JPH0625450A - Surface-modified rubber article and its production - Google Patents
Surface-modified rubber article and its productionInfo
- Publication number
- JPH0625450A JPH0625450A JP14074992A JP14074992A JPH0625450A JP H0625450 A JPH0625450 A JP H0625450A JP 14074992 A JP14074992 A JP 14074992A JP 14074992 A JP14074992 A JP 14074992A JP H0625450 A JPH0625450 A JP H0625450A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- modified
- monomer
- film
- rubber product
- 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.)
- Pending
Links
Landscapes
- Gloves (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ゴム手袋等の、ゴムラ
テックスからなる皮膜を有するゴム製品に関し、より詳
細には、上記皮膜の表面の粘着性が改善された表面改質
ゴム製品と、その製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber product, such as a rubber glove, having a film made of rubber latex, and more specifically, a surface-modified rubber product having an improved surface tackiness of the film, The present invention relates to a manufacturing method thereof.
【０００２】[0002]
【従来の技術】天然ゴムラテックス等のゴムラテックス
から、各種のラテックス浸漬法により製造されるゴム製
品、特にゴム手袋は、そのままでは粘着性が強過ぎて、
付け外しが困難であるため、 タルク、雲母粉、澱粉等の打粉もしくは離型剤を表
面に付着させる、 表面をハロゲンで処理する、等の方法により、表面
の粘着性を低下させることが行われている。2. Description of the Related Art Rubber products produced by various latex dipping methods from rubber latex such as natural rubber latex, especially rubber gloves, are too sticky as they are,
Since it is difficult to attach and remove, it is possible to reduce the tackiness of the surface by methods such as applying a dusting agent such as talc, mica powder, starch, or a release agent to the surface, treating the surface with halogen, etc. ing.
【０００３】しかし、上記の方法は、粉が取れると効
力を失うという問題がある他、取れた粉が食品等を汚染
するおそれもある。また、上記の方法では、有毒な塩
素を使用するため、環境衛生上、安全上の配慮が必要で
あり、また、製品の変色を伴うことが多い。ゴム製品の
表面に紫外線を照射する方法もあるが、他の方法に比べ
て効果が小さく、実用化されるに至っていない。However, the above method has a problem that the powder loses its effectiveness when it is taken off, and the powder taken out may contaminate foods and the like. Further, in the above method, since toxic chlorine is used, it is necessary to consider safety in terms of environmental hygiene, and the product is often discolored. There is also a method of irradiating the surface of a rubber product with ultraviolet rays, but the effect is smaller than other methods, and it has not been put to practical use.
【０００４】上記の問題を解決するために、２−ヒドロ
キシエチルメタクリレート（ＨＥＭ Ａ）を必須の成分とし、これにメタクリル酸（ＭＡＡ）
およびエチルヘキシルアクリレート（ＥＨＡ）のうち少
なくとも１種のモノマーを組み合わせた共重合体すなわ
ち、 ＨＥＭＡ＋ＭＡＡ＋ＥＨＡ ＨＥＭＡ＋ＭＡＡ ＨＥＭＡ＋ＥＨＡ の何れかの組み合わせからなる共重合体の塗膜をコーテ
ィングした、天然ゴム製のゴム手袋が提案された（特表
昭５９−５０１５００号）。In order to solve the above problems, 2-hydroxyethyl methacrylate (HEMA) is used as an essential component, and methacrylic acid (MAA) is added to this.
A rubber glove made of natural rubber is proposed, which is a copolymer in which at least one monomer selected from ethyl hexyl acrylate (EHA) is combined, that is, a copolymer of any combination of HEMA + MAA + EHA HEMA + MAA HEMA + EHA. (Special Table Sho 59-501500).
