JPH01170682A - Water-swellable sealing material - Google Patents
Water-swellable sealing materialInfo
- Publication number
- JPH01170682A JPH01170682A JP62331289A JP33128987A JPH01170682A JP H01170682 A JPH01170682 A JP H01170682A JP 62331289 A JP62331289 A JP 62331289A JP 33128987 A JP33128987 A JP 33128987A JP H01170682 A JPH01170682 A JP H01170682A
- Authority
- JP
- Japan
- Prior art keywords
- water
- swellable
- sealing material
- resin
- urethane prepolymer
- 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
Links
- 239000003566 sealing material Substances 0.000 title claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000009257 reactivity Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000007795 chemical reaction product Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 9
- 229920001577 copolymer Polymers 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 3
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract 1
- 230000008961 swelling Effects 0.000 description 14
- 239000000565 sealant Substances 0.000 description 9
- 125000002843 carboxylic acid group Chemical group 0.000 description 7
- 239000013505 freshwater Substances 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical class CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NPERTKSDHFSDLC-UHFFFAOYSA-N ethenol;prop-2-enoic acid Chemical compound OC=C.OC(=O)C=C NPERTKSDHFSDLC-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業との利用分骨〉
本発明は、鉄製品やコンクリート製品等の止水に用いら
れろ水膨潤性のシーリング材に関するものである。[Detailed Description of the Invention] <Industrial Applications> The present invention relates to a water-swellable sealing material used for water-stopping iron products, concrete products, etc.
〈従来の技術とその問題点〉
従来から、軟質樹脂やゴム類に高吸水性樹脂を混合した
水膨潤性シーリング材は数多く知られているう
しかしながら、これらはいずれも機械的物性と膨潤率の
バランスが悪く、必ずしも、満足できるものがなかった
。<Conventional technologies and their problems> Many water-swellable sealants have been known that are made by mixing super absorbent resins with soft resins or rubbers. However, all of these have poor mechanical properties and swelling rates. It was unbalanced, and I wasn't always satisfied with it.
例えば、シーリング材の膨潤率を高くするため、高吸水
性樹脂を多く使用すると、該シーリング材のｍ満車は高
くなるが、膨潤後の機械的強度が極端に低下する。For example, if a large amount of superabsorbent resin is used to increase the swelling rate of the sealant, the m-fullness of the sealant will increase, but the mechanical strength after swelling will be extremely reduced.
一方、天然ゴムに水膨潤性ウレタンをグラフトしたもの
が知られているが、これは、真水と海水との膨潤率の差
はほとんどないが、膨潤率が低く、また止水に要する時
間が長い等止水性能に問題があった。On the other hand, natural rubber grafted with water-swellable urethane is known, but although there is almost no difference in swelling rate between fresh water and seawater, the swelling rate is low and it takes a long time to stop water. There was a problem with water stopping performance.
そこで本発明者らは、と記の問題点を解決するため、す
でに、水膨潤性ウレタンプレポリマー＾およびこれと反
応しうる高吸水性樹脂■を反応させたもの０を、軟質樹
脂またはゴム類に混合したものを用いる方法を提案した
（特願昭しかしながら、シーリング材の耐久性の点にお
いては、まだ不十分であった。Therefore, in order to solve the problems mentioned above, the present inventors have already developed a material 0 that has been reacted with a water-swellable urethane prepolymer ^ and a superabsorbent resin However, the durability of the sealant was still insufficient.
〈問題点を解決するための手段〉
本発明は、膨潤率と機械的強度のバランスがすぐれ、か
つ耐久性にもすぐれている水膨潤性シーリング材を提供
するものである。<Means for Solving the Problems> The present invention provides a water-swellable sealing material that has an excellent balance between swelling rate and mechanical strength, and also has excellent durability.
