JPH06200224A - Highly adhesive hydrogel composition - Google Patents
Highly adhesive hydrogel compositionInfo
- Publication number
- JPH06200224A JPH06200224A JP35866192A JP35866192A JPH06200224A JP H06200224 A JPH06200224 A JP H06200224A JP 35866192 A JP35866192 A JP 35866192A JP 35866192 A JP35866192 A JP 35866192A JP H06200224 A JPH06200224 A JP H06200224A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- hydrogel composition
- polymerization
- acrylamido
- 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.)
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- Medicinal Preparation (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高い粘着性を有するハイ
ドロゲル組成物に関する。ハイドロゲルは、基本的に水
と親和性の高いイオン性基を有するポリマーで、一般に
ポリマー分子相互間に架橋構造をもっており、土木・建
築分野、農園芸分野、食品分野、医療分野、化粧分野、
電気分野、その他に広範な適用場面がある極めて有用な
物質である。TECHNICAL FIELD The present invention relates to a hydrogel composition having high tackiness. Hydrogel is basically a polymer having an ionic group having a high affinity for water, and generally has a cross-linking structure between polymer molecules, and is used in civil engineering / construction fields, agricultural / horticultural fields, food fields, medical fields, cosmetic fields,
It is a very useful substance that has a wide range of applications in the electric field and elsewhere.
【０００２】[0002]
【従来の技術】これら適用場面は、それぞれハイドロゲ
ルの種々の特性、すなわち、吸水性、保水性、膨潤性、
柔軟性、粘着性、導電性等を巧みに利用したことにに基
づいている。これら特性は互いに相関するが、粘着性
は、例えば、医療分野におけるパップ剤用基剤、生体電
極等の電気導電性基材などへの適用において特に考慮さ
れるべき特性である。2. Description of the Related Art These application scenes have various properties of hydrogels, namely, water absorption, water retention, swelling property,
It is based on the skillful use of flexibility, adhesiveness and conductivity. Although these properties correlate with each other, tackiness is a property to be particularly considered in application to, for example, a base for poultices in the medical field, an electrically conductive substrate such as a bioelectrode, and the like.
【０００３】粘着性はハイドロゲルの主要な特性の一つ
であり、ハイドロゲルにより高い粘着性を付与すること
は、上記パップ剤用基剤、生体電極等の電気導電性基材
の実用化において極めて重要である。同時に、ハイドロ
ゲルを皮膚に付着させて使用する場合にはハイドロゲル
中に残存するモノマーは安全性の面からできるだけ少な
いことが要求される。Adhesiveness is one of the main characteristics of hydrogels, and imparting higher adhesiveness to hydrogels is important for practical application of the above-mentioned bases for poultices, electrically conductive base materials such as bioelectrodes. Extremely important. At the same time, when the hydrogel is used by adhering to the skin, it is required that the monomer remaining in the hydrogel is as small as possible in terms of safety.
【０００４】しかしながら、十分な粘着性を有し、且つ
残存モノマーが少ない２−アクリルアミド−２−メチル
プロパンスルホン酸を使用したハイドロゲル組成物は未
だ提案されていない。僅かに、20〜60重量％の２−アク
リルアミド−２−メチルプロパンスルホン酸および／ま
たはその塩、10〜40重量％の多価アルコ−ル、10〜50重
量％の水、 0.1〜５重量％の架橋剤を必須成分とする生
体電極用組成物（特公昭63-59334号参照）が挙げられる
が、この組成物は一応の粘着力は有するものの、実際に
製造する場合は60〜100 ℃に加熱し架橋重合させるため
に重合に２時間以上を必要とする上、残存モノマーが多
い等の点でさらに改良が要求される。その他、２−アク
リルアミド−２−メチルプロパンスルホン酸架橋体を得
る方法として、重合開始剤として1000ppm/液程度の過硫
酸アンモニウムを添加し、55〜60℃、20分間加熱し重合
を完結させる方法（特開昭51ー1909 号公報参照）が提案
されているが、この場合では重合開始剤添加直後から重
合が始まるために、シートなどに成型する場合には作業
に時間的制約を生じ作業時間の確保が困難となり、工業
的な製造方法としては不適であると云わざるを得ない。However, a hydrogel composition using 2-acrylamido-2-methylpropanesulfonic acid having sufficient tackiness and a small amount of residual monomer has not been proposed yet. Slightly 20 to 60% by weight of 2-acrylamido-2-methylpropanesulfonic acid and / or its salt, 10 to 40% by weight of polyhydric alcohol, 10 to 50% by weight of water, 0.1 to 5% by weight. There is a composition for a bioelectrode (see Japanese Patent Publication No. 63-59334), which contains the crosslinking agent as an essential component. Although this composition has a tentative adhesive force, it