JPH052704B2 - - Google Patents
Info
- Publication number
- JPH052704B2 JPH052704B2 JP59092048A JP9204884A JPH052704B2 JP H052704 B2 JPH052704 B2 JP H052704B2 JP 59092048 A JP59092048 A JP 59092048A JP 9204884 A JP9204884 A JP 9204884A JP H052704 B2 JPH052704 B2 JP H052704B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- swellable
- rubber
- substance
- parts
- 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.)
- Expired - Lifetime
Links
- 239000000126 substance Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- 239000011396 hydraulic cement Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 description 26
- 239000005060 rubber Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- -1 carboxylic acid imides Chemical class 0.000 description 7
- 239000004568 cement Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000768 polyamine Chemical class 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- SCBKKGZZWVHHOC-UHFFFAOYSA-N 2,2-bis(sulfanyl)propanoic acid Chemical compound CC(S)(S)C(O)=O SCBKKGZZWVHHOC-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- HSMAVZYQDXUJLK-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C)C HSMAVZYQDXUJLK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 description 1
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical class O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は水膨潤性組成物に関し、特に水を吸収
して膨脹た後、乾燥しても収縮が少ない水膨潤性
組成物に関するものである。
〔従来技術及び問題点〕
従来、水膨潤性シール材としては、ポリアクリ
ル酸ソーダ、でんぷん、カルボキシメチルセルロ
ース、ポリエチレングライコール等の吸水物質を
ゴム或いはプラスチツク等に添加して水膨潤性を
付与したものが使用されているが、これらはいず
れも乾燥すると殆んどもとの状態まで収縮してし
まう。又、これらの水膨潤性シール材は、上記吸
水物質が水溶性で溶出してしまうため次第に水膨
潤割合が落ちてくる。
更に、これらの水膨潤性シール材は、海水に接
すると淡水に比較して半分以下の膨脹しか得られ
ない。
〔問題点を解決するための手段〕
本発明は上記問題点を改良した新規水膨潤性組
成物を提供するものである。
本発明の水膨潤性組成物は、必須成分として水
膨潤性ウレタン樹脂（）と水硬性物質（）と
を含有するものである。
本発明に使用する上記ウレタン樹脂としては、
水硬性物質と混合する際ペースト状のものあるい
はエラストマーが好ましいが、特にペースト状の
ものが好ましい。
ペースト状水膨潤ポリウレタン樹脂としては末
端イソシアネート基含有水膨潤性ポリウレタンプ
レポリマーと水及び／又は硬化剤の反応によつて
得られる樹脂がある。
該末端イソシアネート基含有水膨潤性ポリウレ
タンプレポリマーとしては例えば水酸基当量が
400〜6000のエチレンオキサイド・プロピレンオ
キサイドランダム／ブロツク重合ポリオキシアル
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ロピレンオキサイ
ド／エチレンオキサイド比７／３〜０／10のプレ
ポリマーが挙げられる。
該プレポリマーは水又はアミン系、ポリオール
系等の硬化剤によつて常法により部分的に硬化さ
れ、ペースト状態の水膨潤性ポリウレタン樹脂と
することができる。硬化は水と硬化剤を併用して
行なつてもよい。硬化剤としては４，4′−メチレ
ン−ビス−２−クロルアニリン、１，４−ブタン
ジオール、ハイドロキノン−ビス−（β−ヒドロ
キシ）エーテル、レゾルシノール−ビス−（β−
ヒドロキシ）エーテル、１，２−ビス−（２−ア
ミノフエノールチオ）エタン、トリメチレングリ
コール・ジ−ｐ−アミノベンゾエート等を単独な
いし併用して用いることができる。
ここに通常吸水性樹脂と称されているものとし
ては、カルボキシル基、カルボン酸塩、カルボン
酸アミド、カルボン酸イミド、カルボン酸無水物
等のカルボキシル基またはカルボキシル基に誘導
しうる基を分子内に１個もしくは２個有するα，
β−不飽和化合物を主成分とし、必要に応じてそ
の他のα，β−不飽和化合物を加え重合させたも
の或は更にこれらをイソシアネート類等で変性し
たものがあげられる。
このような吸水性樹脂としては、デンプン／ア
クリル酸グラフト共重合体、スチレン−無水マレ
イン酸共重合体の塩、ポリアクリル酸ソーダの架