すなわち、水膨潤性ウレタンプレポリマー（５）および
これと反応しうる高吸水性樹脂■を反応させた（ｑと、
イソシアナート基との反応性を有する軟質樹脂またはゴ
ム類０との混合物を用いることを特徴とする水膨潤性シ
ーリング材である。That is, a water-swellable urethane prepolymer (5) and a superabsorbent resin (2) that can react with the water-swellable urethane prepolymer (5) were reacted (with q,
This is a water-swellable sealing material characterized by using a soft resin having reactivity with isocyanate groups or a mixture with zero rubbers.
本発明に使用されるイソシアナート基との反応性を有す
る軟質樹脂とは、（Ｃ）中のイソシアネート基と反応し
得る、水酸基、カルボン酸基、アンモニウム基、エポキ
シ基、スルフォン酸基等の官能基を分子中に含むもので
あり、例えば、水酸基をもつエチレン−酢酸ビニル共重
合体のケン化物、水酸基をもつエチレン−メタクリル酸
メチル共重合体のケン化物、−カルボキシル基をもつエ
チレン−アクリル酸共重合体、エポキシ基をもつエチレ
ン−グリシジルメタクリレート共重合体、カルボキシル
基をもつスチレン−イソブチレン−スチレンブロック共
重合体、カルボキシル基をもつスチレン−ブタジェン−
スチレンブロック共重合体などの各種の熱可塑性樹脂ま
たは熱可塑性エラストマーが挙げられる。The soft resin that is reactive with isocyanate groups used in the present invention refers to functional groups such as hydroxyl groups, carboxylic acid groups, ammonium groups, epoxy groups, and sulfonic acid groups that can react with the isocyanate groups in (C). Groups in the molecule, such as saponified ethylene-vinyl acetate copolymers with hydroxyl groups, saponified ethylene-methyl methacrylate copolymers with hydroxyl groups, ethylene-acrylic acid with carboxyl groups. copolymer, ethylene-glycidyl methacrylate copolymer with epoxy group, styrene-isobutylene-styrene block copolymer with carboxyl group, styrene-butadiene-with carboxyl group
Examples include various thermoplastic resins or thermoplastic elastomers such as styrene block copolymers.
また、イソシアナート基との反応性を有するゴム類とは
、Ｑ中のイソシアネート基と反応しうるカルボン酸基、
エポキシ基、スルフォン酸基等の官能基を分子中に含む
ものであり、天然ゴムまたは合成ゴムを化学変性して得
られるものである。In addition, rubbers having reactivity with isocyanate groups include carboxylic acid groups that can react with isocyanate groups in Q,
It contains functional groups such as epoxy groups and sulfonic acid groups in its molecules, and is obtained by chemically modifying natural rubber or synthetic rubber.
なお、軟質樹脂またはゴム類は、単独または併用して用
いることができる。Note that the soft resin or rubber can be used alone or in combination.
本発明に用いる水膨潤性ウレタンプレポリマー八として
は、好ましくはエチレンオキサイドとプロピレンオキサ
イドとの共重合体であるポリオキシアルキレングリコー
ルを有機ジイソシアネートと常法により反応せしめて得
られるプレポリマーが例示される。Examples of the water-swellable urethane prepolymer 8 used in the present invention include prepolymers obtained by reacting polyoxyalkylene glycol, which is preferably a copolymer of ethylene oxide and propylene oxide, with an organic diisocyanate in a conventional manner. .
