JP2017095622A - Cutoff agent composition and water leakage cutoff method - Google Patents
Cutoff agent composition and water leakage cutoff method Download PDFInfo
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- JP2017095622A JP2017095622A JP2015230303A JP2015230303A JP2017095622A JP 2017095622 A JP2017095622 A JP 2017095622A JP 2015230303 A JP2015230303 A JP 2015230303A JP 2015230303 A JP2015230303 A JP 2015230303A JP 2017095622 A JP2017095622 A JP 2017095622A
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- water
- mass
- meth
- acrylate
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- ULENOZATXLGIKY-UHFFFAOYSA-L strontium;prop-2-enoate Chemical compound [Sr+2].[O-]C(=O)C=C.[O-]C(=O)C=C ULENOZATXLGIKY-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
本発明は、下水道処理施設のヒュ−ム管路継手部の漏水防止、コンクリ−ト構造物のクラックからの湧水、漏水の防止又は阻止等に使用される含水弾性ゲルを形成する止水剤組成物及びそれを用いた漏水止水工法に関するものである。 The present invention relates to a water-stopping agent for forming a water-containing elastic gel used for preventing leakage of a fume pipe joint of a sewerage treatment facility, spring water from cracks in a concrete structure, prevention or prevention of leakage, etc. The present invention relates to a composition and a water leakage stopping method using the composition.
一般に、コンクリ−ト構造物からの湧水、漏水を止水するために、通常、湧水箇所のクラック幅が大きく、湧水量が多い場合は、ケイ酸ソーダ（水ガラス）またはケイ酸ソーダとセメントの混合物などを漏水箇所に注入して止水する方法が使用されている。また、湧水箇所または微量漏水箇所には微粒子セメントを注入する方法が用いられているが、前者は止水後ケイ酸ソーダのゲル化物が脆く、且つ、収縮率が大きく再漏水を招き易く、一方、後者の微粒子セメント懸濁液注入では、短時間での固結困難であること及び微小ヘヤ−クラックへの浸透深さが浅いこと等などの問題点があり、解決が望まれていた。 In general, in order to stop springs and leaks from concrete structures, when the crack width is large and the amount of springs is large, sodium silicate (water glass) or sodium silicate A method of stopping water by injecting a cement mixture or the like into a leaking point is used. In addition, although a method of injecting fine particle cement is used for the spring water location or the minute water leakage location, the former is brittle gelled sodium silicate after water stoppage, and the shrinkage is large, which easily causes re-leakage, On the other hand, the latter fine cement suspension injection has problems such as difficulty in setting in a short time and a small depth of penetration into micro-hair cracks.
上記コンクリ−ト構造物からの湧水、漏水を止水するための止水剤としては、上記の注入タイプが主流であり、その種類としては、上記セメント系の他に、エポキシ系、ポリウレタン系、（メタ）アクリル酸系などが使用されている。 As a water-stopping agent for stopping spring water and water leakage from the concrete structure, the above-mentioned injection type is the mainstream, and the types thereof include epoxy-based, polyurethane-based in addition to the cement-based materials. (Meth) acrylic acid type is used.
エポキシ系及びポリウレタン系の止水剤は、硬化後におけるコンクリ−ト、木材、金属等からなる漏水部の材料との接着力が強いが、漏水部の材料の温度や振動等の外的環境条件の変化に追随しきれず、接着部から新たな漏水のクラックが生じることがあり、またセメント系材料では、自己収縮によるクラック生成が頻繁に起こることの欠点がある。 Epoxy and polyurethane water-stopping agents have strong adhesive strength with water leakage parts made of concrete, wood, metal, etc. after curing, but external environmental conditions such as temperature and vibration of the water leakage part material In the cemented material, cracks due to self-shrinkage frequently occur. In addition, there is a drawback in that new leakage of water leakage may occur from the bonded portion.