橋物、ポリビニルアルコール／無水マレイン酸反
応体の架橋物、ビニルエステル／エチレン系不飽
和カルボン酸またはその誘導体のケン化物などの
公知の高吸水性高分子をあげることができる。
又、本発明に於いて、水硬化性物質（）とし
ては、水硬性セメントが好ましくその他石コウ、
潜在水硬性物質も使用できる。又、水硬性物質に
セメント系急硬剤を添加するのが更に好ましい。
ここで水硬性セメントとしては、普通、白色、
早強等の各種ポルトランドセメント、高炉セメン
ト等の特殊セメント或は粒子径で分類されたコロ
イドセメント等を適宜用いることができる。
セメント系急硬剤としては、カルシウムアルミ
ネート系無機物、即ち3CaO・Al2O3、CaO・
Al2O3、12CaO・7Al2O3、CaO・2Al2O3、CaO・
6Al2O3等のCaOとAl2O3の焼成物、熔融混合物、
或はこれに石コウ等を混合したカルシウムスルホ
アルミネート等を挙げることができ、市販品とし
てはデンカES（電気化学(株)商品名）などが挙げら
れる。
水膨潤性物質（）の含有量は、水膨潤性組成
物から得られる成形品の水膨潤率が10〜350（容
量）％となる様な量が好ましく、40〜250（容量）
％となる様な量が更に好ましい。特に水膨潤性物
質（）が水膨潤ウレタン樹脂の場合、ゴムを併
用するのが好ましく、ゴム100部（重量基準、以
下同じ）に対し水膨潤ウレタン樹脂20〜250部特
に60〜180部を用いるのが好ましい。
このようなゴムを併用することにより、本組成
物の物性、特に強度を向上させることができる。
本発明に用いられるゴムとしては天然ゴム、合
成ゴム又は再生ゴムがあり、例えば天然ゴム、ス
チレンブタジエンゴム、イソプレンゴム、アクリ
ロニトリルブタジエンゴム、クロロプレンゴム、
エチレンプロピレンターポリマー、ブチルゴムと
それらの再生ゴムなどのうちから用途及び目的に
よつて選択される。
本発明においては、また上記ゴムにかえ、ある
いはゴムとともにエラストマーを使用でき、この
ようなエラストマーとしては、ポリウレタン、ポ
リオレフイン、ポリスチレン等がある。
さらに本発明の組成物は無機添加物を含有する
ことができる。無機添加物としては、ゴムに添加
される様に微粉砕されたものが好ましく、白艶
華、亜鉛華、微粉シリカ、炭酸マグネシウム等が
好ましく、その他ベントナイト、粘土、その他の
珪酸カルシウム、アルミナ、チヨーク等も添加で
きる。その他目的に応じて、ガラスミクロ球、ガ
ラス繊維、炭素繊維等の充填剤も適当量配合して
用いることも可能である。
このような無機添加物を添加することにより、
本組成物の混合性、成形性を容易にするか、或い
は成形品の物性、特に強度、弾力性等を良好にす
ることが出来る。
水硬性物質（）の含有量は、本発明の水膨潤
性組成物の成形品の水膨潤率及び物性との関係で
適宜選択できるが、水膨潤性物質（）及びゴム
等が添加されている場合には、その合計量100部
に対して水硬性物質（）20〜300部が好ましく、
50〜150部が更に好ましい。又、その他に無機添
加物、特にゴム或はエラストマー、プラスチツク
に通常添加されるフイラーを添加することが出来
る。
又、更に上記水硬性物質にセメント系急硬剤を
添加する場合は、その添加量は水硬性物質100部
に対し30〜150部が好ましく、特に50〜100部が好
ましい。更に、水硬性物質（）、無機添加物及
びセメント系急硬剤の合計量は、水膨潤性物質
（ゴム等が添加されている場合にはその合計量）
100部に対して、20〜500部が好ましく、特に100
〜300部が好ましい。
本発明の水膨潤性組成物は、適宜の方法で成形
し、シール材として使用出来るが、特にゴムエラ
ストマー等を添加した場合には、ロール、ニーダ
ー、バンバリーミキサーなど通常のゴム混練機を
用いて配合し、押出成形機、プレス成形機により
成形するのが好ましい。この場合、分子間に橋か
けを生じさせる物質を添加した方が成形品の物性
を向上させるので好ましい。又、この様にして得
られた成形品には、使用目的に応じて表面に粘着
剤、被覆剤、老化防止剤、膨脹調整等を塗布する
ことが好ましい。
本発明に用いられる分子間に橋かけを生じさせ
る物質とは水膨潤性物質、ゴム各分子間に橋かけ
結合を生じさせることのできるような物質であ
り、イオウ、塩化イオウ、有機過酸化物、有機イ
オウ化合物、金属酸化物、アルキルフエノール樹
脂等のゴム加硫剤、ポリチオール化合物、ポリア
ミン化合物、アゾ化合物等を用いることができ
る。イオウ及び有機過酸化物による架橋が特に好
ましい。
イオウは粉末イオウが好ましく、適当な有機過
酸化物としてはベンゾイルパーオキシド、ジクミ
ルパーオキシド、メチルエチルケトンパーオキシ
ド、ラウリルパーオキシド、シクロヘキサノンパ
ーオキシド、ｔ−ブチルパーベンゾエート、ｔ−
ブチルヒドロパーオキシド、ｔ−ブチルベンゼン
パーオキシド、クメンヒドロパーオキシド、ｔ−
ブチルパーオクトエート等がある。
適当な有機イオウ化合物としては、テトラメチ
ルチウラムジスルフイド（TT）、Ｎ，N′−ジチ
オビスモルホリン等がある。
適当は金属酸化物としては亜鉛華、マグネシ
ア、リサージ等がある。
適当なアルキルフエノール樹脂としては、メチ
ロール基を７〜10％含むアルキルフエノールホル
ムアルデヒド樹脂がある。
適当なポリチオール化合物としては、トリメチ
ロールプロパントリチオグリコレート、トリメチ
ロールプロパントリ（３−メルカプトプロピオネ
ート）、グリコールジメルカプトプロピオネート、
グリコールジメルカプトアセテート、ペンタエリ
スリトールテトラ（３−メルカプトプロピオネー
ト）、ペンタエリスリトールテトラチオグリコレ
ート、ジペンタエリスリトールヘキサ（３−メル
カプトプロピオネート）等がある。
適当なポリアミン化合物としては、アルデヒド
−アミン縮合物、グアニジン類等がある。
適当なアゾ化合物としては、アゾビスイソブチ
ルニトリル、２−ｔ−ブチルアゾ−２−シアノ−
４−メチルペンタン、４−ｔ−ブチルアゾ−４−
シアノ−吉草酸等がある。