本発明に用いられる水膨潤性ウレタンプレポリマー（ハ
）と反応しうる高吸水性樹脂とは、分子中１と水酸基、
カルボン酸基、スルフォン酸基等の券能基を含む高吸水
性樹脂であり、例えば、酢酸ビニル−アクリル酸メチル
共重合体のケン化物、イソブチレン−無水マレイン酸の
架橋物の塩およびその変性物（いずれもカルボン酸基を
含むもの）、ポリアクリル酸の架橋物の塩およびその変
性物（いずれもカルボン酸基を含むもの）、スチレン−
無水マレイン酸共重合体の架橋物の塩およびその変性物
（いずれもカルボン酸基を含むもの）などが具体例とし
てあげられるが、これらに限定されるものではなく、ま
たこれを１種または２種以上併用してもよい。The super absorbent resin that can react with the water-swellable urethane prepolymer (c) used in the present invention includes 1 and hydroxyl groups in the molecule,
A super absorbent resin containing functional groups such as carboxylic acid groups and sulfonic acid groups, such as saponified vinyl acetate-methyl acrylate copolymers, salts of isobutylene-maleic anhydride crosslinked products, and modified products thereof. (all containing carboxylic acid groups), salts of crosslinked polyacrylic acids and modified products thereof (all containing carboxylic acid groups), styrene-
Specific examples include salts of crosslinked maleic anhydride copolymers and modified products thereof (all containing carboxylic acid groups), but are not limited to these. More than one species may be used in combination.
なお、八と反応しうる高吸水性樹脂βのうち、融点を持
だな−）ものは、あらかじめ機械粉砕等により微粉にし
て用いるのが好ましく、その粒径は１００μ以下が好ま
しい。It should be noted that among the superabsorbent resins β that can react with 8, those having a melting point are preferably used in advance by being pulverized into fine powder by mechanical pulverization or the like, and the particle size thereof is preferably 100 μm or less.
また、本発明に用いられる水膨潤性ウレタンプレポリマ
ー八と高吸水性樹脂ｅを反応させたもの◎は、例えば八
と◎を機械的に混合するだけで得られる。Further, ◎, which is obtained by reacting water-swellable urethane prepolymer 8 and superabsorbent resin e used in the present invention, can be obtained, for example, by simply mixing 8 and ◎ mechanically.
この場合式と（ハ）を温合して得られる反応物◎は、ペ
ースト状となり、該反応物（Ｃ）は、通常の方法によっ
て、イソシアナート基との反応性を有する軟′Ｊｔ樹脂
またはゴム類急に容易に混合することができる。In this case, the reaction product ◎ obtained by heating the formula and (c) becomes a paste, and the reaction product (C) is converted into a soft Jt resin having reactivity with isocyanate groups or Rubbers can be quickly mixed easily.
（Ａ） ／ （Ｂ）の混合割合は使用目的によって決め
られ特に制限はないが、通常（Ａ）／■＝に２／１〜５
／１の範囲が好ましい。また八とβの反応物（Ｃ）の添
加割合も使用目的によって決められ特に制限はないが軟
′Ｒ樹脂またはゴム類０１００重量部に対して１０〜２
０Ｏｔｆｉ部が好ましく、さらに好ましくは３０〜１０
０重量部である。The mixing ratio of (A) / (B) is determined depending on the purpose of use and is not particularly limited, but usually (A) / ■ = 2/1 to 5
A range of /1 is preferred. Also, the addition ratio of the reactant (C) of 8 and β is determined depending on the purpose of use and is not particularly limited, but it is 10 to 2 parts by weight per 100 parts by weight of the soft R resin or rubber.
0 Otfi part is preferable, more preferably 30 to 10
It is 0 parts by weight.
一般に、水膨潤性シーリング材の膨潤率を大きくするた
めには、高吸水性ａ脂（ハ）の混合割合を多くし、かつ
、軟質樹脂やゴム類◎に対する添加割合を多くする必要
がある。また、ｗ？ｉｌｌ率を低くし、耐久性を重視す
る場合には、水膨潤性ポリウレタンプレポリマー（２）
の混合割合を多くし、かつ、軟質樹脂やゴム類０に対す
る添加割合は、前者の場合より少なくてもよい。Generally, in order to increase the swelling rate of a water-swellable sealant, it is necessary to increase the mixing ratio of highly water-absorbent A-fat (c) and the addition ratio to the soft resin or rubber ◎. Also, w? When lowering illumination rate and emphasizing durability, water-swellable polyurethane prepolymer (2)
The mixing ratio may be increased, and the addition ratio relative to the soft resin or rubber may be smaller than in the former case.