can be manufactured at 60 to 100 ° C. Further, it takes 2 hours or more for the polymerization to be carried out by heating and cross-linking polymerization, and further improvement is required in that many residual monomers are contained. In addition, as a method for obtaining a crosslinked 2-acrylamido-2-methylpropanesulfonic acid, a method of adding about 1000 ppm / liquid ammonium persulfate as a polymerization initiator and heating at 55 to 60 ° C. for 20 minutes to complete the polymerization (special However, in this case, since the polymerization starts immediately after the addition of the polymerization initiator, there is a time constraint on the work when molding into a sheet, etc., and work time is secured. Therefore, it is difficult to say that it is not suitable as an industrial manufacturing method.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、これら従来
法の問題点を解決し、高い粘着性を有し、且つ残存モノ
マーが少ないハイドロゲル組成物を効率よく製造、提供
することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to solve the problems of these conventional methods and to efficiently produce and provide a hydrogel composition having high tackiness and less residual monomer. To do.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決すべく種々検討した結果、紫外線照射が該課題解決に
対し極めて有効であることを見出し、この知見に基づき
なされたものである。The present invention has been made on the basis of this finding as a result of various studies to solve the above-mentioned problems, and as a result, it was found that UV irradiation is extremely effective in solving the problems.
【０００７】なお、本発明に到る過程において、紫外線
照射は、前述の特公昭63-59334号公報記載の組成物に対
しては重合後の組成物の表面が平滑になり粘着力が極端
に低下してしまい、その効果を得ることができなかっ
た。この時点において、重合時間が加熱重合法に比べて
極端に短い紫外線照射による重合法は、粘着性を有する
ハイドロゲルを得る方法としては不適であるかと思われ
た。ところが、意外にも、該従来法の加熱重合法におい
て添加する架橋剤量 0.1〜５重量％が必須であるとして
いたものを、紫外線照射による重合法においては架橋剤
量を 0.1重量％に満たない極めて低濃度にすることで、
従来法に比べて高い粘着力が発現し、且つ残存モノマー
量が従来法に比べて約１／６と大幅に減少でき、しかも
短時間に効率よく高粘着性ハイドロゲル組成物が得られ
ることを見い出し本発明を完成した。In the process of reaching the present invention, irradiation with ultraviolet rays makes the surface of the composition after polymerization smoother than that of the composition described in Japanese Patent Publication No. 63-59334, and the adhesive strength is extremely high. It decreased, and it was not possible to obtain the effect. At this point, it seems that the polymerization method by ultraviolet irradiation, which has a polymerization time extremely shorter than that of the heat polymerization method, is not suitable as a method for obtaining a hydrogel having tackiness. However, surprisingly, the amount of the crosslinking agent to be added in the conventional heating polymerization method of 0.1 to 5% by weight was essential, but the amount of the crosslinking agent was less than 0.1% by weight in the polymerization method by ultraviolet irradiation. By making it extremely low,
A high adhesive strength is exhibited compared with the conventional method, the amount of residual monomer can be greatly reduced to about 1/6 compared with the conventional method, and a highly adhesive hydrogel composition can be obtained efficiently in a short time. Found and completed the present invention.
【０００８】すなわち、本発明は、20〜60重量部の２−
アクリルアミド−２−メチルプロパンスルホン酸または
その塩と0.03〜0.08重量部の架橋性モノマーを、20〜60
重量部の多価アルコールおよび10〜50重量部の水性媒体
中、ｐＨ 5.5以上で紫外線照射することにより共重合さ
せて得られる高粘着性ハイドロゲル組成物、を要旨とす
るものである。That is, the present invention comprises 20-60 parts by weight of 2-
Acrylamido-2-methylpropanesulfonic acid or a salt thereof and 0.03 to 0.08 parts by weight of a crosslinkable monomer, 20 to 60
A high-adhesive hydrogel composition obtained by copolymerization by irradiating ultraviolet rays at pH 5.5 or higher in a polyhydric alcohol of 10 parts by weight and an aqueous medium of 10 to 50 parts by weight.
