JPH05123641A - Surface treatment of rubber product - Google Patents

Surface treatment of rubber product

Info

Publication number
JPH05123641A
JPH05123641A JP28799891A JP28799891A JPH05123641A JP H05123641 A JPH05123641 A JP H05123641A JP 28799891 A JP28799891 A JP 28799891A JP 28799891 A JP28799891 A JP 28799891A JP H05123641 A JPH05123641 A JP H05123641A
Authority
JP
Japan
Prior art keywords
rubber
weight
rubber product
modified urethane
urethane emulsion
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
JP28799891A
Other languages
Japanese (ja)
Other versions
JPH0738967B2 (en
Inventor
Itaru Horiguchi
至 堀口
Shinichi Kumakura
伸一 熊倉
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.)
Okamoto Industries Inc
Original Assignee
Okamoto 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 Okamoto Industries Inc filed Critical Okamoto Industries Inc
Priority to JP3287998A priority Critical patent/JPH0738967B2/en
Publication of JPH05123641A publication Critical patent/JPH05123641A/en
Publication of JPH0738967B2 publication Critical patent/JPH0738967B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To impart nonstickiness and lubricity to the surface of a rubber prod uct by coating the surface of the rubber body with a surface treating agent made of a modified urethane emulsion and forming a coating film by drying. CONSTITUTION:The surface of the rubber body of a rubber product is coated with a surface treating agent made of a modified urethane emulsion and a coating film is formed by drying. Since the modified urethane emulsion has very high compatibility with diene rubber, adhesive strength is enhanced as compared with the case of an ordinary urethane, acrylic or silicone emulsion and a tough coating film is permanently formed on the surface of the rubber product. The nonstickiness and physical property (strength) of the rubber product are improved, lubricity is imparted and exfoliation is not caused even at the time of use and by elongation.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は天然ゴム及びジエン系合
成ゴムよりなるゴム製品の表面処理方法、詳しくは非粘
着及び滑性を付与されたゴム製品を得る方法に関するも
のである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment method for a rubber product made of natural rubber and a diene-based synthetic rubber, and more particularly to a method for obtaining a rubber product provided with non-adhesion and lubricity.

【0002】[0002]

【従来の技術】従来、天然ゴム及びジエン系合成ゴムか
らなるゴム製品の表面を処理する方法としては、(1) 塩
素を表面に付加する(塩素化)、(2) 溶剤処理による表
面脱脂、(3) 強酸処理、プラズマ処理、コロナ処理など
の表面酸化、(4) ブラスト処理による表面粗面化、(5)
シリカ、タルク、スターチ類の粉体付着、(6) シリコー
ン、フッ素樹脂などの樹脂付着等があった。
2. Description of the Related Art Conventionally, as a method for treating the surface of a rubber product composed of natural rubber and diene-based synthetic rubber, (1) chlorine is added to the surface (chlorination), (2) surface degreasing by solvent treatment, (3) Surface oxidation such as strong acid treatment, plasma treatment, corona treatment, (4) surface roughening by blast treatment, (5)
There were adhesion of powder of silica, talc, starch, and (6) adhesion of resin such as silicone and fluororesin.

【0003】[0003]

【発明が解決しようとする問題点】しかしながら、これ
らの方法は作業に手間が掛るとともに、有害物質や強酸
化剤の使用による作業環境の低下や高エネルギーの使用
による設備コストの増大など、多くの問題があった。
However, these methods are labor-intensive, and the use of harmful substances and strong oxidants lowers the working environment and increases the cost of equipment due to the use of high energy. There was a problem.

【0004】更に、塩素化をしたものについては、洗浄
後の乾燥条件によりゴム製品上に水跡が残ることがあ
り、かつ塩素化されるためゴムの表面が硬化して微小な
亀裂を生じると云う問題もあった。
Further, with respect to the chlorinated product, water marks may remain on the rubber product depending on the drying condition after washing, and the chlorinated product may harden the surface of the rubber to cause minute cracks. There was also a problem.

【0005】また表面への樹脂付着については、これら
ゴム製品の素材である天然及び合成ゴム類は、その組成
から、官能基が少いため、表面に樹脂類が付着すること
は出来るが、付着力が弱いと云う欠点があった
Regarding the resin adhesion to the surface, the natural and synthetic rubbers, which are the raw materials of these rubber products, have few functional groups because of their composition, so that the resins can adhere to the surface, but the adhesive force There was a defect that was weak

【0006】また、シリコンオイルや粉体などは短時間
の使用でゴム表面から除去され、粘着感が出ると云う欠
点があり、かつ他の合成樹脂類も、付着力が弱いためゴ
ム製品を伸ばした場合には、クラックが入り部分的に簡
単に剥離、除去されるため長時間の使用が困難であっ
た。
[0006] Silicone oil and powders have the drawback that they are removed from the rubber surface after a short period of use, giving a sticky feeling, and other synthetic resins also have a weak adhesive force and thus extend rubber products. In such a case, cracks are formed and are easily peeled off and partially removed, which makes it difficult to use for a long time.