本発明の水膨潤性シーリング材には必要に応じて無機添
加剤を添加することができる。この−無機
色
添加剤は微粉砕されたものが好ましく、また件艶華、亜
鉛華、微粉シリカ、炭酸カルシウム、ソフトクレー、ベ
ントナイト等が好ましく、その他セメント類、石膏等も
使用できる。その他必要に応じて通常ゴム類の加硫に用
いられている加硫剤、加硫助剤、加硫促進剤、軟化剤、
可塑剤、カーボンブラック、着色剤、シランカップリン
グ剤、ラジカル発生剤など通常用いられているものを使
用することができる。Inorganic additives can be added to the water-swellable sealant of the present invention, if necessary. The inorganic color additive is preferably finely pulverized, and preferably includes porcelain, zinc white, finely divided silica, calcium carbonate, soft clay, bentonite, etc. Other cements, gypsum, etc. can also be used. Other vulcanizing agents, vulcanization aids, vulcanization accelerators, and softening agents that are normally used in the vulcanization of rubber, as required.
Commonly used plasticizers, carbon black, colorants, silane coupling agents, radical generators and the like can be used.
また、本発明の水膨潤性シーリング材は、通常行われて
いる公知の方法で容易に製造することができる。すなわ
ち、各種配合物質をロール、ニーダ−、バンバリーミキ
サ−１等通常の混練後を用いて混合、混練し、成形機と
しては、スクリュー式押出機、各種インジェクション、
プレス成形機、カレンダーロール、ロートキュアアー等
通常の各種成形機および加硫機が用いられる。Further, the water-swellable sealant of the present invention can be easily produced by a commonly used and known method. That is, various compounded materials are mixed and kneaded using a conventional kneading machine such as a roll, a kneader, or a Banbury mixer 1, and as a molding machine, a screw extruder, various injection machines, etc.
Various conventional molding machines and vulcanizers such as press molding machines, calendar rolls, rotocures, etc. are used.
〈実施例〉
つぎに、実施例を詳述するが、これら鍵実施例は単に、
例示的なものであって本発明はこれらに限定されるもの
ではない。<Example> Next, examples will be described in detail, but these key examples are simply:
These are merely illustrative and the present invention is not limited thereto.
参考例１
エチレンオキサイド／プロピレンオキサイドの共重合体
を有機ジイソシアネートと反応して得られた水膨潤性ウ
レタンプレポリマー（バンデノクス■ＴＰ−６５４、大
日本インキ工業製）１００重量部に対し、酢酸ビニル−
アクリル酸メチル共重合体のケン化物である高吸水性樹
脂（スミカゲル■５ｒ−５２０、住友化学工業製）（０
重量部を室温で混合し、ペースト状の反応物０を得た。Reference Example 1 Vinyl acetate-
Super water-absorbent resin (Sumikagel ■5r-520, manufactured by Sumitomo Chemical Industries), which is a saponified product of methyl acrylate copolymer (0
Parts by weight were mixed at room temperature to obtain a paste-like reaction product 0.
この反応物を、２０°Ｃの真水に１時間浸漬したところ
約１８０倍に膨潤し、また、真水に１週間浸漬しても両
者の脱離や溶解はほとんど認められなかった。When this reaction product was immersed in fresh water at 20°C for 1 hour, it swelled approximately 180 times, and even after being immersed in fresh water for 1 week, almost no desorption or dissolution of the two was observed.
参考例２
水膨潤性ウレタンプレポリマー（バンデックス■ＴＰ−
６５４、大日本インキ工業製）１００ｉ［１部に対し、
イソブチレン−無水マレイン酸の架橋物の塩の変性物で
あり、カルボン酸基を有する高吸水性樹脂（クラレＫｌ
ゲル２０１Ｋ、クラレ製）５０重量部を室温でよく混合
し、ペースト状の反応物◎を得た。Reference Example 2 Water-swellable urethane prepolymer (Vandex TP-
654, manufactured by Dainippon Ink Industries) 100i [for 1 part,
It is a modified salt of a crosslinked product of isobutylene-maleic anhydride, and is a highly water-absorbent resin having a carboxylic acid group (Kuraray Kl).