【０００９】本発明においては、20〜60重量部の２−ア
クリルアミド−２−メチルプロパンスルホン酸と0.03〜
0.08重量部の架橋性モノマーにより架橋重合体が得られ
る。２−アクリルアミド−２−メチルプロパンスルホン
酸の使用形態は酸またはその塩であってよい。塩として
は、ナトリウム塩、カリウム塩、アンモニウム塩などが
一般的である。In the present invention, 20 to 60 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid and 0.03 to
A crosslinked polymer is obtained with 0.08 part by weight of the crosslinkable monomer. The usage form of 2-acrylamido-2-methylpropanesulfonic acid may be an acid or a salt thereof. As the salt, sodium salt, potassium salt, ammonium salt and the like are common.
【００１０】本発明において使用される架橋剤として
は，少なくとも２個の官能基を有するもので、メチレン
ビスアクリルアミド、エチレングリコールジメタクリレ
ート、２−ヒドロキシエチルメタクリレートなどが挙げ
られる。この内、メチレンビスアクリルアミドが臭気も
なく特に好適である。添加量は、0.03〜0.08重量部、好
ましくは、0.04〜0.07重量部の範囲である。0.03重量部
未満ではゲル化せず、また0.08重量部を越えると十分な
粘着性が得られない。The cross-linking agent used in the present invention has at least two functional groups, and examples thereof include methylenebisacrylamide, ethylene glycol dimethacrylate, and 2-hydroxyethyl methacrylate. Of these, methylenebisacrylamide is particularly suitable because it has no odor. The amount added is in the range of 0.03 to 0.08 parts by weight, preferably 0.04 to 0.07 parts by weight. If it is less than 0.03 parts by weight, no gelation occurs, and if it exceeds 0.08 parts by weight, sufficient tackiness cannot be obtained.
【００１１】本発明では多価アルコールは湿潤剤として
の役割を果たす。適用できる好ましい多価アルコールと
してはグリセリン、プロピレングリコール、ソルビトー
ル、ポリエチレングリコールなどが挙げられる。多価ア
ルコールは20重量部未満ではハイドロゲルシートは乾燥
しやすくなり長時間の使用に耐え難くなり、一方60重量
部を越えると過剰になり粘着力をむしろ下げるように作
用する。In the present invention, the polyhydric alcohol serves as a wetting agent. Preferable applicable polyhydric alcohols include glycerin, propylene glycol, sorbitol, polyethylene glycol and the like. If the amount of the polyhydric alcohol is less than 20 parts by weight, the hydrogel sheet will be easily dried and will not be able to withstand long-term use, while if it exceeds 60 parts by weight, the amount will be excessive and the adhesive force will be rather lowered.
【００１２】本発明において使用される水性媒体とは、
水が主体である媒体を意味するが水そのものであっても
構わない。この水はいかなる種類のものでもよいが、蒸
留または脱イオン化またはそれに類似する処理を施すこ
とは好ましい。水性媒体が10重量部未満では、２−アク
リルアミド−２−メチルプロパンスルホン酸またはその
塩を溶解するには不十分であり均質なハイドロゲルシー
トを得ることができない。また、水性媒体が50重量部を
越えると湿潤剤が少なくなるためハイドロゲルは乾燥し
やすく長時間の使用には耐え難くなる。The aqueous medium used in the present invention is
It means a medium mainly composed of water, but water itself may be used. The water may be of any kind, but it is preferred that it be subjected to distillation or deionization or similar treatment. If the amount of the aqueous medium is less than 10 parts by weight, it is insufficient to dissolve 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, and a homogeneous hydrogel sheet cannot be obtained. Further, when the amount of the aqueous medium exceeds 50 parts by weight, the amount of the wetting agent is reduced, so that the hydrogel is liable to dry and it becomes difficult to withstand long-term use.
【００１３】反応系のｐＨは、5.5 以上、好ましくは
5.5〜7.5 に調整する。5.5 未満では２−アクリルアミ
ド−２−メチルプロパンスルホン酸が自然重合を引き起
し易くなるので危険である。The pH of the reaction system is 5.5 or higher, preferably
Adjust to 5.5 to 7.5. If it is less than 5.5, 2-acrylamido-2-methylpropanesulfonic acid is likely to cause spontaneous polymerization, which is dangerous.
