for Determining Physical Properties, etc.] (1) Spinnability Roll speed / spinning speed when the speed of the take-off roll is increased until thread breakage starts = maximum spinning ratio. Good ”, 50 to 10“ somewhat good ”, 10
The following were determined to be "bad". (2) Degree of luster The degree of luster of polyvinyl chloride was indicated as 1, the degree of luster of human hair was indicated as 5, and the interval between them was indicated as rank 2, 3, 4, or 5. Mattes that were more matte than human hair were labeled 6,7. (3) Thermal Shrinkage Rate Twelve multifilaments of 20 cm length were suspended in a gear oven at 90 ° C., and among the shrinkage rates of each sample after 15 minutes, an intermediate value of 10 pieces was averaged to obtain a heat shrinkage rate. The heat shrinkage is preferably 4% or less.
【００２６】[0026]
【表１】 [Table 1]
【００２７】表１の結果から明らかななように、エンレ
ン・酢ビ／塩ビグラフト重合樹脂を配合しない場合には
紡糸性に劣り、一方、その配合量が多すぎると繊維の耐
熱性が著しく低下する。As is evident from the results in Table 1, the spinnability is poor when the enylene / vinyl acetate / vinyl chloride graft polymer resin is not blended, while the heat resistance of the fiber is significantly reduced when the blending amount is too large. I do.
【００２８】［実施例４〜６、比較例３及び４］下記の
表２に示すように、使用する塩化ビニル樹脂の重合度を
変更した樹脂組成物を用い、温度条件を変更した以外
は、実施例１、２と同じ方法で紡糸した。結果を表２に
示した。[Examples 4 to 6, Comparative Examples 3 and 4] As shown in Table 2 below, a resin composition was used in which the degree of polymerization of the vinyl chloride resin used was changed, except that the temperature conditions were changed. Spinning was performed in the same manner as in Examples 1 and 2. The results are shown in Table 2.
【００２９】[0029]
【表２】 [Table 2]
【００３０】［実施例７及び８］使用した塩化ビニル樹
脂のみ下記表３に示す組成の塩化ビニル系共重合樹脂に
置き換えた以外は実施例２と同じ樹脂組成で同じ方法で
紡糸した。結果を表３に示した。[Examples 7 and 8] Spinning was carried out in the same manner as in Example 2, except that the vinyl chloride resin used was replaced by a vinyl chloride copolymer resin having the composition shown in Table 3 below. The results are shown in Table 3.
【００３１】[0031]
【表３】 [Table 3]
【００３２】［実施例９］混合する塩素化ポリ塩化ビニ
ル樹脂において、原料塩化ビニルの重合度及び塩素含有
量を下記の表４に示す様に置き換えた以外は、実施例２
と同じ樹脂組成で同じ方法で紡糸した。結果を表４に示
した。Example 9 Example 2 was repeated except that the degree of polymerization and the chlorine content of the raw material vinyl chloride in the chlorinated polyvinyl chloride resin to be mixed were changed as shown in Table 4 below.
The spinning was carried out by the same method with the same resin composition as in Example 1. The results are shown in Table 4.
【００３３】[0033]
【表４】 [Table 4]
【００３４】〔実施例１０及び１１、比較例５及び６〕
配合するエチレン・酢ビ／塩ビグラフト重合樹脂のエチ
レン−酢酸ビニル共重合体（ＥＶＡ）中の酢酸ビニル
（酢ビ）含量と、エチレン・酢ビ／塩ビグラフト重合樹
脂の配合部数を変更した以外は、実施例２と同じ樹脂組
成で同じ方法で紡糸した。結果を表５に示した。[Examples 10 and 11, Comparative Examples 5 and 6]
Except that the content of vinyl acetate (vinyl acetate) in the ethylene / vinyl acetate / vinyl acetate copolymer (EVA) of the ethylene / vinyl acetate / vinyl graft copolymer resin to be blended and the number of parts of the ethylene / vinyl acetate / vinyl graft copolymer resin were changed The spinning was performed using the same resin composition and the same method as in Example 2. Table 5 shows the results.
【００３５】[0035]
【表５】 [Table 5]
【００３６】表５の結果から明らかなように、配合する
エチレン・酢ビ／塩ビグラフト重合樹脂のエチレン−酢
酸ビニル共重合体中の酢酸ビニル含量が高すぎる場合
や、エチレン・酢ビ／塩ビグラフト重合樹脂の配合量が
多すぎる場合には、繊維の耐熱性が悪くなり、又、艶消
し性も低下する。As is clear from the results in Table 5, the ethylene-vinyl acetate / vinyl graft copolymer resin to be blended has too high a vinyl acetate content in the ethylene-vinyl acetate copolymer, If the amount of the polymer resin is too large, the heat resistance of the fiber becomes poor, and the matting property also decreases.