【０００５】しかし、この場合には、粘着性の低下が十
分でなく、しかもモノマーの重合、コーティング液の調
製、塗布、乾燥等の工程に加えて、天然ゴムと塗膜とを
十分に密着させるために、下地を処理する必要もある
等、多数の工程を要するという問題がある。本発明は、
以上の事情に鑑みてなされたものであって、表面の粘着
性が改善されているとともに、その効力が半永久的に持
続する表面改質ゴム製品と、この表面改質ゴム製品を、
より少ない工程で、簡単かつ安価に製造するための製造
方法とを提供することを目的としている。However, in this case, the adhesiveness is not sufficiently lowered, and in addition to the steps of polymerizing the monomer, preparing the coating solution, coating and drying, the natural rubber and the coating film are sufficiently adhered. Therefore, there is a problem that a large number of steps are required, such as the need to process the base. The present invention is
In view of the above circumstances, the surface-modified rubber product having improved surface tackiness and its effect semipermanently, and the surface-modified rubber product,
It is an object of the present invention to provide a manufacturing method for manufacturing easily and inexpensively with fewer steps.
【０００６】[0006]
【課題を解決するための手段および作用】上記課題を解
決するための、本発明の表面改質ゴム製品は、ゴムラテ
ックスからなる皮膜を有するゴム製品の、当該皮膜の表
面が、重合性の炭素−炭素二重結合を有するモノマー、
そのオリゴマー、および、そのポリマーのうちの少なく
とも１種を含む表面改質剤の塗布と、その後の紫外線照
射により改質されていることを特徴としている。また、
本発明の製造方法は、ゴムラテックスからなる皮膜を有
するゴム製品の、当該皮膜の表面に、重合性の炭素−炭
素二重結合を有するモノマー、そのオリゴマー、およ
び、そのポリマーのうちの少なくとも１種を含む表面改
質剤を塗布した後、紫外線を照射することを特徴とす
る。Means and Actions for Solving the Problems In order to solve the above problems, a surface-modified rubber product of the present invention is a rubber product having a film made of rubber latex, and the surface of the film is a polymerizable carbon. A monomer having a carbon double bond,
It is characterized in that it is modified by applying a surface modifier containing at least one of the oligomer and the polymer and then irradiating it with ultraviolet rays. Also,
The production method of the present invention is a rubber product having a film made of rubber latex, and at least one of a monomer having a polymerizable carbon-carbon double bond, an oligomer thereof, and a polymer thereof on the surface of the film. It is characterized in that after applying a surface modifying agent containing, ultraviolet rays are irradiated.
【０００７】上記構成からなる、本発明によれば、表面
改質剤の塗布と紫外線照射の２工程の処理で、ゴム製品
表面の粘着性を改善することができる。また、有毒な塩
素等を使用しないので安全である。しかも、表面改質剤
中のモノマー、オリゴマー、ポリマーは、紫外線の照射
により、重合反応あるいは架橋反応により、高い耐性を
有し、かつ、ゴム皮膜と一体化した改質層を構成するの
で、粘着性改善の効力は半永久的に持続する。According to the present invention having the above structure, the tackiness of the surface of the rubber product can be improved by the two-step treatment of applying the surface modifier and irradiating the ultraviolet rays. In addition, it is safe because it does not use toxic chlorine. Moreover, the monomers, oligomers, and polymers in the surface modifier have high resistance to the polymerization reaction or cross-linking reaction upon irradiation with ultraviolet rays, and form a modified layer integrated with the rubber film. The effect of sex improvement lasts semipermanently.
