JPH08245801A - Crosslinking agent - Google Patents
Crosslinking agentInfo
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- JPH08245801A JPH08245801A JP34880495A JP34880495A JPH08245801A JP H08245801 A JPH08245801 A JP H08245801A JP 34880495 A JP34880495 A JP 34880495A JP 34880495 A JP34880495 A JP 34880495A JP H08245801 A JPH08245801 A JP H08245801A
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- water
- crosslinking agent
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- salt
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水溶性ビニルモノ
マー用架橋剤に関するものであり、詳しくは、新規な架
橋ポリマーを与える水溶性ビニルモノマー用架橋剤に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinking agent for a water-soluble vinyl monomer, and more particularly to a crosslinking agent for a water-soluble vinyl monomer which gives a novel crosslinked polymer.
【０００２】[0002]
【従来の技術】水溶性ビニルモノマーは、ビニル基によ
る重合性と親水基による水溶性を活かし、その単独の線
状ポリマーは、各種の用途に利用されている。例えば、
アクリル酸アミドから得られるポリアクリルアミドは、
代表的な水溶性ポリマーであり、凝集剤、紙力増強剤、
増粘剤などとして利用されている。2. Description of the Related Art A water-soluble vinyl monomer utilizes the polymerizability of a vinyl group and the water solubility of a hydrophilic group, and a single linear polymer is used for various purposes. For example,
Polyacrylamide obtained from acrylamide,
Representative water-soluble polymer, flocculant, paper strength agent,
It is used as a thickener.
【０００３】ところで、水溶性ビニルモノマーを架橋し
て得られる３次元ポリマーは、その水不溶性と親水基に
よる機能を活かして例えばイオン交換樹脂などとしての
用途が期待されるが、未だ、共重合性を含めて満足し得
る架橋剤は提案されていない様である。A three-dimensional polymer obtained by crosslinking a water-soluble vinyl monomer is expected to be used as, for example, an ion-exchange resin by utilizing its water-insolubility and the function of a hydrophilic group. It seems that no satisfactory cross-linking agent has been proposed.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記実情に
鑑みなされたものであり、その目的は、新規な架橋ポリ
マーを与える水溶性ビニルモノマー用架橋剤を提供する
ことにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a crosslinking agent for a water-soluble vinyl monomer which gives a novel crosslinked polymer.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明の要旨
は、ジアリルイソシアヌレート塩から成ることを特徴と
する水溶性ビニルモノマー用架橋剤に存する。That is, the gist of the present invention resides in a crosslinking agent for a water-soluble vinyl monomer, comprising a diallyl isocyanurate salt.
【０００６】以下、本発明を詳細に説明する。本発明に
おいて、架橋剤として好適に使用されるジアリルイソシ
アヌレート塩は、次の一般式で表される。Hereinafter, the present invention will be described in detail. In the present invention, a diallyl isocyanurate salt suitably used as a crosslinking agent is represented by the following general formula.
【０００７】[0007]
【化１】 Embedded image
【０００８】上記の一般式中、Ｍは、一価の金属、例え
ば、Ｌｉ、Ｎａ、Ｋなどを表す。好適な一価の金属はＮ
ａである。In the above general formula, M represents a monovalent metal, for example, Li, Na, K and the like. Preferred monovalent metals are N
a.
【０００９】本発明において、ジアリルイソシアヌレー
ト塩は、金属に対してジアリルイソシアヌレート単位が
２個以上結合した塩であってもよい。例えば、二価の金
属としては、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃ
ｄなどが挙げられる。In the present invention, the diallyl isocyanurate salt may be a salt in which two or more diallyl isocyanurate units are bonded to a metal. For example, as the divalent metal, Be, Mg, Ca, Sr, Ba, Zn, C
d and the like.
【００１０】本発明で使用するジアリルイソシアヌレー
ト塩は、その塩型のため水溶性である。最も好ましいジ
アリルイソシアヌレート塩は、ジアリルイソシアヌレー
トＮａ塩である。The diallyl isocyanurate salt used in the present invention is water-soluble because of its salt form. The most preferred diallyl isocyanurate salt is diallyl isocyanurate Na salt.