【００３７】[0037]
【発明の効果】以上のように、本発明に係るポリ塩化ビ
ニル系繊維は、耐熱性に優れ、又、艶や風合いもコント
ロールされており、人造毛髪用として好適に使用でき
る。しかも、紡糸（曳糸）性に優れており生産性も高く
低コストで生産が可能であり、人造毛髪用以外の産業資
材分野等にも応用可能である。As described above, the polyvinyl chloride fiber according to the present invention is excellent in heat resistance, and has a controlled gloss and texture, and can be suitably used for artificial hair. Moreover, it is excellent in spinning (spinning) properties, has high productivity, can be produced at low cost, and can be applied to industrial materials other than artificial hair.
Claims (5)
５〜５０重量％の塩素化ポリ塩化ビニル樹脂の混合物１
００重量部に対し、エチレン・酢ビ／塩ビグラフト重合
樹脂を５〜４０重量部配合した樹脂組成物からなること
を特徴とするポリ塩化ビニル系繊維。1. A mixture 1 of 50 to 95% by weight of a vinyl chloride resin and 5 to 50% by weight of a chlorinated polyvinyl chloride resin.
A polyvinyl chloride fiber comprising a resin composition in which 5 to 40 parts by weight of an ethylene / vinyl acetate / vinyl chloride graft resin is blended with respect to 00 parts by weight.
が５８〜７０重量％である請求項１記載のポリ塩化ビニ
ル系繊維。2. The polyvinyl chloride fiber according to claim 1, wherein the chlorinated polyvinyl chloride resin has a chlorine content of 58 to 70% by weight.
が、酢酸ビニル含量１０〜５０重量％のエチレン−酢酸
ビニル共重合体に、塩化ビニルを重合度５００〜１５０
０でグラフト重合した樹脂である請求項１記載のポリ塩
化ビニル系繊維。3. An ethylene / vinyl acetate / vinyl chloride graft polymerization resin is prepared by adding vinyl chloride to an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 50% by weight and a polymerization degree of 500 to 150.
2. The polyvinyl chloride fiber according to claim 1, which is a resin graft-polymerized with 0.
化ビニル系繊維。4. The polyvinyl chloride fiber according to claim 1, which is for artificial hair.
５〜５０重量％の塩素化ポリ塩化ビニル樹脂の混合物１
００重量部に対し、エチレン・酢ビ／塩ビグラフト重合
樹脂を５〜４０重量部配合した樹脂組成物を溶融紡糸す
ることを特徴とするポリ塩化ビニル系繊維の製造法。5. A mixture 1 of 50 to 95% by weight of a vinyl chloride resin and 5 to 50% by weight of a chlorinated polyvinyl chloride resin.
A process for producing polyvinyl chloride fibers, comprising: melt-spinning a resin composition containing 5 to 40 parts by weight of an ethylene / vinyl acetate / vinyl chloride graft resin with respect to 00 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25426696A JP3600928B2 (en) | 1996-09-26 | 1996-09-26 | Polyvinyl chloride fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25426696A JP3600928B2 (en) | 1996-09-26 | 1996-09-26 | Polyvinyl chloride fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10102317A true JPH10102317A (en) | 1998-04-21 |
| JP3600928B2 JP3600928B2 (en) | 2004-12-15 |
Family
ID=17262595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25426696A Expired - Lifetime JP3600928B2 (en) | 1996-09-26 | 1996-09-26 | Polyvinyl chloride fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3600928B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100311658B1 (en) * | 1999-06-16 | 2001-10-17 | 김종찬 | Polyvinylchloride Yarn having Improved Thermal shrinkage |
| CN1089820C (en) * | 1997-03-11 | 2002-08-28 | 钟渊化学工业株式会社 | Vinyl chloride fibers and process for preparing the same |
| US6875507B2 (en) | 2001-12-19 | 2005-04-05 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition, polyvinyl chloride fibers and process for producing the same |
| JPWO2004090208A1 (en) * | 2003-04-04 | 2006-07-06 | 電気化学工業株式会社 | Polyvinyl chloride fiber, its production method and its use |
| WO2019235055A1 (en) * | 2018-06-07 | 2019-12-12 | デンカ株式会社 | Fiber for artificial hair and hair decorating product |
-
1996
- 1996-09-26 JP JP25426696A patent/JP3600928B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089820C (en) * | 1997-03-11 | 2002-08-28 | 钟渊化学工业株式会社 | Vinyl chloride fibers and process for preparing the same |
| KR100311658B1 (en) * | 1999-06-16 | 2001-10-17 | 김종찬 | Polyvinylchloride Yarn having Improved Thermal shrinkage |
| US6875507B2 (en) | 2001-12-19 | 2005-04-05 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition, polyvinyl chloride fibers and process for producing the same |
| JPWO2004090208A1 (en) * | 2003-04-04 | 2006-07-06 | 電気化学工業株式会社 | Polyvinyl chloride fiber, its production method and its use |