【００１４】本発明における紫外線の照射条件は、波長
450nm 以下、出力１〜1000Ｗ／ｍ2、好ましくは10〜100
Ｗ／ｍ2 、照射時間１〜3600秒、好ましくは60〜1800
秒の条件で適宜設定すればよい。この際、光開始剤とし
ては、例えば、ベンゾフェノン、ベンゾイン、ベンゾイ
ンアルキルエーテル、アンスラキノンなどから選択され
る１種または２種以上のものが使用される。これら使用
量は、通常対液10〜500ppmである。In the present invention, the ultraviolet irradiation conditions are as follows:
450 nm or less, output 1-1000 W / m 2 , preferably 10-100
W / m 2 , irradiation time 1 to 3600 seconds, preferably 60 to 1800
It may be set appropriately according to the condition of seconds. At this time, as the photoinitiator, for example, one kind or two or more kinds selected from benzophenone, benzoin, benzoin alkyl ether, anthraquinone and the like are used. The amount used of these is usually 10 to 500 ppm for the liquid.
【００１５】以下に、本発明の一実施態様を示す。ま
ず、20〜60重量部の２−アクリルアミド−２−メチルプ
ロパンスルホン酸またはその塩を10〜50重量部の水性媒
体に完全に溶かし、溶液のｐＨを 5.5〜7.5に調整す
る。この溶液に20〜60重量部の多価アルコールを加え撹
拌する。さらに、0.03〜0.08重量部の架橋性モノマーを
加え十分撹拌する。An embodiment of the present invention will be shown below. First, 20 to 60 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof is completely dissolved in 10 to 50 parts by weight of an aqueous medium, and the pH of the solution is adjusted to 5.5 to 7.5. 20-60 parts by weight of polyhydric alcohol is added to this solution and stirred. Further, 0.03 to 0.08 parts by weight of the crosslinkable monomer is added and the mixture is sufficiently stirred.
【００１６】次に、反応系から窒素置換、真空脱泡等に
より酸素を除いた後、型枠に流し込み、紫外線を照射し
重合を開始する。真空脱泡は必ずしも必要ではないが、
重合率の向上およびシート中の気泡の除去のためには、
重合前に真空脱泡することが望ましい。重合中に酸素の
影響を除くために、重合物の表面を窒素でシールしても
よく、あるいは酸素バリアー性のフィルムなどで酸素の
拡散を防ぐ方法も重合をより完結させるためには有効で
ある。Next, oxygen is removed from the reaction system by nitrogen substitution, vacuum defoaming, etc., and then poured into a mold and irradiated with ultraviolet rays to start polymerization. Vacuum degassing is not always necessary,
In order to improve the polymerization rate and remove bubbles in the sheet,
Vacuum degassing before polymerization is desirable. In order to remove the influence of oxygen during the polymerization, the surface of the polymer may be sealed with nitrogen, or a method of preventing oxygen diffusion with a film having an oxygen barrier property is also effective for further completing the polymerization. .
【００１７】[0017]
【発明の効果】本発明によれば、高い粘着力を有し、且
つ残存モノマーの少ないハイドロゲル組成物を効率よく
製造、提供することができる。EFFECTS OF THE INVENTION According to the present invention, it is possible to efficiently produce and provide a hydrogel composition having a high adhesive force and a small amount of residual monomers.
【００１８】[0018]
【実施例】以下、本発明を実施例に基づいて説明するな
お、ハイドロゲルシートの粘着力の評価は、シートに10
0gの分銅を押し当ててからひっくり返し、分銅が落下す
るまでの時間で示した。ゲル強度の目安としては、長さ
50mm、幅20mm、厚さ1.5mm のゲル片に12.5g の加重をか
けて長さの伸張度が５倍未満のものを良好（○）、５〜
８倍のものを柔らかいが使用可（△）と判定した。ま
た、残存モノマーの測定はハイドロゲルシートからメタ
ノールで２−アクリルアミド−２−メチルプロパンスル
ホン酸を抽出し、高速液体クロマトグラフィー（波長20
0nm)にて行った。[Examples] Hereinafter, the present invention will be described based on Examples. The evaluation of the adhesive strength of the hydrogel sheet was carried out by using 10 sheets.
The time from pressing the weight of 0 g to turning it over was shown, and the time until the weight fell was shown. As a measure of gel strength, length
A gel piece with a width of 50 mm, a width of 20 mm and a thickness of 1.5 mm is loaded with 12.5 g and the elongation of the length is less than 5 times is good (○), 5
It was judged that 8 times softer but usable (△). For measurement of residual monomers, 2-acrylamido-2-methylpropanesulfonic acid was extracted from the hydrogel sheet with methanol and subjected to high performance liquid chromatography (wavelength 20 nm).