以上の橋かけ剤は１種又は２種以上を適宜組合
せて用いることが可能であり、その配合量はゴム
100部に対して0.5〜10部が適当である。
上記水膨潤性物質（）とゴムに橋かけ剤を加
え、さらに加硫促進剤、加硫助剤、軟化剤、老化
防止剤、粘着剤等の一般的ゴム配合剤を適宜選択
して配合し、さらに水硬性物質（）、セメント
急硬剤、無機添加剤等を加え、次いで練りロー
ル、バンバリーミキサー等、を用いて混練りを行
なう。これを必要ならば成型後プレス、加硫剤等
により、加硫処理（通常は120℃以上）を行なつ
て水膨潤組成物を得る。
加硫処理は熱加硫、蒸気加硫、熱空気加硫に限
らず自然加硫、熱湯加硫、冷加硫でもよい。
橋かけ剤を使用した場合はこのように水膨潤性
組成物においては水膨潤性物質（）とゴムが相
互に一体となつて架橋されているのが特徴であ
る。
また本発明の水膨潤性組成物は架橋剤に不定形
ないしパテ状で施工し、自然架橋（自然加硫）に
より硬化した状態とするような態様で用いること
でき、形状が複雑で定形シール材を適用すること
のできないような箇所にも好ましく実施できる。
〔発明の効果〕
本発明の水膨潤性組成物は、水膨潤性にすぐ
れ、形状が自由に変えられ、パテ、コーキング材
として用いられる他、ゴム或はエラストマーを添
加したものは、成形品として機械的特性、止水特
性に優れ、止水材、パツキング材等として広範な
用途に用いられる。
本発明の水膨潤性組成物は、水を吸収後水硬性
物質の骨格（マトリツクス）ができるので水中で
安定性がよく乾燥しても収縮が少ない。さらに海
水でも淡水と同程度の膨潤が得られる。
〔実施例〕
以下、実施例により本発明を更に詳述する。
実施例１〜６及び比較例１〜２
表１に示す配合（単位は重量部）を20cmオープ
ンロールで混練し、配合品１〜７を作成した。
[Industrial Application Field] The present invention relates to a water-swellable composition, and particularly to a water-swellable composition that absorbs water and expands, and then shrinks little even when dried. [Prior art and problems] Conventionally, water-swellable sealants have been made by adding water-absorbing substances such as sodium polyacrylate, starch, carboxymethyl cellulose, and polyethylene glycol to rubber or plastic to impart water-swellability. are used, but all of these shrink to almost their original state when dried. Further, in these water-swellable sealing materials, the water-swelling rate gradually decreases because the water-absorbing substance becomes water-soluble and is eluted. Furthermore, when these water-swellable sealants come into contact with seawater, they expand less than half as much as they do with fresh water. [Means for Solving the Problems] The present invention provides a new water-swellable composition that improves the above problems. The water-swellable composition of the present invention contains a water-swellable urethane resin () and a hydraulic substance () as essential components. The urethane resin used in the present invention includes:
When mixed with a hydraulic substance, a paste or an elastomer is preferred, and a paste is particularly preferred. Examples of pasty water-swellable polyurethane resins include resins obtained by reacting a water-swellable polyurethane prepolymer containing terminal isocyanate groups with water and/or a curing agent. The water-swellable polyurethane prepolymer containing terminal isocyanate groups has, for example, a hydroxyl equivalent of