【０００８】以下に、本発明を説明する。ゴム製品、例
えばゴム手袋は、従来と同様に、通常の浸漬法や、感熱
法、凝着法等の、従来公知の種々のラテックス浸漬法に
より形成したゴムの皮膜を加硫することで製造される。
上記ラテックス浸漬法のうち通常の浸漬法は、手袋用の
型、または、手袋の形にした織布や不織布（裏材にな
る）を、天然ゴムラテックスや合成ゴムラテックス等の
ゴムラテックス中に浸漬し、引き上げて乾燥させる工程
を１回または複数回繰り返してゴムの皮膜を形成する方
法である。また、感熱法は、感熱凝固剤を添加したゴム
ラテックス中に予熱した型等を浸漬して、その表面に、
ゲル化したゴムラテックスを付着させた後、引き上げて
乾燥させる方法である。さらに、凝着法は、型の表面に
陽イオン（カルシウムイオン等）を付着させておいて、
負に帯電したラテックス中のゴム粒子を型の表面に凝集
させた後、引き上げて乾燥させる方法である。The present invention will be described below. Rubber products, for example, rubber gloves, are manufactured by vulcanizing a rubber film formed by various conventionally known latex dipping methods such as a normal dipping method, a heat-sensitive method, and an adhesion method, as in the past. It
Among the above-mentioned latex dipping methods, the usual dipping method involves dipping a glove mold or a woven or non-woven fabric (which will be the backing material) in the shape of a glove into rubber latex such as natural rubber latex or synthetic rubber latex. Then, the step of pulling up and drying is repeated once or plural times to form a rubber film. Further, the heat-sensitive method is to immerse a preheated mold or the like in rubber latex containing a heat-sensitive coagulant,
This is a method in which gelled rubber latex is attached and then pulled up and dried. Furthermore, in the adhesion method, cations (calcium ions etc.) are attached to the surface of the mold,
This is a method in which the rubber particles in the negatively charged latex are aggregated on the surface of the mold and then pulled up and dried.
【０００９】上記ゴム製品の表面に塗布される表面改質
剤としては、重合性の炭素−炭素二重結合を有するモノ
マー、そのオリゴマー、および、そのポリマーのうちの
少なくとも１種を含むものが使用される。モノマーとし
ては、たとえばスチレン、メタクリル酸、４−ビニルピ
リジン、２−ヒドロキシエチルメタクリレート、メチル
アクリレート、エチルアクリレート、メチルメタクリレ
ート、アクリル酸、アクリルアミド、アリルアルコー
ル、アリルグリシジルエーテル等の、従来公知の種々の
モノマーがあげられる他、とくに分子中にケイ素原子ま
たはフッ素を含有するモノマーが好適に使用される。As the surface modifier applied to the surface of the rubber product, one containing at least one of a monomer having a polymerizable carbon-carbon double bond, an oligomer thereof and a polymer thereof is used. To be done. Examples of the monomer include various conventionally known monomers such as styrene, methacrylic acid, 4-vinylpyridine, 2-hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, acrylamide, allyl alcohol, and allyl glycidyl ether. In addition to these, a monomer containing a silicon atom or fluorine in the molecule is particularly preferably used.
【００１０】分子中にケイ素原子を含有するモノマーと
しては、たとえば式(1) ：Examples of the monomer containing a silicon atom in the molecule include those represented by the formula (1):
【００１１】[0011]
【化１】 [Chemical 1]
【００１２】（式中ｎは５０〜７０の正の数を示す）で
表される両末端変性シリコーンオイル、式(2) ：Silicone oil modified at both ends represented by the formula (n is a positive number of 50 to 70), and the formula (2):
【００１３】[0013]
【化２】 [Chemical 2]
【００１４】（式中ｍは５０〜７０の正の数を示す）で
表される片末端変性シリコーンオイルおよびγ−メタク
リロキシプロピルトリメトキシシラン等があげられる。
また、分子中にフッ素を含有するモノマーとしては、た
とえば２，２，３，３−テトラフルオロプロピルメタク
リレート、２−（パーフルオロオクチル）エチルアクリ
レート、パーフルオロオクチルエチレン、２−（パーフ
ルオロオクチル）エチルメタクリレート等があげられ
る。One end-modified silicone oil represented by the formula (m represents a positive number of 50 to 70), γ-methacryloxypropyltrimethoxysilane and the like can be mentioned.
Examples of the monomer containing fluorine in the molecule include 2,2,3,3-tetrafluoropropyl methacrylate, 2- (perfluorooctyl) ethyl acrylate, perfluorooctylethylene, and 2- (perfluorooctyl) ethyl. Examples include methacrylate.
【００１５】上記モノマーは単独で使用される他、２種
以上を併用することもできる。オリゴマーとしては、上
記各モノマーの１種または２種以上を原料とする、分子
量１００００以下程度の低重合体があげられる。さらに
ポリマーとしては、上記モノマーまたはオリゴマーの１
種または２種以上を原料とする、直鎖状あるいは分枝岐
状の重合体があげられる。The above monomers may be used alone or in combination of two or more. Examples of the oligomer include low polymers having a molecular weight of about 10,000 or less, which are prepared from one or more of the above monomers as raw materials. Further, as the polymer, one of the above-mentioned monomers or oligomers is used.