0 nm).
【００１９】実施例１ ２−アクリルアミド−２−メチルプロパンスルホン酸の
ナトリウム塩 38gをイオン交換水 23.6gに溶解しｐＨ
6.0に調整した。これにグリセリン 38gを加えたのち架
橋性モノマーとしてメチレンビスアクリルアミド 0.020
〜0.10重量部を加え、さらに光開始剤としてベンゾイン
エチルエーテル対液150ppmを加えてよく混合してから真
空脱泡した。この溶液を型枠に流し込み、ポリエステル
フィルムでシールしてから室温にて15Ｗの低圧水銀灯を
15分間照射し重合を行った。結果を表−１に示す。Example 1 38 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid was dissolved in 23.6 g of ion-exchanged water to adjust pH.
Adjusted to 6.0. After adding 38 g of glycerin to this, methylenebisacrylamide 0.020 was added as a crosslinkable monomer.
˜0.10 parts by weight was added, and further 150 ppm of benzoin ethyl ether solution was added as a photoinitiator and mixed well, followed by degassing under vacuum. This solution is poured into a mold, sealed with a polyester film, and then a 15W low-pressure mercury lamp is used at room temperature.
Polymerization was carried out by irradiation for 15 minutes. The results are shown in Table-1.
【００２０】 [0020]
【００２１】比較例１ ２−アクリルアミド−２−メチルプロパンスルホン酸の
ナトリウム塩 38gをイオン交換水 23.6gに溶解しｐＨ
6.0に調整した。これにグリセリン 38gを加えたのち架
橋性モノマーとしてエチレングリコールジメタクリレー
ト 0.1〜1.0 重量部を加えてよく混合してから真空脱泡
した。これを60℃、２時間加熱し重合を行った。結果を
表−２に示す。Comparative Example 1 38 g of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid was dissolved in 23.6 g of ion-exchanged water to pH.
Adjusted to 6.0. To this, 38 g of glycerin was added, 0.1 to 1.0 part by weight of ethylene glycol dimethacrylate was added as a crosslinkable monomer, and they were mixed well and degassed in vacuum. This was heated at 60 ° C. for 2 hours to carry out polymerization. The results are shown in Table-2.
【００２２】 [0022]
【００２３】比較例２ 架橋性モノマーをメチレンビスアクリルアミドに変えた
以外は比較例１と同様に行った。結果を表−３に示す。Comparative Example 2 Comparative Example 2 was repeated except that methylenebisacrylamide was used as the crosslinkable monomer. The results are shown in Table-3.
【００２４】 [0024]
Claims (1)
メチルプロパンスルホン酸またはその塩と0.03〜0.08重
量部の架橋性モノマーを、20〜60重量部の多価アルコー
ルおよび10〜50重量部の水性媒体中、ｐＨ 5.5以上で紫
外線照射することにより共重合させて得られる高粘着性
ハイドロゲル組成物。1. 20 to 60 parts by weight of 2-acrylamido-2-
Copolymerization of methyl propane sulfonic acid or its salt with 0.03 to 0.08 parts by weight of a crosslinking monomer in 20 to 60 parts by weight of a polyhydric alcohol and 10 to 50 parts by weight of an ultraviolet medium at pH 5.5 or higher. A highly viscous hydrogel composition obtained by the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35866192A JPH06200224A (en) | 1992-12-28 | 1992-12-28 | Highly adhesive hydrogel composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35866192A JPH06200224A (en) | 1992-12-28 | 1992-12-28 | Highly adhesive hydrogel composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06200224A true JPH06200224A (en) | 1994-07-19 |
Family
ID=18460468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35866192A Pending JPH06200224A (en) | 1992-12-28 | 1992-12-28 | Highly adhesive hydrogel composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06200224A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245241A1 (en) * | 2001-03-30 | 2002-10-02 | The Procter & Gamble Company | Polymerized hydrogel adhesives comprising low amounts of residual monomers |
| EP1245240A1 (en) * | 2001-03-30 | 2002-10-02 | The Procter & Gamble Company | Skin-compatible hydrogel adhesives and personal care products containing them |
| JP2006507370A (en) * | 2002-03-29 | 2006-03-02 | ザ プロクター アンド ギャンブル カンパニー | Hydrogel adhesive for use on surfaces occupied by hair or fibers |
| JP2008522001A (en) * | 2004-12-03 | 2008-06-26 | スリーエム イノベイティブ プロパティズ カンパニー | Method for producing a pressure sensitive adhesive hydrogel |