ウレタン系止水剤としては、例えば、特許文献１（特開２００１−３２９１６３号公報）、特許文献２（特開２００２−３８２１号公報）に芳香族親水性ポリオ−ルを用いた耐久性に優れたウレタン系止水剤が提案されている。しかしながら、このようなポリウレタン系止水剤であっても、漏水止水後、経時的に乾燥収縮及び水膨張性がないための再漏水防止機能が十分でなく、恒久的に止水効果を持続することができない場合が多い。 As the urethane water-stopping agent, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2001-329163) and Patent Document 2 (Japanese Patent Laid-Open No. 2002-3821) are excellent in durability using an aromatic hydrophilic polyol. Urethane waterproofing agents have been proposed. However, even with such a polyurethane water-stopping agent, the water leakage prevention function is not sufficient due to lack of drying shrinkage and water expandability over time after the water leakage stoppage, and the water-stopping effect is permanently maintained. There are many cases where this is not possible.
他方、このような欠点を考慮して、（メタ）アクリル酸エステル系の注入型止水剤が開発され、使用されている。このような止水剤は、例えば、特許文献３（特公昭５７−１５６３１号公報）、特許文献４（特開２００４−１１５６４６号公報）、特許文献５（特開２００７−９９９１１号公報）には、大量のポリエチレングリコ−ルモノ（メタ）アクリレ−ト、少量のポリエチレングリコ−ルジ（メタ）アクリレ−ト及びアクリル酸若しくはメタアクリル酸の金属塩とからなる三成分混合物に重合触媒を加えた止水剤が提案されている。いずれも、大量のポリエチレングリコ−ルモノ（メタ）アクリレ−トに対して少量のポリエチレングリコ−ルジ（メタ）アクリレ−トの配合の止水剤であり、圧縮すると破壊し易く、復元性の機能が十分とは言えない。特許文献６（特開昭５８−２０６６８０号公報）、特許文献７（特開昭６１−２３１０８１号公報）は、ポリエチレングリコ−ルモノ（メタ）アクリレ−トとポリエチレングリコ−ルジ（メタ）アクリレ−トの二成分混合物止水剤である。いずれも、ゲル化物（硬化物）は圧縮復元性に乏しく、ゲル化物（硬化物）は脆い。 On the other hand, in view of such drawbacks, (meth) acrylic ester-based injection-type water-stopping agents have been developed and used. Such water-stopping agents are disclosed in, for example, Patent Document 3 (Japanese Patent Publication No. 57-15631), Patent Document 4 (Japanese Patent Laid-Open No. 2004-115646), and Patent Document 5 (Japanese Patent Laid-Open No. 2007-99911). Water-stopping in which a polymerization catalyst is added to a ternary mixture comprising a large amount of polyethylene glycol mono (meth) acrylate, a small amount of polyethylene glycol di (meth) acrylate and acrylic acid or a metal salt of methacrylic acid Agents have been proposed. Both are water-stoppers containing a small amount of polyethylene glycol di (meth) acrylate with a large amount of polyethylene glycol mono (meth) acrylate. That's not enough. Patent Document 6 (Japanese Patent Laid-Open No. 58-206680) and Patent Document 7 (Japanese Patent Laid-Open No. 61-231081) describe polyethylene glycol mono (meth) acrylate and polyethylene glycol di (meth) acrylate. It is a two-component mixture water-stopping agent. In any case, the gelled product (cured product) is poor in compression recovery and the gelled product (cured product) is brittle.
一方、特許文献８（特開６２−３４９７７号公報）は、特許文献６〜７に記載の混合物に水硬性セメントを加えたものであるが、依然として上記圧縮復元性及び水膨張性がの問題は十分に解消されていない。また、特許文献９（特開２００３−１９３０３２号公報）の止水剤組成物は、ポリエチレングリコ−ルジ（メタ）アクリレ−トとアクリル酸、メタアクリル酸、及びそれらの塩の構成に、さらに防凍剤を混合したものであるが、圧縮時におけるゲル化物の破壊、経時的乾燥収縮が大きく、また、水浸漬膨張性に乏しいことから、再漏水の問題が完全に解決されているとは言えない。 On the other hand, Patent Document 8 (Japanese Patent Application Laid-Open No. 62-34977) is a mixture obtained by adding hydraulic cement to the mixture described in Patent Documents 6 to 7, but the problems of the above-described compression recovery property and water expandability still remain. It has not been fully resolved. In addition, the water-stopping composition of Patent Document 9 (Japanese Patent Application Laid-Open No. 2003-193032) has a structure of polyethylene glycol di (meth) acrylate, acrylic acid, methacrylic acid, and salts thereof, and further anti-freeze. However, it cannot be said that the problem of re-leakage has been completely solved due to the large destruction of gelled product during compression, the shrinkage with drying over time, and poor water immersion expansion. .