【００１１】ジアリルイソシアヌレートの一価の金属塩
は、例えば、ジアリルイソシアヌレートと金属水酸化物
の水溶液との中和反応により、また、ジアリルイソシア
ヌレートの二価の金属塩は、例えば、一価の金属塩と二
価の金属塩化物との複分解反応により、容易に得ること
が出来る。The monovalent metal salt of diallyl isocyanurate can be produced, for example, by a neutralization reaction of diallyl isocyanurate with an aqueous solution of a metal hydroxide, and the divalent metal salt of diallyl isocyanurate can be produced, for example, by monovalent metal salt. Can be easily obtained by a metathesis reaction between a metal salt of the above and a divalent metal chloride.
【００１２】本発明の架橋剤が適用される水溶性ビニル
モノマーは、特に限定されないが、好適な水溶性ビニル
モノマーとしては、ジアリル四級アンモニウム塩、（メ
タ）アクリル酸、（メタ）アクリル酸エステル、（メ
タ）アクリル酸アミド、ビニルピロリドンの群から選択
された１種である。ここに、「（メタ）アクリル酸」の
用語は、アクリル酸およびメタクリル酸の総称を意味す
る。The water-soluble vinyl monomer to which the crosslinking agent of the present invention is applied is not particularly limited, but preferred water-soluble vinyl monomers include diallyl quaternary ammonium salts, (meth) acrylic acid, and (meth) acrylic acid esters. , (Meth) acrylamide and vinylpyrrolidone. Here, the term “(meth) acrylic acid” means a general term for acrylic acid and methacrylic acid.
【００１３】上記の各モノマーは、イオン性基、水酸
基、アミド基、アミノ基の様に水との強い相互作用を有
する官能基（特性基）を分子中に有しているため、水溶
性である。本発明において、「水溶性」の程度は、任意
の割合の水と相互溶解する程に大きくなくてもよい。何
故ならば、水に対して少量でも溶解し得れば、溶解した
モノマーから順次に架橋反応が生起するからである。し
かしながら、本発明においては、通常、水に対する溶解
度（２０℃）が１．５重量％以上の水溶性ビニルモノマ
ーが好適に使用される。Each of the above-mentioned monomers has a functional group (characteristic group) having strong interaction with water, such as an ionic group, a hydroxyl group, an amide group, and an amino group, in the molecule. is there. In the present invention, the degree of “water solubility” does not have to be so great as to be mutually soluble with any proportion of water. This is because, if a small amount can be dissolved in water, a crosslinking reaction occurs sequentially from the dissolved monomer. However, in the present invention, usually, a water-soluble vinyl monomer having a solubility in water (20 ° C.) of 1.5% by weight or more is preferably used.
【００１４】ジアリル四級アンモニウム塩において、２
個のアリル以外の他の置換基としては、メチル基、エチ
ル基、プロピル基、ラウリル基、ステアリル基などの各
種アルキル基、ベンジル基などが挙げられる。ジアリル
四級アンモニウム塩代表例としては、ジアリルジメチル
アンモニウムクロライドが挙げられる。（メタ）アクリ
ル酸エステルの具体例としては、メチル（メタ）アクリ
レート、エチルアクリレート、エチレングリコールジ
（メタ）アクリレート、ジエチレングリコールジ（メ
タ）アクリレート、２−ヒドロキシエチル（メタ）アク
リレート、２−ヒドロキシプロピル（メタ）アクリレー
ト、２−ヒドロキシブチル（メタ）アクリレート、２−
（メタ）アクリロイルオキシエチルトリメチルアンモニ
ウムクロライド等が挙げられる。特に好ましい（メタ）
アクリル酸エステルは、ヒドロキシアルキル（メタ）ア
クリレート類である。In the diallyl quaternary ammonium salt, 2
Examples of the substituent other than allyl include various alkyl groups such as a methyl group, an ethyl group, a propyl group, a lauryl group, and a stearyl group, and a benzyl group. Representative examples of diallyl quaternary ammonium salts include diallyl dimethyl ammonium chloride. Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-
(Meth) acryloyloxyethyltrimethylammonium chloride and the like. Particularly preferred (meta)
Acrylic esters are hydroxyalkyl (meth) acrylates.