| US7629048B2 (en) | 2003-04-04 | 2009-12-08 | Denki Kagaku Kogyo Kabushiki Kaisha | Polyvinyl chloride fiber, process for producing the same, and use thereof |
| JP4491414B2 (en) * | 2003-04-04 | 2010-06-30 | 電気化学工業株式会社 | Polyvinyl chloride fiber, its production method and its use |
| WO2019235055A1 (en) * | 2018-06-07 | 2019-12-12 | デンカ株式会社 | Fiber for artificial hair and hair decorating product |
| CN112135540A (en) * | 2018-06-07 | 2020-12-25 | 电化株式会社 | Fiber for artificial hair and hair decorative product |
| JPWO2019235055A1 (en) * | 2018-06-07 | 2021-08-05 | デンカ株式会社 | Textiles for artificial hair and hair decoration products |
| US11807747B2 (en) | 2018-06-07 | 2023-11-07 | Denka Company Limited | Fiber for artificial hair and hair decorating product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3600928B2 (en) | 2004-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101256689B1 (en) | Polyvinyl chloride fiber with excellent style changeability | |
| CN112899799B (en) | Artificial hair fiber | |
| JP5491213B2 (en) | Artificial hair fiber and headdress | |
| JP4889635B2 (en) | Fiber bundle for artificial hair and hair decoration product using the same | |
| WO1998040545A1 (en) | Vinyl chloride fibers and process for preparing the same | |
| JP5085116B2 (en) | Resin composition and fiber comprising the same | |
| JP2010100966A (en) | Polyvinyl chloride fiber for artificial hair, artificial hair, and hairdressing product composed thereof | |
| JP2008002041A (en) | Fiber for artificial hair and method for producing the same | |
| JP3600928B2 (en) | Polyvinyl chloride fiber and method for producing the same | |
| JPWO2006038447A1 (en) | Vinyl chloride resin composition, vinyl chloride fiber and method for producing the same, and artificial hair fiber | |
| JP3804200B2 (en) | Vinyl chloride fiber and method for producing the same | |
| JPH01282309A (en) | Polyamide fiber for artificial hair | |
| JP5210856B2 (en) | Method for producing vinyl chloride resin fiber | |
| JP2004156149A (en) | Polyvinyl chloride fiber | |
| KR100473043B1 (en) | Synthetic Hair Comprising Polyvinylchloride and Method of Preparing the Same | |
| US20060237869A1 (en) | Method for producing a fiber for an artificial hair by polyvinyl chloride/acryl-copolymer blends | |
| JP3813893B2 (en) | Method for determining the amount of chlorinated polyvinyl chloride resin added to polyvinyl chloride fiber | |
| JP3791177B2 (en) | Vinyl chloride fiber and method for producing the same | |
| JPH11217720A (en) | Vinyl chloride-based fiber and its production | |
| JP2000154293A (en) | Resin composition for polyvinyl chloride fiber and fiber made of that | |
| JP4935050B2 (en) | Artificial hair fiber | |
| JP2003193329A (en) | Polyvinyl chloride-based fiber | |
| JP2002266160A (en) | Vinyl chloride-based resin fiber | |
| JP2000191871A (en) | Resin composition for polyvinyl chloride fiber and fiber prepared from this | |
| KR950005426B1 (en) | Process for the preparation of polyurethane mono elastomeric yarn by melt spinning |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040518 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040601 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040802 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040824 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20040802 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040906 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071001 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081001 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081001 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091001 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091001 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101001 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111001 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121001 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121001 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131001 Year of fee payment: 9 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131001 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |