JPH04119102A - Production of vinyl chloride resin globe - Google Patents

Production of vinyl chloride resin globe

Info

Publication number
JPH04119102A
JPH04119102A JP2228198A JP22819890A JPH04119102A JP H04119102 A JPH04119102 A JP H04119102A JP 2228198 A JP2228198 A JP 2228198A JP 22819890 A JP22819890 A JP 22819890A JP H04119102 A JPH04119102 A JP H04119102A
Authority
JP
Japan
Prior art keywords
vinyl chloride
globe
chloride resin
mold
synthetic resin
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
JP2228198A
Other languages
Japanese (ja)
Other versions
JPH0753922B2 (en
Inventor
Chikashi Toyoda
豊田 史
Tadao Nishimatsu
忠男 西松
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.)
Honny Chemicals Co Ltd
Hirono Kagaku Kogyo KK
Original Assignee
Honny Chemicals Co Ltd
Hirono Kagaku Kogyo KK
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 Honny Chemicals Co Ltd, Hirono Kagaku Kogyo KK filed Critical Honny Chemicals Co Ltd
Priority to JP22819890A priority Critical patent/JPH0753922B2/en
Publication of JPH04119102A publication Critical patent/JPH04119102A/en
Publication of JPH0753922B2 publication Critical patent/JPH0753922B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Gloves (AREA)

Abstract

PURPOSE:To produce the subject globe having excellent detachability and dust protectivity by dipping a globe mold having a vinyl chloride resin layer formed on the surface thereof in a specific synthetic resin emulsion, lifting, heating the coated globe mold under a prescribed condition, cooling and subsequently reversing and demolding the formed laminated films. CONSTITUTION:A globe mold having a vinyl chloride resin layer formed on the surface thereof is dipped for 1-3min in a synthetic resin emulsion such as an urethane resin emulsion containing an organic filler such as a (meth)acrylate ester polymer filler having an average particle diameter of 0.5-20mum, preferably 1-4mum. in an amount of 10-60 pts.wt. per 100 pts.wt. of the resin solid content. The globe mold is lifted and cooled, followed by reversing and demolding the formed laminated films to provide the objective globe.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、手にフィツトし、かつ告脱が容易で塵の発生
しない塩化ビニル樹脂製手袋の製造方法に関するもので
ある。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing vinyl chloride resin gloves that fit the hand, are easy to put on and take off, and do not generate dust.

〔従来の技術〕[Conventional technology]

従来、塩化ビニル樹脂製手袋は、主として家庭用に使用
されていたが、近年、精密工業における作業用にも、そ
の使用が増加している。しかしながら、塩化ビニル樹脂
製手袋は、柔軟性付与の為め多量の可塑剤が配合されて
おり、そしてこの可塑剤が表面にブリードするため、粘
谷性を示し、手袋製造時における手型からの離型性や、
使用時における着脱性に劣るという欠点があった。そこ
で、手袋内面にパイル植毛や無機物微粉末による打粉処
理が施されているが、クリーンルーム内で精密加工を行
う場合、植毛繊維や打粉成分が塵の発生原因となり、そ
の改善が要望されていた。
Conventionally, gloves made of vinyl chloride resin have been used mainly for household use, but in recent years, their use has also increased for work in the precision industry. However, gloves made of vinyl chloride resin contain a large amount of plasticizer to give them flexibility, and this plasticizer bleeds onto the surface, resulting in viscous properties and viscous properties. Mold releasability,
It had the disadvantage of being poor in attachment and detachment during use. Therefore, the inner surface of gloves is treated with pile flocking or dusting with inorganic fine powder, but when precision processing is carried out in a clean room, the flocked fibers and dusting ingredients can generate dust, and there has been a desire to improve this.

このような問題を解決する方法として、手型に塩化ビニ
ル樹脂層を形成した後、微粒子シリカを含有する合成樹
脂エマルジョンに浸漬処理して製膜し、冷却後、反転脱
型する方法が提案されている。(特公平2−19203
号公報参照)〔発明が解決しようとする課題〕 上記従来の方法は、有機の合成樹脂エマルジョン中に、
無機の微粒子シリカを配分分散させるため、表面の凹凸
形成によってスリップ性は向上する。しかしながら、表
面にブリードした可塑剤が合成樹脂を可塑化すると同時
に、シリカ内部にも吸着され、その結果、粘着性を完全
に抑えることができないという問題があった。
As a method to solve these problems, a method has been proposed in which a vinyl chloride resin layer is formed on a hand mold, the film is formed by immersion in a synthetic resin emulsion containing fine silica particles, and after cooling, the mold is reversed and removed. ing. (Tokuhei 2-19203
(Refer to the above publication) [Problems to be Solved by the Invention] The above conventional method involves the use of organic synthetic resin emulsions containing
Since the inorganic fine particles of silica are distributed and dispersed, the slip property is improved by forming irregularities on the surface. However, there is a problem in that the plasticizer that bleeds onto the surface plasticizes the synthetic resin and is also adsorbed inside the silica, resulting in the inability to completely suppress stickiness.

本発明は、従来の技術における上記のような問題点を解
決することを目的としてなされたものである。したがっ
て、本発明の目的は、スリップ性に優れ、着脱が容易で
塵の発生しない塩化ビニル樹脂製手袋を製造する方法を
提供することにある〔課題を解決するための手段及び作
用〕上記目的を達成するため、本発明者等は、微粒子シ
リカに代えて、有機充填剤を使用したところ合成樹脂エ
マルジョンとのなじみに優れ、紅時によっても有機充填
剤が沈降分離せず、かつ着脱が容易な塩化ビニル樹脂製
手袋を製造することができることを見出だし、しかも有
機充填剤の使用により感触がドライとなり傷付きにくい
という付随的効果も発揮されることを見出だし、本発明
を完成するに至った。
The present invention has been made to solve the above-mentioned problems in the conventional technology. Therefore, an object of the present invention is to provide a method for manufacturing vinyl chloride resin gloves that have excellent slip properties, are easy to put on and take off, and do not generate dust. In order to achieve this, the present inventors used an organic filler instead of fine-particle silica, which had excellent compatibility with the synthetic resin emulsion, the organic filler did not settle and separate even when heated, and was easy to attach and detach. The inventors discovered that it was possible to manufacture gloves made of vinyl chloride resin, and also discovered that the use of an organic filler had the additional effect of making them dry to the touch and making them less susceptible to scratches, leading to the completion of the present invention. .

本発明の塩化ビニル樹脂製手袋の製造方法は、表面に塩
化ビニル樹脂層を形成した手袋用平型を、平均粒径0.
5節〜20節の有機充填剤を樹脂固形分100重量部に
対して10〜60重量部配合してなる合成樹脂エマルジ
ョン中に041〜1分浸漬し、次いで引き上げ、160
〜200℃で1〜3分加熱した後、冷却して、形成され
た積層膜反転脱型することを特徴とする。
In the method for manufacturing vinyl chloride resin gloves of the present invention, a flat type glove having a vinyl chloride resin layer formed on the surface is prepared with an average particle size of 0.
It is immersed in a synthetic resin emulsion containing 10 to 60 parts by weight of an organic filler of 5 to 20 parts per 100 parts by weight of resin solids for 0.41 to 1 minute, and then pulled up to 160 parts by weight.
It is characterized by heating at ~200° C. for 1 to 3 minutes, cooling, and then inverting and demolding the formed laminated film.

次に、本発明について詳細に説明する。Next, the present invention will be explained in detail.

表面に塩化ビニル樹脂層を形成した手袋用平型は、通常
一般に実施されている方法によって製造することができ
る。即ち、金属製又は陶磁蒸製の丁型を、塩化ビニルベ
ーストレジンに可塑剤、安定剤、顔料、および必要に応
してゲル化剤、希釈剤、充填剤等を添加混練して得られ
る塩化ビニル樹脂ゾルに浸漬して、平型表面に塩化ビニ
ル樹脂ゾルのは薄層を形成させ、次いで、それを加熱し
てゲル化させればよく、それによって手形表面に塩化ビ
ニル樹脂層が形成される。
A flat type glove having a vinyl chloride resin layer formed on its surface can be manufactured by a commonly used method. That is, vinyl chloride obtained by kneading a metal or ceramic mold by adding a plasticizer, stabilizer, pigment, and if necessary a gelling agent, diluent, filler, etc. to a vinyl chloride base resin. All you have to do is immerse it in a resin sol to form a thin layer of vinyl chloride resin sol on the flat surface, and then heat it to gel it, thereby forming a vinyl chloride resin layer on the handprint surface. .

本発明においては、上記のようにして得られた、表面に
塩化ビニル樹脂層を形成した手袋用の丁型を、有機充填
剤を配合した合成樹脂エマルジョンに浸漬し、ついで引
き上げて加熱処理し、平型表面の塩化ビニル樹脂層の上
に、さらに有機充填剤含有合成樹脂層を形成させる。
In the present invention, the glove shape obtained as described above and having a vinyl chloride resin layer formed on its surface is immersed in a synthetic resin emulsion containing an organic filler, then pulled up and heat-treated, A synthetic resin layer containing an organic filler is further formed on the vinyl chloride resin layer on the surface of the flat mold.

本発明において使用する合成樹脂エマルジョンとしては
、塩化ビニル樹脂、塩化ビニリデン樹脂、ウレタン樹脂
、(メタ)アクリル酸エステル樹脂、塩化ビニル−(メ
タ)アクリル酸エステル共重合体、塩化ビニル−塩化ビ
ニリデン共重合体、塩化ビニリデン−(メタ)アクリル
酸エステル共重合体等の一種又は二種以上の混合物の水
分散体があげられる。
The synthetic resin emulsion used in the present invention includes vinyl chloride resin, vinylidene chloride resin, urethane resin, (meth)acrylic ester resin, vinyl chloride-(meth)acrylic ester copolymer, and vinyl chloride-vinylidene chloride copolymer. Examples include aqueous dispersions of one type or a mixture of two or more of vinylidene chloride-(meth)acrylic acid ester copolymers and the like.

合成樹脂エマルジョンは、樹脂固型分濃度5〜20重量
%の範囲で使用するのが好ましい。使用に際しては、通
常用いられる界面活性剤、増粘剤、消泡剤、レベリング
剤等の各種添加剤を添加することが好ましい。
The synthetic resin emulsion is preferably used at a resin solid content concentration of 5 to 20% by weight. When used, it is preferable to add various commonly used additives such as surfactants, thickeners, antifoaming agents, and leveling agents.

本発明において使用する有機充填剤としては、(メタ)
アクリル酸エステル重合体、(メタ)アクリル酸エステ
ル共重合体、ポリスチレン又はそれらの架橋体、ポリア
クリロニトリル、ポリエチレン又はそれらの架橋体、エ
チレン−アクリル酸共重合体、ポリプロピレン、ナイロ
ン12、ナイロン6/12共重合体、尿素・ホルムアル
デヒド縮合体、メラニン・ホルムアルデヒド縮合体、ベ
ンゾグアナミン・メラニン・ホルムアルデヒド縮合体、
ベンゾグアナミン・ホルムアルデヒド縮合体、4フツ化
エチレン重合体、シリコン架橋体等があげられる。
The organic filler used in the present invention includes (meth)
Acrylic ester polymer, (meth)acrylic ester copolymer, polystyrene or crosslinked products thereof, polyacrylonitrile, polyethylene or crosslinked products thereof, ethylene-acrylic acid copolymer, polypropylene, nylon 12, nylon 6/12 Copolymer, urea/formaldehyde condensate, melanin/formaldehyde condensate, benzoguanamine/melanin/formaldehyde condensate,
Examples include benzoguanamine/formaldehyde condensate, tetrafluoroethylene polymer, and silicon crosslinked product.

これ等の有機充填剤は、その粒径が0.5〜25−の範
囲のものが適しており、好ましくは1〜4pのい範囲の
ものである。粒径が、0.5 mr1未満の場合には、
表面の凹凸がなくなり、スリップ性が低下して着脱が困
難となる。一方、粒径が2otIMを越えると、表面の
凹凸が粗すぎ、フィツト感が減少してザラザラした感じ
を生じる。
These organic fillers suitably have a particle size in the range of 0.5 to 25p, preferably in the range of 1 to 4p. If the particle size is less than 0.5 mr1,
The surface becomes uneven and the slip property decreases, making it difficult to attach and detach. On the other hand, if the particle size exceeds 2 otIM, the surface irregularities will be too rough, resulting in a reduced fit and a rough feel.

本発明においては、これ等有機充填剤は、前記合成樹脂
エマルジョン中に、合成樹脂固形分100重量部に対し
て、10〜60重量部の範囲で配合する。
In the present invention, these organic fillers are blended in the synthetic resin emulsion in an amount of 10 to 60 parts by weight based on 100 parts by weight of the synthetic resin solid content.

有機充填剤の配合量が10重量部未満の場合には、有機
充填剤の配合効果が得られなくなり、一方、60重量部
を越える場合には、塗膜にクラックを生じ、外観を損な
うと同時に、ザラザラした感が生じ、商品価値を損なう
ようになる。
If the amount of organic filler blended is less than 10 parts by weight, the effect of organic filler blending will not be obtained, while if it exceeds 60 parts by weight, cracks will occur in the coating film, impairing the appearance and at the same time , a rough feeling occurs, which impairs the product value.

本発明において、塩化ビニル樹脂層を形成した平型を有
機充填剤を配合した合成樹脂エマルジョン中に浸漬する
際の浸漬時間は、一般には0.1〜1分の範囲でよい。
In the present invention, the immersion time when the flat mold with the vinyl chloride resin layer formed thereon is immersed in a synthetic resin emulsion containing an organic filler may generally be in the range of 0.1 to 1 minute.

合成樹脂エマルジョンにおける樹脂濃度および粘度は、
合成樹脂の膜厚が1〜5加になるように調整すればよく
、一般には、樹脂濃度5〜15重量%、粘度1[1〜5
0CPSの範囲が好ましい。
The resin concentration and viscosity in the synthetic resin emulsion are
The film thickness of the synthetic resin may be adjusted to 1 to 5%, and generally, the resin concentration is 5 to 15% by weight and the viscosity is 1 to 5%.
A range of 0 CPS is preferred.

又、合成樹脂エマルジョンの浴温としては、40〜60
℃の範囲が、膜の形成を促進し、浸漬時間の短縮につな
がるので好ましい。
In addition, the bath temperature of the synthetic resin emulsion is 40 to 60
A temperature range of 0.degree. C. is preferable because it promotes film formation and leads to shortening of dipping time.

上記のように平型を有機充填剤を配合した合成樹脂エマ
ルジョンに浸漬した後、平型を引き上げ、加熱処理を行
う。加熱処理は、160〜200℃の雰囲気中で1〜3
分間保持することにより行われる。それによって、最表
層に有機充填剤含有合成樹脂層、その下に塩化ビニル樹
脂層が形成された平型が得られる。最後に、この手形を
゛冷却し、平型上に形成された積層膜を反転脱型する。
After the flat mold is immersed in a synthetic resin emulsion containing an organic filler as described above, the flat mold is pulled up and subjected to heat treatment. Heat treatment is performed in an atmosphere of 160 to 200°C for 1 to 3
This is done by holding it for a minute. As a result, a flat mold having an organic filler-containing synthetic resin layer as the outermost layer and a vinyl chloride resin layer formed therebelow is obtained. Finally, the hand shape is cooled, and the laminated film formed on the flat mold is reversed and removed from the mold.

それにより塩化ビニル樹脂製手袋が製造される。As a result, vinyl chloride resin gloves are manufactured.

有機充填剤含有合成樹脂層は、その表面を三次元粗さ計
でfill定したところ、非常に緻密な凹凸が形成され
ており、この結果、手にフィツトして一体感が増し、か
つ着脱が容易になるものと考えられる。
When the surface of the organic filler-containing synthetic resin layer was measured using a three-dimensional roughness meter, it was found that extremely fine irregularities were formed. It is thought that it will become easier.

〔実施例〕〔Example〕

以下、本発明の実施例を詳細に説明する。 Examples of the present invention will be described in detail below.

実施例1 常法に従って、塩化ビニルベーストレジン(商品名:ゼ
オン121、日本ゼオン社製) 100重量部、可塑剤
:D、o、  p、  70重量部、およびエポキシ系
安定剤(商品名ニアデカサイザーロー13叶、アデカア
ーガス社製)8部を配合することによって得られたゾル
中に、磁器製平型を0.1分間浸漬し、次いでゾルが滴
下しない速さで引き上げた後、雰囲気温度250℃の加
熱炉に入れて回転させながら1分間保持した。
Example 1 According to a conventional method, 100 parts by weight of vinyl chloride-based resin (trade name: Zeon 121, manufactured by Nippon Zeon Co., Ltd.), 70 parts by weight of plasticizers: D, O, P, and an epoxy stabilizer (trade name: Niadeka) were added. A porcelain flat mold was immersed for 0.1 minute in the sol obtained by blending 8 parts of SIZERRO 13 leaves (manufactured by Adeka Argus), and then lifted at a speed that would prevent the sol from dripping, and then lowered to the ambient temperature. It was placed in a heating furnace at 250°C and held for 1 minute while rotating.

次に、固形分45%の塩化ビニル樹脂エマルジョン40
部と、固形分80%のポリメチルメタクリレートエマル
ジョン60部との混合物を樹脂固形分濃度20重量%に
調整し、平均粒径2節の尿素・ホルムアルデヒド縮合体
12部を配合して、有機充填剤濃度33重量%の混合樹
脂水分散液を調製した。この混合樹脂水分散液中に、上
記の平型を10秒間浸漬した。なお、混合樹脂水分散液
は、調製する。その後、平型を引上げ、雰囲気温度16
0℃の加熱炉内で1.5分間保持した。ついで空気中で
冷却し、平型から反転離型させて塩化ビニル樹脂製手袋
を得た。
Next, a vinyl chloride resin emulsion 40% with a solid content of 45% was prepared.
and 60 parts of a polymethyl methacrylate emulsion with a solid content of 80% was adjusted to a resin solid content concentration of 20% by weight, and 12 parts of a urea/formaldehyde condensate with an average particle size of 2 knots was blended to form an organic filler. A mixed resin aqueous dispersion having a concentration of 33% by weight was prepared. The above flat mold was immersed in this mixed resin aqueous dispersion for 10 seconds. Note that the mixed resin aqueous dispersion is prepared. After that, the flat mold was pulled up and the ambient temperature was 16
It was held in a heating oven at 0° C. for 1.5 minutes. Then, it was cooled in the air and then inverted and released from the flat mold to obtain vinyl chloride resin gloves.

実施例2〜5および比較例1〜5 実施例1の方法において、有機充填剤の種類、および/
又は配合量を第1表に示すように代えた以外は、すべて
同じ方法を実施して、塩化ビニル樹脂製手袋を得た。
Examples 2 to 5 and Comparative Examples 1 to 5 In the method of Example 1, the type of organic filler and/or
Alternatively, vinyl chloride resin gloves were obtained by carrying out the same method except for changing the blending amounts as shown in Table 1.

得られた結果を第1表に示す。なお、第1表中、n’P
価l&準は次の通りである。
The results obtained are shown in Table 1. In addition, in Table 1, n'P
The values l & quasi are as follows.

仕上り外観:塗膜面を目視で判定した。O・・・クラッ
ク発生なし、×・・・クラック発生あり。
Finished appearance: The coating surface was visually judged. O: No cracks occurred, ×: Cracks occurred.

感触:塗膜面の手触り感で判定した。◎・・・粘着又は
ざらつき感なし、0・・・粘着又はざらつき感殆どなし
、×・・・粘着感あり。
Feel: Judgment was made based on the feel of the coating surface. ◎...No sticky or rough feeling, 0...Almost no sticky or rough feeling, ×... Sticky feeling.

手袋の脱着性二〇・・・非常に良好、O・・・良好、×
・・・不良。
Glove detachability 20: Very good, O: Good, ×
...Bad.

塗膜面の傷付き性:塗膜面を爪で引っ掻き、判定した。Scratchability of paint film surface: The paint film surface was scratched with a fingernail to judge.