50 parts by weight of Gel 201K (manufactured by Kuraray) were thoroughly mixed at room temperature to obtain a paste-like reaction product ◎.
この反応物は、２０℃の真水に１時間浸漬した場合約１
２０倍に膨潤し、また真水に１週間浸漬しても両者の脱
離や溶解はほとんど認められなかった。When immersed in fresh water at 20°C for 1 hour, this reactant produces approximately 1
It swelled 20 times, and even after being immersed in fresh water for one week, almost no desorption or dissolution of the two was observed.
参考例８
市販の未変性天然ゴム（ＲＳ Ｓ ｇ ４ ） １００
重量部に、無水マレイン酸２重量部およびジクミルペル
オキシド０．２重量部を加え、ミキシングロールでよく
混練後、１８０″Ｃの熱オーブンに入れ８０分間処理し
て酸変性型天然ゴムを得た。Reference Example 8 Commercially available unmodified natural rubber (RS S g 4 ) 100
2 parts by weight of maleic anhydride and 0.2 parts by weight of dicumyl peroxide were added to the parts by weight, and after kneading well with a mixing roll, the mixture was placed in a heated oven at 180"C and treated for 80 minutes to obtain acid-modified natural rubber. .
実施例１
エチレン−酢酸ビニル−ビニルアルコール三元共重合体
（ＭＩ＝４０．ＶＡ＝８５％、０Ｈ＝５％）１００ｉ量
部に対し、参考例１で得たペースト状の反応物（０２０
重量部を加え、ミキシングロールでよく混練後、厚さ約
２ｍのシート状に成形した。Example 1 The paste-like reaction product obtained in Reference Example 1 (020
After adding parts by weight and thoroughly kneading with a mixing roll, the mixture was formed into a sheet with a thickness of about 2 m.
得られたシート（２部ｍｘ２０■×２ｔ）を用いて、物
性を測定するとともに２０’Ｃの真水に浸漬し、膨潤率
及び、その経時変化を求めた。得られた結果を表１に示
した。The obtained sheet (2 parts m x 20 cm x 2 tons) was used to measure the physical properties and was immersed in fresh water at 20'C to determine the swelling ratio and its change over time. The results obtained are shown in Table 1.
実施例２および８
表２に示す配合によりミキシングロールでよく混練した
のち、１２０″Ｃで６分間ゴム加硫プレスを用いて、実
施例１と同様にして、物性、膨潤率及びその経時変化を
求めた。Examples 2 and 8 After thoroughly kneading the formulation shown in Table 2 with a mixing roll, the physical properties, swelling ratio, and changes over time were evaluated in the same manner as in Example 1 using a rubber vulcanization press at 120"C for 6 minutes. I asked for it.
得られた結果を表８に示した。The results obtained are shown in Table 8.
比較例１
実施例１で用いたエチレン−酢酸ビニル−ビニルアルコ
ール三元共重合体に替えてエチレン−酢酸ビニル共重合
体（ＭＩ＝４０、ＶＡ＝４０％）１００を置部を用い、
参考例１で得たペースト状の反応物◎を２０に＠部を加
え、ミキシングロールでよく混線後、厚さ約２１１ｍ１
のシートを得た。得られたシートの物性、膨潤率及び、
その経時変化の値を表１に示した。Comparative Example 1 In place of the ethylene-vinyl acetate-vinyl alcohol terpolymer used in Example 1, 100 ethylene-vinyl acetate copolymer (MI = 40, VA = 40%) was used,
Add @ part of the paste-like reaction product ◎ obtained in Reference Example 1 to 20 and mix well with a mixing roll to form a mixture with a thickness of about 211 m1.
I got a sheet of Physical properties, swelling ratio, and
Table 1 shows the values of the changes over time.