【0007】[0007]

【問題点を解決するための手段】本発明は、このような
事情に鑑みてなされたものであり、その手段は、ゴム製
本体の表面に、変性ウレタンエマルジョンを塗布して、
乾燥皮膜を設けることである。
The present invention has been made in view of such circumstances, and means for applying a modified urethane emulsion to the surface of a rubber main body,
It is to provide a dry film.

【0008】[0008]

【実施例】本発明の実施例について説明するに、ゴム製
本体は此種の技術分野において周知な天然ゴム及びジエ
ェン系合成ゴムよりなる各種のゴム製品、例えば指サッ
ク、医療用具(氷のう、ドレージバック、カテーテルバ
ルーン、尿道カテーテル)、チューブ、手袋、パッキン
グゴム、輪ゴム等であり、これらは浸漬方法、押出し方
法など周知の製造方法によって得られたもので、その表
面、すなわち外面又は内面或いは内外両面に、変性ウレ
タンエマルジョンをコーティング、吹付け、浸漬など任
意な方法で塗布し、乾燥して皮膜を設ける。
EXAMPLES Examples of the present invention will be described. The rubber main body is made of various kinds of rubber products made of natural rubber and diene-based synthetic rubber, which are well known in the technical field of this kind, such as finger cots, medical devices (ice packs). , Drapeback, catheter balloon, urethral catheter), tube, glove, packing rubber, rubber band, etc., which are obtained by well-known manufacturing methods such as dipping method and extrusion method, and the surface thereof, that is, the outer surface or inner surface or The modified urethane emulsion is coated on both the inner and outer surfaces by an arbitrary method such as coating, spraying, dipping, and dried to form a film.

【0009】変性ウレタンエマルジョンの組成は、ポリ
オール類,ジイソシアネート類,鎖延長剤(多価アルコ
ール類,多価アミン類)の共重合体よりなるものであっ
て、モノマーとして選定される要因としては、親水性、
高反応性、密着性、摩擦係数が低い等を考慮し、性能の
良いポリオール類としてはポリ−ε−カプロラクトン、
ポリヘキサメチレンカーボネート、ポリブタジエンポリ
オール、シリコーンポリオール等であり、また、ジイソ
シアネート類としてはトリレンジイソシアネート、4−
4´−ジフェニルメタンジイソシアネート、ヘキサメチ
レンジイソシアネート、4−4´−メチレンビス(シク
ロヘキシルイソシアネート)、イソホロンジイソシアネ
ート等である。また、鎖延長剤は多価アルコール類では
エチレングリコール、1,4ブタンジオール等であり、
多価アミン類としてはイソホロンジアミン、4−4´−
ジフェニルメタンジアミン、ヒドラジン等である。特に
性能の高いポリオール類はポリヘキサメチレンカーボネ
ート、ポリブタジエンポリオール、シリコーンポリオー
ル等である。又これらを共重合体の基本ポリオールとし
て他のポリオールとの併用を行うこと、すなわち変性ポ
リオールを単独もしくはこれら他の変性ウレタン同士を
ブレンドしたものを用いる事は可能である。
The composition of the modified urethane emulsion is composed of a copolymer of polyols, diisocyanates and chain extenders (polyhydric alcohols, polyhydric amines), and factors selected as monomers include Hydrophilic,
Considering high reactivity, adhesion, low coefficient of friction, etc., good performance polyols include poly-ε-caprolactone,
Examples of the polyisocyanate include polyhexamethylene carbonate, polybutadiene polyol, and silicone polyol, and the diisocyanates include tolylene diisocyanate and 4-
4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4-4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate and the like. Further, the chain extender is polyhydric alcohol such as ethylene glycol and 1,4 butanediol,
As polyvalent amines, isophoronediamine, 4-4'-
Examples include diphenylmethanediamine and hydrazine. Particularly high-performance polyols are polyhexamethylene carbonate, polybutadiene polyol, silicone polyol and the like. It is also possible to use these as the basic polyol of the copolymer in combination with other polyols, that is, to use the modified polyol alone or a blend of these other modified urethanes.