特許文献１０（特開昭６１−２２１２８１号公報）は、ポリエチレングリコ−ルジ（メタ）アクリレ−トとアクリル酸、メタアクリル酸、及びそれらの塩の構成からなる止水剤であるが、圧縮復元性及び水浸漬膨張性に乏しく応力負荷破壊の課題は解決されていない。 Patent Document 10 (Japanese Patent Application Laid-Open No. 61-212281) is a water-stopping agent composed of polyethylene glycol di (meth) acrylate, acrylic acid, methacrylic acid, and salts thereof. The problem of stress load fracture has not been solved due to poor water solubility and water immersion expansibility.
特許文献１１（特開６２−２２８８２号公報）は、例えば、ポリエチレングリコ−ルジ（メタ）アクリレ−トとアクリル酸、メタアクリル酸、及びそれらの金属塩、並びにジメチルアミノエチルメタクリレ−ト、その塩およびその第４級化物の三成分混合物と重合触媒かなる止水剤は、破壊強度及び膨潤度に課題があり、解決されていない。 Patent Document 11 (Japanese Patent Laid-Open No. 62-22882) discloses, for example, polyethylene glycol di (meth) acrylate and acrylic acid, methacrylic acid, and metal salts thereof, and dimethylaminoethyl methacrylate, A water-stopping agent comprising a ternary mixture of a salt and a quaternized product thereof and a polymerization catalyst has problems in breaking strength and swelling degree and has not been solved.
前記に示す通り、公知の止水剤組成物は汎用化されているが、耐久性、圧縮復元性、乾燥後の水浸漬再膨張性、耐衝撃性の止水剤組成物は未だ実用化されていない。 As shown above, known water-stopping compositions have been widely used, but water-stopping compositions with durability, compression recovery, water immersion re-expandability after drying, and impact resistance are still in practical use. Not.
前述のように、公知の止水剤組成物においては、圧縮復元性、乾燥後の水浸漬再膨潤性、耐衝撃性、さらには、耐久性が、まだ十分な性能に達していないために、さらなる改善がのぞまれている。 As described above, in the known water-stopper composition, since the compression recovery property, the water immersion re-swellability after drying, the impact resistance, and the durability have not yet reached sufficient performance, Further improvements are expected.
従って、本発明の目的は、前記の欠点を解消し、圧縮復元性、乾燥後の水浸漬再膨潤による再漏水防止性及び耐衝撃性に優れ、そして、耐久性に優れた止水剤組成物を提供するものである。 Accordingly, an object of the present invention is to solve the above-mentioned drawbacks, and to provide a water-stopping agent composition that is excellent in compression recovery, re-leakage prevention due to water re-swelling after drying and impact resistance, and excellent in durability. Is to provide.
上記課題を解決するために、本発明者が鋭意検討を行った結果、ポリエチレングリコ−ルモノ（メタ）アクリレ−トと、ポリエチレングリコ−ルジ（メタ）アクリレ−トと、末端（メタ）アクリロイル基含有多価金属塩とを所定割合で使用し、かつ、ポリエチレングリコ−ルジ（メタ）アクリレ−トを、ポリエチレングリコ−ルモノ（メタ）アクリレ−トと同じか、それよりも多量に使用した（メタ）アクリル酸エステル系止水剤組成物は、架橋密度、重合反応速度の向上のみならず、驚くべきことに、反応速度を低下させることなく、圧縮復元性、乾燥後の水浸漬再膨潤による再漏水防止性、耐衝撃性、長期の耐久性、動水固結特性及び圧縮強度等が飛躍的に向上することが可能であることが明らかとなった。 In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, and terminal (meth) acryloyl group are contained. A polyvalent metal salt was used in a predetermined ratio, and polyethylene glycol di (meth) acrylate was used in the same or larger amount as polyethylene glycol mono (meth) acrylate (meth). Acrylic ester-based water-stopper composition not only improves the crosslink density and polymerization reaction rate, but also surprisingly, without reducing the reaction rate, compression recovery, re-leakage due to water re-swell after drying It became clear that the prevention, impact resistance, long-term durability, dynamic water consolidation characteristics, compressive strength, and the like can be dramatically improved.