比較例２および８
表２に示す配合により他は実施例２〜３と同様にしてプ
レスシートを得た。得られたシートの物性、ｗ？ＩＩ率
及び、その経時変化の直を表８に示す。Comparative Examples 2 and 8 Press sheets were obtained in the same manner as in Examples 2 to 3 except for the formulations shown in Table 2. Physical properties of the obtained sheet, w? Table 8 shows the II rate and its change over time.
なお、真水での膨潤率はつぎの式により求めた。The swelling ratio in fresh water was determined using the following formula.
Ａ−膨潤前の重さ（ｇ）
Ｂ＝膨潤後の重さくｙ）
表−２
〈発明の効果〉
以上の結果から明らかのように、比較例に比べ、本発明
による水膨潤性シーリング材は、機械的強度が高く、か
つ、長期水浸漬試験においても膨潤率の低下が少なく耐
久性にすぐれていた。A - Weight before swelling (g) B = Weight after swelling y) Table 2 <Effects of the invention> As is clear from the above results, compared to the comparative example, the water-swellable sealant according to the present invention , had high mechanical strength, and exhibited excellent durability with little decrease in swelling rate even in long-term water immersion tests.
また、本発明の方法によると、水膨潤性シーリング材か
らの水膨潤性ウレタンプレポリマーのブリードアウトに
よるセグメント等への接着性の低下も認められなかった
。Further, according to the method of the present invention, no decrease in adhesion to segments etc. due to bleed-out of the water-swellable urethane prepolymer from the water-swellable sealant was observed.
（以下余白）(Margin below)
Claims (1)
しうる高吸水性樹脂（Ｂ）を反応させたもの（Ｃ）と、
イソシアナート基との反応性を有する軟質樹脂またはゴ
ム類（Ｄ）との混合物を用いることを特徴とする水膨潤
性シーリング材。A product (C) obtained by reacting a water-swellable urethane prepolymer (A) and a superabsorbent resin (B) that can react with the same,
A water-swellable sealing material characterized by using a mixture with a soft resin or rubber (D) having reactivity with isocyanate groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62331289A JP2604613B2 (en) | 1987-12-26 | 1987-12-26 | Water-swellable sealing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62331289A JP2604613B2 (en) | 1987-12-26 | 1987-12-26 | Water-swellable sealing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01170682A true JPH01170682A (en) | 1989-07-05 |
| JP2604613B2 JP2604613B2 (en) | 1997-04-30 |
Family
ID=18242023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62331289A Expired - Lifetime JP2604613B2 (en) | 1987-12-26 | 1987-12-26 | Water-swellable sealing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2604613B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120653A (en) * | 1982-12-27 | 1984-07-12 | Sumitomo Chem Co Ltd | Water-absorptive and water-retaining material |
| JPS59164332A (en) * | 1983-03-10 | 1984-09-17 | Saitama Gomme Kogyo Kk | Production of water-swellable water-stopping agent |
| JPS6042416A (en) * | 1983-08-17 | 1985-03-06 | Kao Corp | Production of polyurethane resin excellent in water absorption and water retention |
| JPS62256884A (en) * | 1986-04-30 | 1987-11-09 | C I Kasei Co Ltd | Water-swelling waterproofing material |
-
1987
- 1987-12-26 JP JP62331289A patent/JP2604613B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120653A (en) * | 1982-12-27 | 1984-07-12 | Sumitomo Chem Co Ltd | Water-absorptive and water-retaining material |
| JPS59164332A (en) * | 1983-03-10 | 1984-09-17 | Saitama Gomme Kogyo Kk | Production of water-swellable water-stopping agent |
| JPS6042416A (en) * | 1983-08-17 | 1985-03-06 | Kao Corp | Production of polyurethane resin excellent in water absorption and water retention |
| JPS62256884A (en) * | 1986-04-30 | 1987-11-09 | C I Kasei Co Ltd | Water-swelling waterproofing material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2604613B2 (en) | 1997-04-30 |
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