Examples include prepolymers having a propylene oxide/ethylene oxide ratio of 7/3 to 0/10 obtained by reacting 400 to 6000 ethylene oxide/propylene oxide random/block polymerized polyoxyalkylene glycol with an organic diisocyanate in a conventional manner. The prepolymer can be partially cured by a conventional method with water or an amine-based or polyol-based curing agent to form a water-swellable polyurethane resin in the form of a paste. Curing may be carried out using a combination of water and a curing agent. As curing agents, 4,4'-methylene-bis-2-chloroaniline, 1,4-butanediol, hydroquinone-bis-(β-hydroxy)ether, resorcinol-bis-(β-
Hydroxy) ether, 1,2-bis-(2-aminophenolthio)ethane, trimethylene glycol di-p-aminobenzoate, etc. can be used alone or in combination. Here, water-absorbing resins that are usually referred to as resins include carboxyl groups, carboxylic acid salts, carboxylic acid amides, carboxylic acid imides, carboxylic acid anhydrides, and other groups that have a carboxyl group or a group that can be derived into a carboxyl group in the molecule. α having one or two,
Examples include those containing a β-unsaturated compound as a main component and polymerizing other α,β-unsaturated compounds as necessary, or those further modified with isocyanates or the like. Examples of such water-absorbing resins include starch/acrylic acid graft copolymers, salts of styrene-maleic anhydride copolymers, crosslinked products of sodium polyacrylate, crosslinked products of polyvinyl alcohol/maleic anhydride reactants, and vinyl Known super absorbent polymers such as saponified products of esters/ethylenically unsaturated carboxylic acids or derivatives thereof can be used. In addition, in the present invention, as the hydraulic substance (), hydraulic cement is preferable, and other materials such as gypsum,
Latent hydraulic materials can also be used. Further, it is more preferable to add a cement-based quick hardening agent to the hydraulic material. Here, the hydraulic cement is normal, white,
Various types of early-strength Portland cement, special cements such as blast furnace cement, colloidal cements classified by particle size, etc. can be used as appropriate. As cement-based quick hardening agents, calcium aluminate-based inorganic substances, namely 3CaO・Al 2 O 3 , CaO・
Al 2 O 3 , 12CaO・7Al 2 O 3 , CaO・2Al 2 O 3 , CaO・
Calcined products, molten mixtures of CaO and Al 2 O 3 such as 6Al 2 O 3 ,
Alternatively, calcium sulfoaluminate mixed with gypsum or the like may be used, and commercially available products include Denka ES (trade name of Denki Kagaku Co., Ltd.). The content of the water-swellable substance () is preferably such that the water swelling rate of the molded article obtained from the water-swellable composition is 10 to 350 (volume)%, and 40 to 250 (volume)%.