Examples thereof include straight-chain or branched-chain polymers using one or two or more as raw materials.
【００１６】上記モノマー、オリゴマーおよびポリマー
のうち後の２者は、常態において固体の場合、適当な溶
媒や重合性希釈剤中に溶解または分散させて、表面改質
剤が構成される。一方、前者のモノマーは、常態におい
て液体であるため、それ自身を、表面改質剤として使用
することができる。そして、この場合には、表面改質剤
の調製等の手間がかからないので、表面改質ゴム製品
を、より一層少ない工程で、簡単かつ安価に製造できる
という利点がある。もちろん、モノマーを使用する際
に、溶媒や重合性希釈剤を併用してもよいことは、言う
までもない。なお、上記モノマーは、同系のモノマーか
らなるオリゴマーやポリマーの重合性希釈剤として使用
することもできる。When the latter two of the above-mentioned monomers, oligomers and polymers are normally solid, they are dissolved or dispersed in a suitable solvent or polymerizable diluent to form a surface modifier. On the other hand, since the former monomer is normally a liquid, it can be used as a surface modifier by itself. In this case, there is no need for preparation of the surface modifier, and therefore, there is an advantage that the surface modified rubber product can be manufactured easily and inexpensively in a smaller number of steps. Of course, it goes without saying that a solvent and a polymerizable diluent may be used together when the monomer is used. The above-mentioned monomer can also be used as a polymerizable diluent for an oligomer or polymer composed of the same type of monomer.
【００１７】溶媒や重合性開始剤の使用量は特に限定さ
れず、モノマー、オリゴマー、ポリマーの種類、目的と
する表面改質剤の粘度や流動性等に応じて、適宜量を使
用すればよい。表面改質剤をゴム皮膜の表面に塗布する
方法としては、スプレー法、浸漬法、フローコート法、
バーコート法、刷毛塗り法等、従来公知の種々の塗布方
法の中から、ゴム製品の形状等に応じて、適宜の方法を
選択すればよい。The amount of the solvent and the polymerizable initiator used is not particularly limited, and may be used in an appropriate amount depending on the types of the monomer, the oligomer and the polymer, the viscosity and fluidity of the target surface modifier, and the like. . As a method of applying the surface modifier to the surface of the rubber film, a spray method, a dipping method, a flow coating method,
An appropriate method may be selected from various conventionally known coating methods such as a bar coating method and a brush coating method according to the shape of the rubber product.
【００１８】モノマー、オリゴマーおよびポリマーは、
紫外線を照射すると、活性化してラジカルを生じ、重合
反応や架橋反応を開始するが、その開始作用はあまり大
きくないので、通常は、ベンゾイン等の光活性物質を、
紫外線増感剤として併用するのが好ましい。紫外線増感
剤は、通常、上記表面改質剤中に配合されるが、表面改
質剤を塗布する前のゴム皮膜の表面や、ゴム皮膜の表面
に塗布された表面改質剤の塗膜の表面に、上記紫外線増
感剤を含む溶液を塗布してもよい。The monomers, oligomers and polymers are
When it is irradiated with ultraviolet rays, it is activated to generate radicals and initiates a polymerization reaction or a cross-linking reaction, but since the initiation action is not so large, a photoactive substance such as benzoin is usually added.
It is preferably used in combination as an ultraviolet sensitizer. The UV sensitizer is usually blended in the above surface modifier, but the surface of the rubber film before the surface modifier is applied, or a coating film of the surface modifier applied to the surface of the rubber film. You may apply the solution containing the said ultraviolet sensitizer to the surface of this.