【００１５】その他の水溶性ビニルモノマーの具体例と
しては、Ｎ，Ｎ−ジメチルアクリルアミド、アクリロイ
ルモルフォリン等が挙げられ、更には、アミン変性、カ
ルボン酸変性、ヒドロキシル変性、エーテル変性した各
種のビニルモノマーが挙げられる。Specific examples of other water-soluble vinyl monomers include N, N-dimethylacrylamide, acryloylmorpholine, and the like. Furthermore, various vinyl monomers modified with an amine, a carboxylic acid, a hydroxyl, and an ether are used. Is mentioned.
【００１６】本発明の架橋剤が適用される最も好ましい
水溶性ビニルモノマーは、次の化学式で表されるジアリ
ルジメチルアンモニウムクロライドである。ジアリルジ
メチルアンモニウムクロライドは、その４級チッソに基
づくイオン性基によって水溶性である。Ｘ- （対イオ
ン）は、通常、Ｃｌ、Ｂｒ等のハロゲン化物イオンであ
る。The most preferred water-soluble vinyl monomer to which the crosslinking agent of the present invention is applied is diallyldimethylammonium chloride represented by the following chemical formula. Diallyldimethylammonium chloride is water-soluble due to its quaternary nitrogen-based ionic groups. X - (counterion) is typically, Cl, Br, etc. halide ions.
【００１７】[0017]
【化２】 Embedded image
【００１８】本発明のジアリルイソシアヌレート塩から
成る架橋剤は、通常、２個または４個のアリル基に基づ
いて２官能または４官能の架橋剤として作用し、水溶性
ビニルモノマーを架橋ポリマー（３次元ポリマー）に変
換する。架橋反応は、公知の水溶性モノマーの共重合反
応に従って行うことが出来る。例えば、重合開始剤とし
ては、２，２−アゾビス［２−メチル−Ｎ−（２−ヒド
ロキシエチル）プロピオンアミド］（ＶＡ−８６）等の
水溶性アゾ系開始剤などを使用することが出来る。The crosslinking agent comprising the diallyl isocyanurate salt of the present invention usually acts as a bifunctional or tetrafunctional crosslinking agent based on two or four allyl groups to convert a water-soluble vinyl monomer into a crosslinked polymer (3). Dimensional polymer). The crosslinking reaction can be performed according to a known copolymerization reaction of a water-soluble monomer. For example, as the polymerization initiator, a water-soluble azo initiator such as 2,2-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (VA-86) can be used.
【００１９】本発明の架橋剤の使用量は、目的とする架
橋ポリマーの種類により広範囲から選択し得るが、水溶
性ビニルモノマーに対し、通常０．１〜１００モル％、
好ましくは１〜５０モル％の範囲から選択される。そし
て、架橋剤の使用割合により、枝分かれした水溶性分岐
ポリマー、高膨潤性架橋ポリマー、低膨潤性架橋ポリマ
ー等を得ることが出来る。そして、その架橋の程度によ
り、凝集剤、吸水性ポリマー、イオン交換樹脂などの用
途に使用することが期待される。The amount of the crosslinking agent used in the present invention can be selected from a wide range depending on the kind of the desired crosslinked polymer, but is usually 0.1 to 100 mol% based on the water-soluble vinyl monomer.
Preferably it is selected from the range of 1 to 50 mol%. Then, depending on the usage ratio of the crosslinking agent, a branched water-soluble branched polymer, a highly swellable crosslinked polymer, a low swellable crosslinked polymer, or the like can be obtained. Then, depending on the degree of crosslinking, it is expected to be used for applications such as flocculants, water-absorbing polymers, and ion-exchange resins.
【００２０】本発明の架橋剤によれば、従来、高分子量
の重合が困難とされていたジアリル四級アンモニウム塩
から水不溶性の３次元ポリマーのみならず任意の高分子
量の水溶性分岐ポリマーを得ることが出来る。According to the crosslinking agent of the present invention, not only a water-insoluble three-dimensional polymer but also a water-soluble branched polymer having an arbitrary high molecular weight can be obtained from diallyl quaternary ammonium salt, which has been conventionally difficult to polymerize. I can do it.