従って、本発明は、
（Ａ）一般式（ａ）：
で表されるポリエチレングリコ−ルモノ（メタ）アクリレ−トの単独（１種類のみ）又はこれらの混合物１０〜４０質量部：及び
（Ｂ）一般式（ｂ）
で表されるポリエチレングリコ−ルジ（メタ）アクリレ−トの単独（１種類のみ）又はこれらの混合物２０〜５０質量部；及び
（Ｃ）（メタ）アクリロイル基を有する多価金属塩（固形分換算）１５〜５０質量部を含み、各質量の合計が１００質量部であって、かつ、（Ｂ）成分の質量が（Ａ）成分の質量と同じか、それよりも多量に含む止水剤組成物；
である。
Therefore, the present invention
(A) General formula (a):
10 to 40 parts by mass of a polyethylene glycol mono (meth) acrylate represented by the formula (single type) or a mixture thereof: and (B) General formula (b)
Polyethylene glycol di (meth) acrylate represented by the formula (only one type) or a mixture thereof in an amount of 20 to 50 parts by mass; and (C) a polyvalent metal salt having a (meth) acryloyl group (in terms of solid content) ) 15 to 50 parts by mass, the total of each mass is 100 parts by mass, and the mass of the component (B) is the same as or greater than the mass of the component (A) object;
It is.
本発明の止水剤組成物の好ましい実施態様を以下に列記する。 Preferred embodiments of the waterstop agent composition of the present invention are listed below.
（１）前記（Ａ）、（Ｂ）及び（Ｃ）の合計１００質量部に対して、（Ｄ）グリコ−ル類を１００〜３００質量部を含んでいる。これにより、長期間空気中に放置しても、乾燥収縮がほとんどなく、重量、寸法安定性に優れた硬化物（ゲル化物）が得られやすい。 (1) The total of 100 parts by mass of (A), (B) and (C) contains (D) glycols in an amount of 100 to 300 parts by mass. Thereby, even if left in the air for a long period of time, there is almost no drying shrinkage, and a cured product (gelled product) excellent in weight and dimensional stability is easily obtained.
（２）さらに、水硬性セメントを含んでいる。強度が大きくなり、漏水箇所のクラック幅が大きい場合に有効である。 (2) Further, hydraulic cement is included. This is effective when the strength is increased and the crack width at the water leakage location is large.
（３）さらに、酸化剤及び還元剤を含んでいる。両者で酸化還元触媒として機能し本発明では重合速度が向上する。 (3) Further, an oxidizing agent and a reducing agent are included. Both function as a redox catalyst, and the polymerization rate is improved in the present invention.
（４）Ｒ１がＲ２及びＲ３がいずれもメチル基である。即ち、一般式（ａ）及び（ｂ）で表される両方の化合物が共に、メタアクリレ−トである。これにより、圧縮復元性、乾燥後の水浸漬再膨潤による再漏水防止性、耐衝撃性等が大幅に向上する。 (4) R 1 is R 2 and R 3 is both a methyl group. That is, both compounds represented by the general formulas (a) and (b) are both metaacrylates. Thereby, the compression recovery property, the re-leakage prevention property by re-swelling with water after drying, the impact resistance, etc. are greatly improved.