【００１９】紫外線増感剤の使用量も、本発明では特に
限定されず、モノマー、オリゴマー、ポリマーの反応性
等に応じて、適宜量を使用すればよい。紫外線の照射に
は、高圧水銀ランプ等を用いた、通常の紫外線照射装置
を使用することができる。なお、本発明の構成は、ゴム
手袋以外にも、例えば指サックやゴム長靴等の、従来公
知の種々のゴム製品に適用することができる。The amount of the UV sensitizer used is not particularly limited in the present invention, and may be used in an appropriate amount depending on the reactivity of the monomer, oligomer or polymer. For the irradiation of ultraviolet rays, an ordinary ultraviolet irradiation device using a high pressure mercury lamp or the like can be used. In addition to the rubber gloves, the configuration of the present invention can be applied to various conventionally known rubber products such as finger cots and rubber boots.
【００２０】[0020]
【実施例】以下に、本発明を、実施例および比較例に基
づいて説明する。実施例１ イオウ、亜鉛華、加硫促進剤、安定剤等を適量配合した
天然ゴムラテックスから、凝着法により作製し、加硫し
たゴム皮膜の表面に、紫外線増感剤としてのベンゾフェ
ノンをアセトンで希釈した溶液（濃度０．２重量％）を
浸漬塗布した後、その上に、スチレンモノマーを、表面
改質剤として同様に浸漬塗布した。EXAMPLES The present invention will be described below based on Examples and Comparative Examples. Example 1 A benzophenone as an ultraviolet sensitizer was acetone-produced on a surface of a vulcanized rubber film, which was prepared by a coagulation method from a natural rubber latex in which an appropriate amount of sulfur, zinc white, a vulcanization accelerator, a stabilizer and the like was mixed. The solution (concentration: 0.2% by weight) diluted with was applied by dip coating, and then a styrene monomer was similarly applied by dip coating as a surface modifier.
【００２１】つぎに、光化学用高圧水銀ランプ（４００
Ｗ、株式会社入江製作所製の品番Ｈ−４００Ｐ）を、上
記ゴム皮膜から２０cm離した位置にセットして紫外線を
照射し、照射２０分後および４０分後の、表面の摩擦係
数を、以下の方法で測定した。摩擦係数の測定 試料としてのゴム皮膜（５cm×６cm）の処理面をアクリ
ル板に密着させ、１８０ｇの荷重をかけた状態で、５０
０mm／分の速度でアクリル板の表面に沿って移動させた
際の摩擦係数を求めた。Next, a high pressure mercury lamp for photochemistry (400
W, product number H-400P manufactured by Irie Seisakusho Co., Ltd. is set at a position 20 cm away from the rubber film and is irradiated with ultraviolet rays. The friction coefficient of the surface 20 minutes after irradiation and 40 minutes after irradiation is as follows. It was measured by the method. Measurement of friction coefficient The treated surface of a rubber film (5 cm x 6 cm) as a sample is adhered to an acrylic plate and a load of 180 g is applied to
The coefficient of friction when moved along the surface of the acrylic plate at a speed of 0 mm / min was determined.
【００２２】実施例２ 表面改質剤としてメタクリル酸モノマーを使用したこと
以外は、上記実施例１と同様にして、ゴム皮膜の表面を
改質し、紫外線照射２０分後および４０分後の、表面の
摩擦係数を測定した。実施例３ 表面改質剤として４−ビニルピリジンモノマーを使用し
たこと以外は、上記実施例１と同様にして、ゴム皮膜の
表面を改質し、紫外線照射２０分後および４０分後の、
表面の摩擦係数を測定した。 Example 2 The surface of the rubber film was modified in the same manner as in Example 1 except that a methacrylic acid monomer was used as the surface modifier, and after 20 minutes and 40 minutes of ultraviolet irradiation, The coefficient of friction of the surface was measured. Example 3 The surface of the rubber film was modified in the same manner as in Example 1 except that 4-vinylpyridine monomer was used as the surface modifier, and after 20 minutes and 40 minutes of ultraviolet irradiation,
The coefficient of friction of the surface was measured.