| EP1505093A4 (en) * | 2002-05-01 | 2008-09-10 | Hokkaido Tech Licensing Office | Hydrogel of (semi)interpenetrating network structure and process for producing the same |
| JP2009227924A (en) * | 2008-03-25 | 2009-10-08 | Sekisui Plastics Co Ltd | Adhesive hydrogel, composition for its manufacture and its use |
| JP2010215925A (en) * | 2010-06-21 | 2010-09-30 | Lintec Corp | Antibacterial adhesive product |
| US8025696B2 (en) | 2004-06-18 | 2011-09-27 | National University Corporation Hokkaido University | Artificial meniscus and process of making thereof |
| US20130064982A1 (en) * | 2011-09-13 | 2013-03-14 | Chakravarthy S. Gudipati | Cation exchange materials prepared in aqueous media |
| WO2013172292A1 (en) * | 2012-05-12 | 2013-11-21 | 国立大学法人北海道大学 | Aqueous gel |
-
1992
- 1992-12-28 JP JP35866192A patent/JPH06200224A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245241A1 (en) * | 2001-03-30 | 2002-10-02 | The Procter & Gamble Company | Polymerized hydrogel adhesives comprising low amounts of residual monomers |
| EP1245240A1 (en) * | 2001-03-30 | 2002-10-02 | The Procter & Gamble Company | Skin-compatible hydrogel adhesives and personal care products containing them |
| WO2002078758A1 (en) * | 2001-03-30 | 2002-10-10 | The Procter & Gamble Company | Polymerized hydrogel adhesives |
| WO2002078757A1 (en) * | 2001-03-30 | 2002-10-10 | The Procter & Gamble Company | Skin-compatible hydrogel adhesives |
| WO2002078756A1 (en) * | 2001-03-30 | 2002-10-10 | The Procter & Gamble Company | Polymerized hydrogel adhesive |
| JP2006507370A (en) * | 2002-03-29 | 2006-03-02 | ザ プロクター アンド ギャンブル カンパニー | Hydrogel adhesive for use on surfaces occupied by hair or fibers |
| US8029824B2 (en) | 2002-05-01 | 2011-10-04 | National University Corporation Hokkaido University | Hydrogel of (semi) interpenetrating network structure and process for producing the same |
| EP1505093A4 (en) * | 2002-05-01 | 2008-09-10 | Hokkaido Tech Licensing Office | Hydrogel of (semi)interpenetrating network structure and process for producing the same |
| US8025696B2 (en) | 2004-06-18 | 2011-09-27 | National University Corporation Hokkaido University | Artificial meniscus and process of making thereof |
| JP2008522001A (en) * | 2004-12-03 | 2008-06-26 | スリーエム イノベイティブ プロパティズ カンパニー | Method for producing a pressure sensitive adhesive hydrogel |
| JP2009227924A (en) * | 2008-03-25 | 2009-10-08 | Sekisui Plastics Co Ltd | Adhesive hydrogel, composition for its manufacture and its use |
| JP2010215925A (en) * | 2010-06-21 | 2010-09-30 | Lintec Corp | Antibacterial adhesive product |
| US20130064982A1 (en) * | 2011-09-13 | 2013-03-14 | Chakravarthy S. Gudipati | Cation exchange materials prepared in aqueous media |
| CN103781810A (en) * | 2011-09-13 | 2014-05-07 | 通用电气公司 | Cation exchange materials prepared in aqueous media |
| JP2014526574A (en) * | 2011-09-13 | 2014-10-06 | ゼネラル・エレクトリック・カンパニイ | Cation exchange materials made in aqueous media |
| US9156933B2 (en) * | 2011-09-13 | 2015-10-13 | General Electric Company | Cation exchange materials prepared in aqueous media |
| TWI558457B (en) * | 2011-09-13 | 2016-11-21 | 奇異電器公司 | Cation exchange materials prepared in aqueous media |
| CN103781810B (en) * | 2011-09-13 | 2017-02-22 | 通用电气公司 | Cation exchange materials prepared in aqueous media |
| WO2013172292A1 (en) * | 2012-05-12 | 2013-11-21 | 国立大学法人北海道大学 | Aqueous gel |
| US9976000B2 (en) | 2012-05-12 | 2018-05-22 | National University Corp. Hokkaido University | Aqueous gel |
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