また本発明は、上記止水剤組成物を、各成分を予め混合し、あるいは各成分を混合しながら、４００ｋｇｆ／ｃｍ２以下の吐出圧にて、注入ノズルの先端から注入ノズルの先端逆止弁を介してコンクリ−ト構造物の漏水箇所に注入することを特徴とする漏水止水工法にもある。 Further, the present invention provides the above-mentioned water-stopper composition, wherein each component is mixed in advance or while mixing each component, at a discharge pressure of 400 kgf / cm 2 or less, from the tip of the injection nozzle to the tip of the injection nozzle. There is also a water leakage stoppage method characterized by injecting water into a leaking portion of a concrete structure through a valve.
本発明によれば、従来のポリエチレングリコ−ル（ＰＥＧ）モノ、ジ（メタ）アクリレ−ト系止水剤の課題となっていた、管路継手部の漏水防止、得られる弾性体（ゲル化物）の切削性、空気中の放置での重量変化安定性、水中浸漬時の膨張性、高圧縮変形後の復元性、耐衝撃性、動水固結性、長期安定性等の特性が大幅に改善されている。 According to the present invention, water leakage prevention at a pipe joint, which has been a problem of conventional polyethylene glycol (PEG) mono- and di (meth) acrylate water-stopping agents, and an elastic body (gelled product) obtained ) Cutting properties, stability in weight change when left in the air, expansibility when immersed in water, resilience after high compression deformation, impact resistance, dynamic water consolidation, long-term stability, etc. It has been improved.
さらに、特に前記（Ｄ）グリコ−ル類を特定の組成比で添加することにより、本発明の止水剤組成物の硬化弾性体を、長時間に空気中に放置しても乾燥収縮がなく、重量・寸法安定性において優れたものとすることができる。これにより再漏水の防止が可能となる。 Furthermore, in particular, by adding the glycols (D) at a specific composition ratio, the cured elastic body of the water-stopper composition of the present invention does not shrink even when left in the air for a long time. , It can be excellent in weight and dimensional stability. As a result, re-leakage can be prevented.
本発明の止水剤組成物は、ポリエチレングリコ−ル（ＰＥＧ）モノ（メタ）アクリレ−ト及びポリエチレングリコ−ル（ＰＥＧ）ジ（メタ）アクリレ−トを主成分として含む基本構成を有する。 The water-stopper composition of the present invention has a basic structure containing polyethylene glycol (PEG) mono (meth) acrylate and polyethylene glycol (PEG) di (meth) acrylate as main components.
本発明に使用される上記ポリエチレングリコ−ル（ＰＥＧ）モノ（メタ）アクリレ−ト（（Ａ）成分）は、下記の一般式（ａ）：
本発明で使用される上記のポリエチレングリコ−ル（ＰＥＧ）ジ（メタ）アクリレ−ト（（Ｂ）成分）は、下記の一般式（ｂ）：
（但し、Ｒ２、Ｒ３が、それぞれ独立して水素原子又はメチル基を表し、そしてｍが２〜５０の整数を表す。）
で表される。
(Wherein, R 2, R 3 are each independently a hydrogen atom or a methyl group, and m represents an integer of 2 to 50.)
It is represented by
本発明は、（Ａ）１０〜４０質量％、（Ｂ）２０〜５０質量％及び（Ｃ）（メタ）アクリロイル基を有する多価金属塩（固形分換算）１５〜５０質量％（各質量％の合計が１００質量％である）を含んでおり、（Ｂ）の質量％が（Ａ）の質量％と同じか、（Ａ）の質量％よりも多い。また上記の本発明の止水剤組成物は、（メタ）アクリル系組成物１００質量部（即ち、（Ａ）＋（Ｂ）＋（Ｃ）の量）に対し、更に、（Ｄ）グリコ−ル類を１００〜３００質量部、好ましくは１２０〜２８０質量部を含むことが好ましい。 In the present invention, (A) 10 to 40% by mass, (B) 20 to 50% by mass and (C) a polyvalent metal salt having a (meth) acryloyl group (in terms of solid content) 15 to 50% by mass (each mass%) The total mass of (B) is the same as the mass% of (A) or more than the mass% of (A). In addition, the water-stopper composition of the present invention described above is based on 100 parts by weight of the (meth) acrylic composition (that is, the amount of (A) + (B) + (C)), and (D) glyco- It is preferable to contain 100 to 300 parts by mass, and preferably 120 to 280 parts by mass of ru.