【００２３】実施例４ ゴム皮膜の表面に紫外線増感剤を全く塗布しなかったこ
と以外は、上記実施例２と同様にして、ゴム皮膜の表面
を改質し、紫外線照射２０分後および４０分後の、表面
の摩擦係数を測定した。比較例１ ゴム皮膜の表面に、紫外線増感剤の溶液と表面改質剤と
を何れも塗布せず、紫外線の照射のみでゴム皮膜の表面
を改質し、紫外線照射２０分後および４０分後の、表面
の摩擦係数を測定した。 Example 4 The surface of the rubber film was modified in the same manner as in Example 2 except that the ultraviolet sensitizer was not applied to the surface of the rubber film, and after 20 minutes of irradiation with ultraviolet rays and 40 times. After minutes, the coefficient of friction of the surface was measured. Comparative Example 1 The surface of the rubber film was not coated with the solution of the UV sensitizer and the surface modifier, and the surface of the rubber film was modified only by irradiation of ultraviolet rays. Later, the coefficient of friction of the surface was measured.
【００２４】以上の結果を、表面を全く改質処理してい
ないゴム皮膜（比較例２）、および、表面を塩素で処理
したゴム皮膜（比較例３）の摩擦係数の測定結果と合わ
せて、表１に示す。The above results are combined with the measurement results of the friction coefficient of the rubber film whose surface is not modified at all (Comparative Example 2) and the rubber film whose surface is treated with chlorine (Comparative Example 3). It shows in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】上記表１の結果より、実施例１〜３は、何
れも、全く改質処理していない比較例２や、紫外線の照
射のみで改質した比較例１に比べて、紫外線照射２０分
後の段階で、摩擦係数を著しく低下させることができ
た。また、紫外線照射４０分後の段階では、表面を塩素
で処理した比較例３よりも摩擦係数を低下させることが
できた。From the results of Table 1 above, in all of Examples 1 to 3, compared with Comparative Example 2 in which no modification treatment was performed and Comparative Example 1 in which modification was performed only by irradiation of ultraviolet rays, ultraviolet irradiation 20 was performed. It was possible to significantly reduce the coefficient of friction at the later stage. Further, at the stage of 40 minutes after the irradiation with ultraviolet rays, the friction coefficient could be lowered as compared with Comparative Example 3 in which the surface was treated with chlorine.
【００２７】また、同じメタクリル酸モノマーを使用
し、紫外線増感剤を全く用いなかった実施例４と紫外線
増感剤を用いた実施例２とを比較すると、実施例４は実
施例２に比べてわずかに摩擦係数が大きいが、それで
も、表面を塩素で処理した比較例３よりも摩擦係数を小
さくできることがわかった。手袋の着用性観察 天然ゴムラテックスから凝着法によって手袋を作製し、
加硫した後、上記実施例１〜３、比較例１，３と同様に
して、その表面を改質処理した。また、比較例２と同様
に、表面を改質しない手袋も用意した。そして、実際に
手に着用して、着用性を観察したところ、全く表面を改
質していない比較例２に相当する手袋は、粘着性が高過
ぎて全く着用できなかった。また、比較例１に相当する
手袋は、紫外線照射２０分後の段階では着用が困難であ
り、紫外線照射４０分後の段階では着用できたが、若干
の粘着を伴った。比較例３に相当する手袋は、他の比較
例より着用が容易であったが、実施例１〜３に相当する
手袋は、さらに着用が容易であった。Further, comparing Example 4 using the same methacrylic acid monomer and using no UV sensitizer with Example 2 using the UV sensitizer, Example 4 compares with Example 2. It was found that the friction coefficient was slightly higher than that of Comparative Example 3 in which the surface was treated with chlorine. Observation of the wearability of gloves Gloves were made from natural rubber latex by the adhesion method,
After vulcanization, the surface was modified in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 3. Also, as in Comparative Example 2, gloves whose surface was not modified were prepared. Then, when actually worn on a hand and observed the wearability, the glove corresponding to Comparative Example 2 in which the surface was not modified at all was too sticky and could not be worn at all. Further, the glove corresponding to Comparative Example 1 was difficult to wear at the stage 20 minutes after the irradiation with ultraviolet rays, and could be worn at the stage 40 minutes after the irradiation with ultraviolet rays, but it was accompanied by some stickiness. The gloves corresponding to Comparative Example 3 were easier to wear than the other Comparative Examples, but the gloves corresponding to Examples 1 to 3 were even easier to wear.