【0010】又、本発明ではこの変性ウレタンエマルジ
ョンの溶液濃度を各ゴム製本体に合う様に調整する必要
があり、0.1 〜10%の範囲が適当であって、通常のゴム
製品では0.5 〜 7%がより効果を発揮し得るものであ
る。
Further, in the present invention, it is necessary to adjust the solution concentration of the modified urethane emulsion so as to be suitable for each rubber body, and the range of 0.1 to 10% is suitable, and 0.5 to 7 for ordinary rubber products. % Can be more effective.

【0011】上記変性ウレタンエマルジョンはその組成
がゴム製品本体と極めて近いものであるため、相溶性が
従来のウレタンより、はるかに良い。したがって、ゴム
製品本体の表面に接着するものである。
Since the composition of the above-mentioned modified urethane emulsion is very close to that of the main body of the rubber product, the compatibility is far better than that of the conventional urethane. Therefore, it adheres to the surface of the rubber product body.

【0012】このようなエマルジョンに対して、耐溶剤
性,耐熱性,耐水性の向上を計るために水溶性メラミン
やエポキシ樹脂等を架橋剤として、有機アミン類もしく
はアンモニュウム塩類を触媒として、ゴムとの接着性の
すぐれたポリブタジエン系ウレタンの滑性をさらに良く
するためエポキシ変性シリコンなどをそれぞれ添加して
表面処理剤となし、さらに滑剤として、良好なもの例え
ばシリコンパウダー,ウレタンパウダー,ポリエチレン
ワックス,フッ素樹脂パウダー等を添加することも可能
であり、ゴム製本体をこの表面処理剤中に浸漬するか或
いは表面処理剤を吹きつけ又はコーティングで表面に塗
布する。
In order to improve the solvent resistance, heat resistance and water resistance of such an emulsion, water-soluble melamine, epoxy resin or the like is used as a cross-linking agent, organic amines or ammonium salts are used as a catalyst, and rubber is used. In order to improve the lubricity of polybutadiene-based urethane, which has excellent adhesiveness, epoxy-modified silicone is added as a surface treatment agent, and a good lubricant such as silicone powder, urethane powder, polyethylene wax, fluorine It is also possible to add resin powder or the like, and the rubber body is dipped in this surface treatment agent, or the surface treatment agent is sprayed or coated on the surface.

【0013】この表面処理剤の処理液配合処方例を示す
と変性ウレタンエマルジョン(40%)100 重量部に対し
て、水300 〜40000 重量部、水溶性エポキシ樹脂 1〜10
重量部及び滑剤を適量である。この塗布量は、乾燥して
皮膜となった際、その厚みを考慮しなければならない
が、できるだけ薄膜に形成しゴム製品の風合いを変える
ことがないようにする。
An example of the formulation of the treatment liquid of this surface treatment agent is as follows: 100 parts by weight of the modified urethane emulsion (40%), 300 to 40,000 parts by weight of water, and 1 to 10 parts of the water-soluble epoxy resin.
Appropriate amount of parts by weight and lubricant. The coating amount should be taken into consideration when it is dried to form a film, but it should be formed as thin as possible so as not to change the texture of the rubber product.

【0014】次に具体的な実施の態様及び比較例(従来
の方法)について詳述する。 実施例1及び比較例1 下記の天然ドライラバー配合を押出法によって、ゴムチ
ューブを形成し、表1に示す工程により加工を施す。実
施例1における表面処理剤の配合例は変性ウレタンエマ
ルジョン(ウレタン固形分40%)100 重量部(ポリブタ
ジエン系ウレタンエマルジョン40重量部とポリカーボネ
ート系ウレタンエマルジョン60重量部)に対して、水30
0 重量部、水溶性エポキシ樹脂(エポキシ架橋剤)4重
量部、シリコーンパウダー1重量部を添加したものであ
る。
Next, specific embodiments and comparative examples (conventional methods) will be described in detail. Example 1 and Comparative Example 1 A rubber tube was formed from the following natural dry rubber compound by an extrusion method and processed by the steps shown in Table 1. The compounding example of the surface treatment agent in Example 1 is 100 parts by weight of the modified urethane emulsion (40% urethane solid content) (40 parts by weight of polybutadiene-based urethane emulsion and 60 parts by weight of polycarbonate-based urethane emulsion) and 30 parts of water.
0 parts by weight, 4 parts by weight of a water-soluble epoxy resin (epoxy crosslinking agent), and 1 part by weight of silicone powder were added.