【００２１】[0021]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明は、その要旨を超えない限り、以下の実
施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
【００２２】比較例１及び２ ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡ
Ｃ）と公知の架橋剤であるテトラアリルアンモニウムク
ロライド（ＴＡＡＣ）のモル比（ＤＡＤＭＡＣ／ＴＡＡ
Ｃ）を９０／１０（比較例１）、７０／３０（比較例
２）となる様に設定し、開始剤としてＶＡ−８６を使用
し、全モノマー濃度２Ｍ、開始剤濃度０．０５Ｍ、温度
８０℃の条件下に水系の共重合を行った。次いで、重合
液をアセトン中に投入してポリマーを沈殿せしめ、得ら
れたポリマーをメタノール・アセトン系にて再沈精製し
た後、水抽出法によりゾルとゲルとを分離した。Comparative Examples 1 and 2 Diallyldimethylammonium chloride (DADMA
C) and the molar ratio of a known crosslinking agent, tetraallylammonium chloride (TAAC) (DADMAC / TAA)
C) was set to 90/10 (Comparative Example 1) and 70/30 (Comparative Example 2), VA-86 was used as an initiator, the total monomer concentration was 2 M, the initiator concentration was 0.05 M, and the temperature was Aqueous copolymerization was carried out at 80 ° C. Next, the polymerization liquid was poured into acetone to precipitate the polymer, and the obtained polymer was purified by reprecipitation in a methanol / acetone system, and then the sol and the gel were separated by a water extraction method.
【００２３】上記の各実施例で得られた架橋ポリマーゲ
ルの膨潤比を測定した結果、膨潤比は同程度であった。
これは、ＤＡＤＭＡＣと架橋剤（ＴＡＡＣ）とが何れも
カチオン性のモノマーであるためによる静電反発によ
り、分子内の架橋反応が阻害されていることによるもの
と推定される。As a result of measuring the swelling ratio of the crosslinked polymer gel obtained in each of the above Examples, the swelling ratio was almost the same.
This is presumed to be due to the fact that both the DADMAC and the cross-linking agent (TAAC) are cationic monomers, thereby inhibiting the intramolecular cross-linking reaction due to electrostatic repulsion.
【００２４】比較例３ ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡ
Ｃ）と公知の架橋剤であるジアリルイソシアヌレート
（ＤＡＩＣ）のモル比（ＤＡＤＭＡＣ／ＤＡＩＣ）を９
５／５となる様に設定し、開始剤としてＶＡ−８６を使
用し、全モノマー濃度２Ｍ、開始剤濃度０．０５Ｍ、温
度８０℃の条件下に水系の共重合を試みたが、ＤＡＩＣ
が水に溶解しないため、架橋反応は殆ど生起しなかっ
た。Comparative Example 3 Diallyldimethylammonium chloride (DADMA)
C) and a known crosslinking agent diallyl isocyanurate (DAIC) in a molar ratio (DADMAC / DAIC) of 9
5/5, VA-86 was used as an initiator, and aqueous copolymerization was attempted under the conditions of a total monomer concentration of 2M, an initiator concentration of 0.05M, and a temperature of 80 ° C.
Did not dissolve in water, so that the crosslinking reaction hardly occurred.
【００２５】実施例１〜３ ジアリルジメチルアンモニウムクロライド（ＤＡＤＭＡ
Ｃ）と本発明の架橋剤であるジアリルイソシアヌレート
Ｎａ塩（ＳＤＡＩＣ）のモル比（ＤＡＤＭＡＣ／ＳＤＡ
ＩＣ）を９５／５（実施例１）、９０／１０（実施例
２）、７０／３０（実施例３）となる様に設定し、開始
剤としてＶＡ−８６を使用し、全モノマー濃度２Ｍ、開
始剤濃度０．０５Ｍ、温度８０℃の条件下に水系の共重
合を行った。次いで、重合液をアセトン中に投入してポ
リマーを沈殿せしめ、得られたポリマーをメタノール・
アセトン系にて再沈精製した後、水抽出法によりゾルと
ゲルとを分離した。Examples 1 to 3 Diallyldimethylammonium chloride (DADMA)
C) and the molar ratio of diallyl isocyanurate Na salt (SDAIC) which is a crosslinking agent of the present invention (DADMAC / SDA)
IC) was set to be 95/5 (Example 1), 90/10 (Example 2), 70/30 (Example 3), VA-86 was used as an initiator, and the total monomer concentration was 2M. Aqueous copolymerization was carried out under the conditions of an initiator concentration of 0.05M and a temperature of 80 ° C. Next, the polymerization solution was poured into acetone to precipitate the polymer, and the obtained polymer was dissolved in methanol.