【００２８】実施例５ 表面改質剤として２，２，３，３−テトラフルオロプロ
ピルメタクリレートモノマーを使用したこと以外は、前
記実施例１と同様にしてゴム皮膜の表面を改質し、紫外
線照射４０分後の表面の摩擦係数を、前記実施例１〜４
と同様の方法で測定した。 Example 5 The surface of the rubber film was modified in the same manner as in Example 1 except that 2,2,3,3-tetrafluoropropylmethacrylate monomer was used as the surface modifier, and ultraviolet irradiation was carried out. The coefficient of friction of the surface after 40 minutes was calculated as in Examples 1 to 4 above.
It measured by the method similar to.
【００２９】実施例６ 表面改質剤として２−（パーフルオロオクチル）エチル
アクリレートモノマーを使用したこと以外は、上記実施
例５と同様にしてゴム皮膜の表面を改質し、紫外線照射
４０分後の表面の摩擦係数を測定した。実施例７ 表面改質剤としてパーフルオロオクチルエチレンモノマ
ーを使用したこと以外は、上記実施例５と同様にしてゴ
ム皮膜の表面を改質し、紫外線照射４０分後の表面の摩
擦係数を測定した。 Example 6 The surface of the rubber film was modified in the same manner as in Example 5 except that 2- (perfluorooctyl) ethyl acrylate monomer was used as the surface modifier, and after 40 minutes of UV irradiation. The coefficient of friction of the surface was measured. Example 7 The surface of the rubber film was modified in the same manner as in Example 5 except that a perfluorooctylethylene monomer was used as the surface modifier, and the friction coefficient of the surface 40 minutes after ultraviolet irradiation was measured. .
【００３０】実施例８ 表面改質剤として２−（パーフルオロオクチル）エチル
メタクリレートモノマーを使用したこと以外は、上記実
施例５と同様にしてゴム皮膜の表面を改質し、紫外線照
射４０分後の表面の摩擦係数を測定した。実施例９ 表面改質剤として前記式(1) で表される両末端変性シリ
コーンオイルを使用したこと以外は、上記実施例５と同
様にしてゴム皮膜の表面を改質し、紫外線照射４０分後
の表面の摩擦係数を測定した。 Example 8 The surface of the rubber film was modified in the same manner as in Example 5 except that 2- (perfluorooctyl) ethyl methacrylate monomer was used as the surface modifier, and after 40 minutes of ultraviolet irradiation. The coefficient of friction of the surface was measured. Example 9 The surface of a rubber film was modified in the same manner as in Example 5 except that the silicone oil modified at both ends represented by the above formula (1) was used as the surface modifier, and the UV irradiation was performed for 40 minutes. The coefficient of friction of the subsequent surface was measured.
【００３１】実施例１０ 表面改質剤として前記式(2) で表される片末端変性シリ
コーンオイルを使用したこと以外は、上記実施例５と同
様にしてゴム皮膜の表面を改質し、紫外線照射４０分後
の表面の摩擦係数を測定した。実施例１１ 表面改質剤としてγ−メタクリロキシプロピルトリメト
キシシランモノマーを使用したこと以外は、上記実施例
５と同様にしてゴム皮膜の表面を改質し、紫外線照射４
０分後の表面の摩擦係数を測定した。 Example 10 The surface of the rubber film was modified in the same manner as in Example 5 except that the one-end modified silicone oil represented by the above formula (2) was used as the surface modifier, and ultraviolet rays were used. The friction coefficient of the surface 40 minutes after irradiation was measured. Example 11 The surface of the rubber film was modified in the same manner as in Example 5 except that γ-methacryloxypropyltrimethoxysilane monomer was used as the surface modifier, and ultraviolet irradiation 4
The coefficient of friction of the surface after 0 minutes was measured.
【００３２】以上の結果を、前記比較例２および比較例
３の摩擦係数の測定結果と合わせて、表２に示す。The above results are shown in Table 2 together with the measurement results of the friction coefficient of Comparative Examples 2 and 3.