一般式（ａ）で表されるポリエチレングリコ−ルモノ（メタ）アクリレ−トにおいては、Ｒ１がメチル基であることが好ましい。即ち、一般式（ａ）の化合物は、メタアクリレ−トである。これにより、圧縮復元性、乾燥後の水浸漬再膨潤による再漏水防止性、耐衝撃性などが大幅に向上する。また一般式（ａ）におけるｎは、エチレンオキサイドの平均付加モル数を意味し、２〜５０の範囲（好ましくは２〜１８、特に好ましくは３〜１２）である２未満の場合は、ゲル（硬化物）の強度が低下するとともに、蒸気圧が高くなり止水剤として安全性の面で好ましくない。平均付加モル数５０を超えると、混合物の粘度が上昇し、ヘヤ−クラックと呼ばれる微小クラック（一般に、幅０．３ｍｍ以下）への浸透が低下し、かつ重合物の架橋密度が低下することから高い強度の弾性ゲルを得ることが困難になる。 In the polyethylene glycol mono (meth) acrylate represented by the general formula (a), R 1 is preferably a methyl group. That is, the compound of the general formula (a) is a metaacrylate. Thereby, the compression recovery property, the re-leakage prevention property due to re-swelling after water immersion after drying, the impact resistance, etc. are greatly improved. Moreover, n in general formula (a) means the average addition mole number of ethylene oxide, and when less than 2 which is the range of 2-50 (preferably 2-18, especially preferably 3-12), it is gel ( The strength of the cured product is decreased, and the vapor pressure is increased, which is not preferable as a water-stopping agent in terms of safety. When the average number of added moles exceeds 50, the viscosity of the mixture increases, penetration into microcracks (generally 0.3 mm or less) called hair cracks decreases, and the crosslinking density of the polymer decreases. It becomes difficult to obtain a high-strength elastic gel.
ＰＥＧモノ（メタ）アクリレ−トとしては、例えばジエチレングリコ−ルモノアクリレ−ト、トリエチレングリコ−ルモノアクリレ−ト、ジエチレングリコ−ルモノメタアクリレ−ト、ＰＥＧ＃２００（平均付加モル数４．５）モノメタクリレ−ト、ＰＥＧ＃２００（平均付加モル数４．５）モノアクリレ−ト、ＰＥＧ＃３５０（平均付加モル数８）モノメタアクリレ−ト、ＰＥＧ＃４００（平均付加モル数１０）モノアクリレ−ト、ＰＥＧ＃６００（平均付加モル数１４）モノメタクリレ−ト、ＰＥＧ＃１０００（平均付加モル数２３）モノアクリレ−ト、ＰＥＧ＃２０００（平均付加モル数４６）モノメタアクリレ−ト、ＰＥＧ＃３０００（平均付加モル数７０）モノメタアクリレ−ト等が挙げられる。これらは単独（１種類）で用いてもよいし、２種類以上を混合して用いても良い。特に、メタクリレ−トが好ましい。 Examples of PEG mono (meth) acrylate include diethylene glycol monoacrylate, triethylene glycol monoacrylate, diethylene glycol monomethacrylate, PEG # 200 (average number of moles added 4.5) monomethacrylate. PEG # 200 (average added mole number 4.5) monoacrylate, PEG # 350 (average added mole number 8) monomethacrylate, PEG # 400 (average added mole number 10) monoacrylate, PEG # 600 (average Addition mole number 14) Monomethacrylate, PEG # 1000 (average addition mole number 23) monoacrylate, PEG # 2000 (average addition mole number 46) monomethacrylate, PEG # 3000 (average addition mole number 70) monomethacrylate Etc. These may be used singly (one kind), or two or more kinds may be mixed and used. In particular, methacrylate is preferred.