After reprecipitation purification in an acetone system, the sol and the gel were separated by a water extraction method.
【００２６】上記の各実施例で得られた架橋ポリマーゲ
ルの膨潤比を測定した結果、膨潤比は、架橋剤の使用割
合の増加と共に減少していた。このことは、本発明の架
橋剤であるジアリルイソシアヌレートＮａ塩（ＳＤＡＩ
Ｃ）がアニオン性であるため、分子間架橋反応および分
子内架橋反応とも活発に生起し、使用したＳＤＡＩＣが
架橋反応に十分に寄与していることによるものと推定さ
れる。As a result of measuring the swelling ratio of the crosslinked polymer gel obtained in each of the above Examples, it was found that the swelling ratio decreased with an increase in the use ratio of the crosslinking agent. This indicates that the cross-linking agent of the present invention, diallyl isocyanurate Na salt (SDAI)
Since C) is anionic, it is presumed that both the intermolecular crosslinking reaction and the intramolecular crosslinking reaction actively occur, and that the SDAIC used sufficiently contributes to the crosslinking reaction.
【００２７】実施例４ Ｎ−ビニルピロリドン（ＶＰ）と本発明の架橋剤である
ジアリルイソシアヌレートＮａ塩（ＳＤＡＩＣ）のモル
比（ＶＰ／ＳＤＡＩＣ）を９０／１０となる様に設定
し、開始剤としてＶＡ−８６を使用し、全モノマー濃度
２Ｍ、開始剤濃度０．００５Ｍ、温度７０℃の条件下に
水系の共重合を行った。次いで、重合液をアセトン中に
投入してポリマーを沈殿せしめ、得られたポリマーをア
セトンで数回洗浄した後、水抽出法によりゾルとゲルと
を分離した。本実施例においては次の反応成績が得られ
た。Example 4 The molar ratio (VP / SDAIC) of N-vinylpyrrolidone (VP) and diallyl isocyanurate Na salt (SDAIC), which is a crosslinking agent of the present invention, was set to be 90/10, and the initiator was set. Was used, and aqueous copolymerization was carried out under the conditions of a total monomer concentration of 2M, an initiator concentration of 0.005M, and a temperature of 70 ° C. Next, the polymerization solution was poured into acetone to precipitate the polymer. The obtained polymer was washed with acetone several times, and then the sol and the gel were separated by a water extraction method. In this example, the following reaction results were obtained.
【００２８】[0028]
【表１】 [Table 1]
【００２９】実施例５ Ｎ−ビニルピロリドン（ＶＰ）と本発明の架橋剤である
ジアリルイソシアヌレートＣａ塩（ＣＤＡＩＣ）のモル
比（ＶＰ／ＣＤＡＩＣ）を９５／５となる様に設定し、
開始剤としてＶＡ−８６を使用し、全モノマー濃度０．
５Ｍ、開始剤濃度０．００３Ｍ、温度７０℃の条件下に
水系の共重合を行った。次いで、重合液をアセトン中に
投入してポリマーを沈殿せしめ、得られたポリマーをア
セトンで数回洗浄した後、水抽出法によりゾルとゲルと
を分離した。本実施例においては次の反応成績が得られ
た。Example 5 The molar ratio (VP / CDAIC) of N-vinylpyrrolidone (VP) and diallyl isocyanurate Ca salt (CDAIC), which is a crosslinking agent of the present invention, was set to be 95/5.
VA-86 was used as the initiator and the total monomer concentration was 0.
Aqueous copolymerization was carried out under the conditions of 5M, initiator concentration of 0.003M and temperature of 70 ° C. Next, the polymerization solution was poured into acetone to precipitate the polymer. The obtained polymer was washed several times with acetone, and then the sol and the gel were separated by a water extraction method. In this example, the following reaction results were obtained.