【００３３】[0033]
【表２】 [Table 2]
【００３４】上記表２の結果より、実施例５〜１１は何
れも、全く改質処理していない比較例２や、表面を塩素
で処理した比較例３よりも摩擦係数を低下させることが
できた。手袋の着用性観察 天然ゴムラテックスから凝着法によって手袋を作製し、
加硫した後、実際に手に着用して着用性を観察したとこ
ろ、未処理の状態では粘着性が高過ぎて全く着用できな
かった。塩素処理すると着用は容易になったが、実施例
６および実施例１１と同じ処理を行った手袋はさらに着
用が容易であった。From the results shown in Table 2 above, in any of Examples 5 to 11, the friction coefficient can be lowered as compared with Comparative Example 2 in which no modification treatment is performed and Comparative Example 3 in which the surface is treated with chlorine. It was Observation of the wearability of gloves Gloves were made from natural rubber latex by the adhesion method,
After vulcanization, when actually worn on the hand and observed the wearability, the tackiness in the untreated state was too high to be worn at all. Chlorine treatment made it easier to wear, but gloves treated in the same manner as in Examples 6 and 11 were even easier to wear.
【００３５】[0035]
【発明の効果】本発明の表面改質ゴム製品とその製造方
法によれば、表面の粘着性が改善されているとともに、
その効力が半永久的に持続する表面改質ゴム製品を、よ
り少ない工程で、簡単かつ安価に製造することができ
る。According to the surface-modified rubber product and the method for producing the same of the present invention, the tackiness of the surface is improved, and
A surface-modified rubber product whose effect lasts semipermanently can be produced easily and inexpensively with fewer steps.
Claims (5)
製品の、当該皮膜の表面が、重合性の炭素−炭素二重結
合を有するモノマー、そのオリゴマー、および、そのポ
リマーのうちの少なくとも１種を含む表面改質剤の塗布
と、その後の紫外線照射により改質されていることを特
徴とする表面改質ゴム製品。1. A rubber product having a film made of rubber latex, wherein the surface of the film contains at least one kind of a monomer having a polymerizable carbon-carbon double bond, an oligomer thereof, and a polymer thereof. A surface-modified rubber product which is modified by applying a surface modifier and then irradiating it with ultraviolet rays.
マーが、分子中にケイ素原子およびフッ素原子のうちの
少なくとも一方を含有するものである請求項１記載の表
面改質ゴム製品。2. The surface-modified rubber product according to claim 1, wherein the monomer having a polymerizable carbon-carbon double bond contains at least one of a silicon atom and a fluorine atom in the molecule.
ム製品。3. The surface-modified rubber product according to claim 1, which is a rubber glove.
製品の、当該皮膜の表面に、重合性の炭素−炭素二重結
合を有するモノマー、そのオリゴマー、および、そのポ
リマーのうちの少なくとも１種を含む表面改質剤を塗布
した後、紫外線を照射することを特徴とする表面改質ゴ
ム製品の製造方法。4. A rubber product having a film made of rubber latex, wherein the surface of the film contains at least one of a monomer having a polymerizable carbon-carbon double bond, an oligomer thereof, and a polymer thereof. A method for producing a surface-modified rubber product, which comprises irradiating with ultraviolet rays after applying a surface-modifying agent.
マーとして、分子中にケイ素原子およびフッ素原子のう
ちの少なくとも一方を含有するものを使用する請求項４
記載の表面改質ゴム製品の製造方法。5. A monomer containing at least one of a silicon atom and a fluorine atom in a molecule is used as a monomer having a polymerizable carbon-carbon double bond.
A method for producing the surface-modified rubber product as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14074992A JPH0625450A (en) | 1992-03-11 | 1992-06-01 | Surface-modified rubber article and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-52675 | 1992-03-11 | ||
| JP5267592 | 1992-03-11 | ||
| JP14074992A JPH0625450A (en) | 1992-03-11 | 1992-06-01 | Surface-modified rubber article and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0625450A true JPH0625450A (en) | 1994-02-01 |
Family
ID=26393310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14074992A Pending JPH0625450A (en) | 1992-03-11 | 1992-06-01 | Surface-modified rubber article and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625450A (en) |
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|---|---|---|---|---|
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-
1992
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