◎・・・傷付きなし、O・・・殆ど傷付きなし、×・・
・傷付きあり。
◎...No scratches, O...Almost no scratches, ×...
・There are scratches.

以下余白 〔発明の効果〕 本発明は、上記のように、特定の平均粒径を有する有機
充填剤を特定量含有する合成樹脂エマルジョンによフて
塩化ビニル樹脂層上に有機充填剤含有合成樹脂層を形成
するから、スリ・ツブ性に優れ、着脱が容易で塵の発生
しない塩化ビニル樹脂製手袋を製造することができる。
Blank space below [Effects of the Invention] As described above, the present invention provides a synthetic resin containing an organic filler on a vinyl chloride resin layer by using a synthetic resin emulsion containing a specific amount of an organic filler having a specific average particle size. Since the layer is formed, it is possible to manufacture vinyl chloride resin gloves that have excellent slip and slip properties, are easy to put on and take off, and do not generate dust.

しかも、本発明によって得られる塩化ビニル樹脂製手袋
は、感触がドライであり、傷付きにくいという利点も有
している。
In addition, the vinyl chloride resin gloves obtained by the present invention have the advantage of being dry to the touch and less likely to be scratched.

Claims (1)

【特許請求の範囲】[Claims] (1)表面に塩化ビニル樹脂層を形成した手型を、平均
粒径0.5μm〜20μmの有機充填剤を樹脂固形分1
00重量部に対して10〜60重量部配合してなる合成
樹脂エマルジョン中に0.1〜1分浸漬し、次いで引き
上げ、160〜200℃で1〜3分加熱した後、冷却し
て、形成された積層膜を反転脱型することを特徴とする
塩化ビニル樹脂製手袋の製造方法。
(1) A hand mold with a vinyl chloride resin layer formed on the surface is coated with an organic filler having an average particle size of 0.5 μm to 20 μm, with a resin solid content of 1
It is immersed in a synthetic resin emulsion containing 10 to 60 parts by weight per 0.00 parts by weight for 0.1 to 1 minute, then pulled out, heated at 160 to 200°C for 1 to 3 minutes, and then cooled to form. A method for producing gloves made of vinyl chloride resin, which comprises inverting and demolding the laminated film.
JP22819890A 1990-08-31 1990-08-31 Method for manufacturing gloves made of vinyl chloride resin Expired - Fee Related JPH0753922B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22819890A JPH0753922B2 (en) 1990-08-31 1990-08-31 Method for manufacturing gloves made of vinyl chloride resin

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Application Number Priority Date Filing Date Title
JP22819890A JPH0753922B2 (en) 1990-08-31 1990-08-31 Method for manufacturing gloves made of vinyl chloride resin

Publications (2)

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JPH04119102A true JPH04119102A (en) 1992-04-20
JPH0753922B2 JPH0753922B2 (en) 1995-06-07

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04289203A (en) * 1991-01-18 1992-10-14 Towa Corp:Kk Glove and production thereof
EP0686004A1 (en) 1993-12-23 1995-12-13 Maxxim Medical, Inc. Flexible polyvinyl chloride article and method of making
US6641879B1 (en) 1999-04-14 2003-11-04 Sumitomo Rubber Industries, Ltd. Acrylic glove with internal coating

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6399303A (en) * 1986-10-09 1988-04-30 尚和化工株式会社 Production of dustproof glove
JPS63175104A (en) * 1987-01-14 1988-07-19 中原 祐士 Production of glove made of vinyl chloride resin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6399303A (en) * 1986-10-09 1988-04-30 尚和化工株式会社 Production of dustproof glove
JPS63175104A (en) * 1987-01-14 1988-07-19 中原 祐士 Production of glove made of vinyl chloride resin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04289203A (en) * 1991-01-18 1992-10-14 Towa Corp:Kk Glove and production thereof
EP0686004A1 (en) 1993-12-23 1995-12-13 Maxxim Medical, Inc. Flexible polyvinyl chloride article and method of making
EP0686004B2 (en) 1993-12-23 2004-12-15 Medline Industries, Inc., Glove and method of making it
US6641879B1 (en) 1999-04-14 2003-11-04 Sumitomo Rubber Industries, Ltd. Acrylic glove with internal coating

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