水溶性を低下させない程度であれば、ポリプロピレングリコ−ルモノアクリレ−ト、メトキシポリエチレングリコ−ルモノアクリレ−ト、エチルジエチレングリコ−ルアクリレ−ト、メチルトリエチレングリコ−ルアクリレ−ト等を併用しても差し支えない。 As long as the water solubility is not lowered, polypropylene glycol monoacrylate, methoxypolyethylene glycol monoacrylate, ethyldiethylene glycol acrylate, methyltriethylene glycol acrylate, etc. may be used in combination.
また、本発明の止水剤組成物の必須成分の（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量％に対して（Ａ）の添加率は１０〜４０質量％である。１０質量％以下ではゲル化物の圧縮復元性が低下する。また、４０質量％以上ではゲル化物は脆くなり過ぎるため、管内に露出したゲル化物を切断、除去する管路断面確保作業に際して、継手箇所のゲル化物の破壊を招き再漏水の原因となる。 Moreover, the addition rate of (A) is 10-40 mass% with respect to 100 mass% of the total amount of (A), (B), and (C) of the essential components of the waterstop agent composition of this invention. If it is 10% by mass or less, the compression recovery property of the gelled product is lowered. Further, when the amount is 40% by mass or more, the gelled product becomes too brittle. Therefore, in the pipe cross-section securing operation for cutting and removing the gelled product exposed in the pipe, the gelated product at the joint portion is destroyed and re-leakage is caused.
本発明の止水剤組成物の必須成分の（Ｂ）のＰＥＧジ（メタ）アクリレ−トとしては、Ｒ２、Ｒ３が、共にメチル基であることが好ましい。即ち、一般式（ｂ）の化合物は、メタクリレ−トである。これにより、圧縮復元性、乾燥後の水浸漬再膨潤による再漏水防止性、耐衝撃性等が大幅に向上する。また、一般式（ｂ）中のｍは、エチレンオキシドの平均付加モル数を意味し、２〜５０の範囲（好ましくは４〜３０、特に好ましくは６〜２５）である。２未満の場合は、ゲル化物は脆く、乾燥収縮後水浸漬中での水膨張率が低下して好ましくない。５０を超えると、混合物の粘度が上昇し、且つ重合物の架橋密度が低下し、ゲル化物の強度が低下し、耐水性も低下するので好ましくない。 In the PEG di (meth) acrylate as the essential component (B) of the water-stopper composition of the present invention, it is preferable that R 2 and R 3 are both methyl groups. That is, the compound of the general formula (b) is methacrylate. Thereby, the compression recovery property, the re-leakage prevention property by re-swelling with water after drying, the impact resistance, etc. are greatly improved. Moreover, m in general formula (b) means the average addition mole number of ethylene oxide, and is the range (preferably 4-30, especially preferably 6-25) of 2-50. If it is less than 2, the gelled product is fragile, and the water expansion coefficient during water immersion after drying shrinkage decreases, which is not preferable. If it exceeds 50, the viscosity of the mixture increases, the crosslinking density of the polymer decreases, the strength of the gelled product decreases, and the water resistance also decreases, which is not preferable.