% is more preferable. In particular, when the water-swellable substance () is a water-swellable urethane resin, it is preferable to use rubber in combination, and 20 to 250 parts, especially 60 to 180 parts, of the water-swellable urethane resin is used per 100 parts of rubber (based on weight, the same applies hereinafter). is preferable. By using such a rubber in combination, the physical properties of the present composition, particularly the strength, can be improved. Rubbers used in the present invention include natural rubber, synthetic rubber, or recycled rubber, such as natural rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber,
It is selected from among ethylene propylene terpolymer, butyl rubber and their recycled rubbers depending on the use and purpose. In the present invention, an elastomer can be used instead of or in addition to the above-mentioned rubber, and such elastomers include polyurethane, polyolefin, polystyrene, and the like. Furthermore, the compositions of the invention can contain inorganic additives. The inorganic additives are preferably finely pulverized so as to be added to rubber, and preferable are white powder, zinc white, finely powdered silica, magnesium carbonate, etc., as well as bentonite, clay, other calcium silicates, alumina, chiyolk, etc. Can be added. Depending on the purpose, fillers such as glass microspheres, glass fibers, and carbon fibers may also be added in appropriate amounts. By adding such inorganic additives,
It is possible to facilitate the mixability and moldability of the present composition, or to improve the physical properties of molded articles, particularly strength, elasticity, etc. The content of the hydraulic substance () can be appropriately selected in relation to the water swelling rate and physical properties of the molded article of the water-swellable composition of the present invention, but the water-swellable substance () and rubber etc. are added. In some cases, 20 to 300 parts of the hydraulic substance () is preferable to 100 parts of the total amount;
More preferably 50 to 150 parts. In addition, inorganic additives, particularly fillers commonly added to rubbers, elastomers, and plastics, can also be added. Furthermore, when a cement-based quick hardening agent is added to the above-mentioned hydraulic substance, the amount added is preferably 30 to 150 parts, particularly preferably 50 to 100 parts, based on 100 parts of the hydraulic substance. Furthermore, the total amount of hydraulic substances (), inorganic additives, and cement-based quick hardening agents is the total amount of water-swellable substances (if rubber, etc. is added).
For 100 parts, 20 to 500 parts is preferable, especially 100 parts.
~300 parts is preferred. The water-swellable composition of the present invention can be molded by an appropriate method and used as a sealing material, but especially when a rubber elastomer or the like is added, it can be molded using a normal rubber kneading machine such as a roll, kneader, or Banbury mixer. It is preferable to mix the ingredients and mold them using an extrusion molding machine or a press molding machine. In this case, it is preferable to add a substance that causes crosslinking between molecules, since this improves the physical properties of the molded article. Furthermore, it is preferable to coat the surface of the molded article thus obtained with an adhesive, a coating agent, an anti-aging agent, an expansion control agent, etc. depending on the purpose of use. Substances that create cross-linking between molecules used in the present invention include water-swellable substances and substances that can create cross-linking between rubber molecules, such as sulfur, sulfur chloride, and organic peroxides. , organic sulfur compounds, metal oxides, rubber vulcanizing agents such as alkylphenol resins, polythiol compounds, polyamine compounds, azo compounds, etc. can be used. Particular preference is given to crosslinking with sulfur and organic peroxides. Sulfur is preferably powdered sulfur, and suitable organic peroxides include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl perbenzoate, t-
Butyl hydroperoxide, t-butylbenzene peroxide, cumene hydroperoxide, t-
Examples include butyl peroctoate. Suitable organic sulfur compounds include tetramethylthiuram disulfide (TT), N,N'-dithiobismorpholine, and the like. Suitable metal oxides include zinc white, magnesia, litharge, and the like. Suitable alkylphenol resins include alkylphenol formaldehyde resins containing 7 to 10% methylol groups. Suitable polythiol compounds include trimethylolpropane trithioglycolate, trimethylolpropane tri(3-mercaptopropionate), glycol dimercaptopropionate,
Examples include glycol dimercaptoacetate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrathioglycolate, dipentaerythritol hexa(3-mercaptopropionate), and the like. Suitable polyamine compounds include aldehyde-amine condensates, guanidines, and the like. Suitable azo compounds include azobisisobutylnitrile, 2-t-butylazo-2-cyano-
4-methylpentane, 4-t-butylazo-4-
Examples include cyano-valeric acid. The above cross-linking agents can be used alone or in an appropriate combination of two or more, and the amount of the cross-linking agent can be adjusted depending on the rubber.