【００３０】[0030]
【表２】 [Table 2]
【００３１】実施例６ アクリルアミド（ＡＡＭ）と本発明の架橋剤であるジア
リルイソシアヌレートＮａ塩（ＳＤＡＩＣ）のモル比
（ＡＡＭ／ＳＤＡＩＣ）を９０／１０となる様に設定
し、開始剤としてＶＡ−８６を使用し、全モノマー濃度
２Ｍ、開始剤濃度０．０１６Ｍ、温度５０℃の条件下に
水系の共重合を行った。次いで、重合液をアセトン中に
投入してポリマーを沈殿せしめ、得られたポリマーをア
セトンで数回洗浄した後、水抽出法によりゾルとゲルと
を分離した。本実施例においては次の反応成績が得られ
た。Example 6 The molar ratio (AAM / SDAIC) of acrylamide (AAM) and diallyl isocyanurate Na salt (SDAIC), which is a crosslinking agent of the present invention, was set to 90/10, and VA- was used as an initiator. Using 86, aqueous copolymerization was carried out under the conditions of a total monomer concentration of 2 M, an initiator concentration of 0.016 M, and a temperature of 50 ° C. Next, the polymerization solution was poured into acetone to precipitate the polymer. The obtained polymer was washed with acetone several times, and then the sol and the gel were separated by a water extraction method. In this example, the following reaction results were obtained.
【００３２】[0032]
【表３】 [Table 3]
【００３３】[0033]
【発明の効果】以上説明した本発明によれば、新規な機
能性架橋ポリマーを与える水溶性ビニルモノマー用架橋
剤が提供され、本発明は、凝集剤、吸水性ポリマー、イ
オン交換樹脂などの分野に寄与するところが大きい。According to the present invention described above, a cross-linking agent for a water-soluble vinyl monomer which provides a novel functional cross-linked polymer is provided. The present invention relates to a field of a flocculant, a water-absorbing polymer, an ion exchange resin and the like. It greatly contributes to
───────────────────────────────────────────────────── フロントページの続き (72)発明者 取溜 博之 福島県いわき市小名浜字高山34番地 日本 化成株式会社研究所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Toritori 34 Takayama, Onahama, Iwaki-shi, Fukushima Japan Chemical Research Laboratory
Claims (3)
とを特徴とする水溶性ビニルモノマー用架橋剤。1. A crosslinking agent for a water-soluble vinyl monomer, comprising a diallyl isocyanurate salt.
アンモニウム塩、（メタ）アクリル酸、（メタ）アクリ
ル酸エステル、（メタ）アクリル酸アミド、ビニルピロ
リドンの群から選択された１種である請求項１に記載の
架橋剤。2. The water-soluble vinyl monomer is one selected from the group consisting of diallyl quaternary ammonium salts, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and vinylpyrrolidone. Item 4. The crosslinking agent according to Item 1.
アンモニウム塩である請求項１に記載の架橋剤。3. The crosslinking agent according to claim 1, wherein the water-soluble vinyl monomer is a diallyl quaternary ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34880495A JP3577152B2 (en) | 1995-01-11 | 1995-12-19 | Crosslinking agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1871095 | 1995-01-11 | ||
| JP7-18710 | 1995-01-11 | ||
| JP34880495A JP3577152B2 (en) | 1995-01-11 | 1995-12-19 | Crosslinking agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08245801A true JPH08245801A (en) | 1996-09-24 |
| JP3577152B2 JP3577152B2 (en) | 2004-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34880495A Expired - Fee Related JP3577152B2 (en) | 1995-01-11 | 1995-12-19 | Crosslinking agent |
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| Country | Link |
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| JP (1) | JP3577152B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005115534A1 (en) * | 2004-05-26 | 2005-12-08 | Tokuyama Corporation | Iontophoresis apparatus |
| JP2011525704A (en) * | 2008-06-24 | 2011-09-22 | ゼネラル・エレクトリック・カンパニイ | Supercapacitor and manufacturing method thereof |
-
1995
- 1995-12-19 JP JP34880495A patent/JP3577152B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005115534A1 (en) * | 2004-05-26 | 2005-12-08 | Tokuyama Corporation | Iontophoresis apparatus |
| JP2011525704A (en) * | 2008-06-24 | 2011-09-22 | ゼネラル・エレクトリック・カンパニイ | Supercapacitor and manufacturing method thereof |
| US9233860B2 (en) | 2008-06-24 | 2016-01-12 | General Electric Company | Supercapacitor and method for making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3577152B2 (en) | 2004-10-13 |
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