【0015】 天然ゴム 100 重量部 S 2 重量部 ZnO 3 重量部 TET 1 重量部 TMT 0.5 重量部 ステアリン酸 1 重量部 老化防止剤 1 重量部Natural rubber 100 parts by weight S 2 parts by weight ZnO 3 parts by weight TET 1 part by weight TMT 0.5 part by weight Stearic acid 1 part by weight Anti-aging agent 1 part by weight

【0016】[0016]

【表1】 [Table 1]

【0017】実施例2及び比較例2 下記の天然ゴムラテックス配合に浸漬方法によって、す
なわち表2に示す工程によりゴム手袋を成形する。実施
例2における表面処理剤は実施例1と同じ配合である。
Example 2 and Comparative Example 2 Rubber gloves are molded in the following natural rubber latex formulation by the dipping method, that is, by the steps shown in Table 2. The surface treatment agent in Example 2 has the same composition as in Example 1.

【0018】 天然ゴムラテックス(DRY) 100重量部 S 1重量部 ZnO 1重量部 ジチオカーバメイト系加硫促進剤 0.8重量部 老化防止剤 1重量部 安定剤 適 量Natural rubber latex (DRY) 100 parts by weight S 1 part by weight ZnO 1 part by weight Dithiocarbamate vulcanization accelerator 0.8 parts by weight Antioxidant 1 part by weight Stabilizer proper amount

【0019】[0019]

【表2】 [Table 2]

【0020】実施例3 上記実施例2に示す天然ゴムラテックス配合によるゴム
フィルムを造り、実施例1における表面処理剤を施した
ゴムフィルムと未処理のゴムフィルムとの物性及び性能
表を表3に示す。
Example 3 A rubber film prepared by blending the natural rubber latex shown in Example 2 above was prepared, and the physical properties and performance tables of the rubber film having the surface treatment agent and the untreated rubber film in Example 1 are shown in Table 3. Show.

【0021】[0021]

【表3】 [Table 3]

【0022】[0022]

【発明の効果】本発明はゴム製本体の表面に、変性ウレ
タンエマルジョンを塗布し乾燥皮膜を設けるから、非粘
着性及び物性(強度)が向上され滑性を付与されること
はもちろん、これらが向上したものが得られ、しかも従
来の方法に比して前処理加工を要することなく極めて簡
単であり、使用に際し及び伸長に対しても剥離のないも
のである。
According to the present invention, the surface of the rubber body is coated with the modified urethane emulsion to form a dry film, so that the non-adhesiveness and the physical properties (strength) are improved and the sliding property is imparted. An improved product is obtained, and it is extremely simple as compared with the conventional method without requiring pretreatment, and is free from peeling during use and elongation.

【0023】すなわち変性ウレタンエマルジョンはジエ
ン系ラバーに対して相溶性が極めて高いため、従来の極
性の高い一般のウレタン,アクリル系及び不活性なシリ
コーン系エマルジョンに比べて接着力の向上が発現し、
強固な皮膜となってゴム製品の表面に恒久的に形成する
ことが出来ると共に粉体等を使用しないから汚染される
ことなく使用時に除去されることがない。
That is, since the modified urethane emulsion has extremely high compatibility with the diene rubber, the adhesive strength is improved as compared with conventional urethane, acrylic and inert silicone emulsions having high polarity.
A strong film can be formed permanently on the surface of the rubber product, and since no powder or the like is used, it is not contaminated and is not removed during use.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 ゴム製本体の表面に、変性ウレタンマ
ルジョンを塗布し、乾燥皮膜を設けることを特徴とする
ゴム製品の表面処理方法。
1. A method for surface treatment of a rubber product, which comprises applying a modified urethane emulsion to the surface of a rubber body to form a dry film.
JP3287998A 1991-11-01 1991-11-01 Surface treatment method for rubber products Expired - Fee Related JPH0738967B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3287998A JPH0738967B2 (en) 1991-11-01 1991-11-01 Surface treatment method for rubber products

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3287998A JPH0738967B2 (en) 1991-11-01 1991-11-01 Surface treatment method for rubber products

Publications (2)

Publication Number Publication Date
JPH05123641A true JPH05123641A (en) 1993-05-21
JPH0738967B2 JPH0738967B2 (en) 1995-05-01

Family

ID=17724484

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3287998A Expired - Fee Related JPH0738967B2 (en) 1991-11-01 1991-11-01 Surface treatment method for rubber products

Country Status (1)

Country Link
JP (1) JPH0738967B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013079975A1 (en) 2011-12-01 2013-06-06 Lrc Products Limited Coated condom

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS627741A (en) * 1985-07-03 1987-01-14 Nok Corp Surface-coated cured rubber molded article and its production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS627741A (en) * 1985-07-03 1987-01-14 Nok Corp Surface-coated cured rubber molded article and its production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013079975A1 (en) 2011-12-01 2013-06-06 Lrc Products Limited Coated condom

Also Published As

Publication number Publication date
JPH0738967B2 (en) 1995-05-01

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