0.5 to 10 parts per 100 parts is appropriate. A cross-linking agent is added to the above water-swellable substance () and rubber, and general rubber compounding agents such as vulcanization accelerators, vulcanization aids, softeners, anti-aging agents, and adhesives are selected and blended as appropriate. Further, a hydraulic substance (2), a cement quick hardening agent, an inorganic additive, etc. are added, and then kneading is performed using a kneading roll, a Banbury mixer, etc. If necessary, after molding, this is subjected to vulcanization treatment (usually at 120° C. or higher) using a press, a vulcanizing agent, etc. to obtain a water-swellable composition. The vulcanization treatment is not limited to heat vulcanization, steam vulcanization, or hot air vulcanization, but may also be natural vulcanization, hot water vulcanization, or cold vulcanization. When a crosslinking agent is used, the water-swellable composition is characterized in that the water-swellable substance (2) and the rubber are crosslinked together. In addition, the water-swellable composition of the present invention can be applied to a crosslinking agent in an amorphous or putty form and cured by natural crosslinking (natural vulcanization). It can be preferably implemented even in places where it is not possible to apply the method. [Effects of the Invention] The water-swellable composition of the present invention has excellent water-swellability and can be freely changed in shape, and can be used as putty and caulking materials.If rubber or elastomer is added, it can be used as a molded product. It has excellent mechanical properties and water-stopping properties, and is used in a wide range of applications such as water-stopping materials and packing materials. The water-swellable composition of the present invention forms a skeleton (matrix) of a hydraulic material after absorbing water, so it is stable in water and shows little shrinkage even when dried. Furthermore, the same degree of swelling can be obtained even in seawater as in freshwater. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1 to 6 and Comparative Examples 1 to 2 The formulations shown in Table 1 (unit: parts by weight) were kneaded using a 20 cm open roll to create formulations 1 to 7.
【表】
この配合品を140℃で10分間プレスし、２mm厚
のシートを得た。シートについてブルーミングの
有無、引張試験（測定法JIS K6301）、水浸漬時
間の膨潤率（浸漬日数12日の容積変化率と乾燥21
日後の厚さ変化率を測定し、変化を調べる）を測
定した。その結果を表２に示す。また配合品に於
て水膨潤性物質或は水硬性物質を使用しないもの
を比較例１〜２とした。[Table] This blended product was pressed at 140°C for 10 minutes to obtain a 2 mm thick sheet. Regarding the sheet, the presence or absence of blooming, tensile test (measurement method JIS K6301), swelling rate of water immersion time (volume change rate after 12 days of immersion and drying 21 days)
The rate of change in thickness after a day was measured to examine the change). The results are shown in Table 2. In addition, Comparative Examples 1 and 2 were prepared in which no water-swellable substance or hydraulic substance was used in the formulation.
Claims (1)
脂（）と水硬性物質（）とを含有することを
特徴とする水膨潤性組成物。 ２ 水硬性物質（）が水硬性セメントである特
許請求の範囲第１項記載の水膨潤性組成物。[Scope of Claims] 1. A water-swellable composition comprising a water-swellable urethane resin () and a hydraulic substance () as essential components. 2. The water-swellable composition according to claim 1, wherein the hydraulic substance () is a hydraulic cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9204884A JPS60235863A (en) | 1984-05-09 | 1984-05-09 | Water-swellable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9204884A JPS60235863A (en) | 1984-05-09 | 1984-05-09 | Water-swellable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60235863A JPS60235863A (en) | 1985-11-22 |
| JPH052704B2 true JPH052704B2 (en) | 1993-01-13 |
Family
ID=14043628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9204884A Granted JPS60235863A (en) | 1984-05-09 | 1984-05-09 | Water-swellable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60235863A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0678520B2 (en) * | 1986-04-08 | 1994-10-05 | 清水建設株式会社 | Water stop method for concrete structure |
| JPH0339387A (en) * | 1989-07-06 | 1991-02-20 | Oozeki Kagaku Kogyo Kk | Protection material for concrete |
| US7866394B2 (en) * | 2003-02-27 | 2011-01-11 | Halliburton Energy Services Inc. | Compositions and methods of cementing in subterranean formations using a swelling agent to inhibit the influx of water into a cement slurry |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5278955A (en) * | 1975-12-25 | 1977-07-02 | Sanyo Chem Ind Ltd | Polyurethane composition |
| JPS58176181A (en) * | 1982-04-09 | 1983-10-15 | ニチアス株式会社 | Castable composition |
| JPS5915424A (en) * | 1982-07-20 | 1984-01-26 | Sanyo Chem Ind Ltd | Production of urethane resin |
-
1984
- 1984-05-09 JP JP9204884A patent/JPS60235863A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5278955A (en) * | 1975-12-25 | 1977-07-02 | Sanyo Chem Ind Ltd | Polyurethane composition |
| JPS58176181A (en) * | 1982-04-09 | 1983-10-15 | ニチアス株式会社 | Castable composition |
| JPS5915424A (en) * | 1982-07-20 | 1984-01-26 | Sanyo Chem Ind Ltd | Production of urethane resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60235863A (en) | 1985-11-22 |
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