一般式（ｂ）で表されるポリエチレングリコ−ルジ（メタ）アクリレ−ト（ＰＥＧジ（メタ）アクリレ−ト）としては、例えばジエチレングリコ−ルジアクリレ−ト、ジエチレングリコ−ルジメタアクリレ−ト、トリエチレングリコ−ルジアクリレ−ト、トリエチレングリコ−ルジメタアクリレ−ト、テトラエチレングリコ−ルジアクリレ−ト、テトラエチレングリコ−ルジメタアクリレ−ト、ＰＥＧ＃１５０（平均付加モル数３）ジメタクリレ−ト、ＰＥＧ＃２００（平均付加モル数４）ジメタクリレ−ト、ＰＥＧ＃２００（平均付加モル数４）ジアクリレ−ト、ＰＥＧ＃４００（平均付加モル数９）ジメタクリレ−ト、ＰＥＧ＃４００（平均付加モル数９）ジアクリレ−ト、ＰＥＧ＃６００（平均付加モル数１４）ジメタクリレ−ト、ＰＥＧ＃１０００（平均付加モル数２３）ジメタクリレ−ト、ＰＥＧ＃２０００（平均付加モル数４６）ジメタクリレ−ト、ＰＥＧ＃３０００（平均付加モル数７０）ジメタクリレ−ト等が挙げることができる。これらは１種類のみを単独で用いてもよいし、２種類以上を混合して用いてもよい。特にメタクリレ−トを用いることが好ましい。 Examples of the polyethylene glycol di (meth) acrylate represented by the general formula (b) (PEG di (meth) acrylate) include diethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol diacrylate. -Triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, PEG # 150 (average number of moles added 3) dimethacrylate, PEG # 200 (average number of moles added 4) ) Dimethacrylate, PEG # 200 (average number of moles added 4) diacrylate, PEG # 400 (average number of moles added 9) dimethacrylate, PEG # 400 (average number of moles added 9) diacrylate, PEG # 600 (Average number of moles added 14) Dimethacrylate, P G # 1000 (average addition mole number 23) Jimetakurire - DOO, PEG # 2000 (average addition mole number 46) Jimetakurire - DOO, PEG # 3000 (average addition mole number 70) Jimetakurire - can bets and the like exemplified. These may be used alone or in combination of two or more. It is particularly preferable to use methacrylate.
水溶性を低下させない程度であれば、ポリプロピレングリコ−ルモノアクリレ−ト、メトキシポリエチレングリコ−ルモノアクリレ−ト、エチルジエチレングリコ−ルアクリレ−ト、メチルトリエチレングリコ−ルアクリレ−ト等を併用しても差し支えない。 As long as the water solubility is not lowered, polypropylene glycol monoacrylate, methoxypolyethylene glycol monoacrylate, ethyldiethylene glycol acrylate, methyltriethylene glycol acrylate, etc. may be used in combination.
また、本発明の止水剤組成物の必須成分の（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量％に対して（Ｂ）の添加率は２０〜５０質量％とし、かつ、（Ｂ）の添加率を（Ａ）の添加率以上にする。（Ｂ）の添加率が低すぎると、三次元分子構造が減少するためゲル化物の強度は低下し、耐久性が劣る。また、（Ｂ）の添加率が多すぎると、圧縮復元性が低下し、圧縮応力付加によりクラックが発生し再漏水するため好ましくない。より好ましくは、（Ｂ）の添加率（質量部）を（Ａ）の添加率（質量部）よりも多くする。 Moreover, the addition rate of (B) shall be 20-50 mass% with respect to 100 mass% of the total amount of (A), (B) and (C) of the essential components of the water-stopper composition of the present invention, and The addition rate of (B) is made higher than the addition rate of (A). When the addition rate of (B) is too low, the three-dimensional molecular structure is reduced, so that the strength of the gelled product is lowered and the durability is inferior. Moreover, when there is too much addition rate of (B), since a compression restoring property falls, a crack generate | occur | produces by compression stress addition and it is not preferable. More preferably, the addition rate (parts by mass) of (B) is made larger than the addition rate (parts by mass) of (A).
さらに、本発明の止水剤組成物においては、必須成分の（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量％に対して（Ｃ）の量は１５〜５０質量％である。１５質量％未満では、ゲル化物は脆くなり、繰り返し圧縮変形への追従性が乏しい。また、５０質量％を超えると、圧縮強度が低下し、漏水圧力が大きい場合は、圧縮変形して止水機能が低下し易くなる。 Furthermore, in the waterstop agent composition of this invention, the quantity of (C) is 15-50 mass% with respect to 100 mass% of total amounts of the essential components (A), (B), and (C). If it is less than 15% by mass, the gelled product becomes brittle and the followability to repeated compression deformation is poor. Moreover, when it exceeds 50 mass%, compressive strength will fall, and when a water leak pressure is large, it will compress-deform and it will become easy to fall a water stop function.
本発明に用いられる上記一般式（ａ）のＰＥＧモノ（メタ）アクリレ−ト（Ａ）及び上記一般式（ｂ）のＰＥＧジ（メタ）アクリレ−ト（Ｂ）は、ＰＥＧモノアクリレ−ト及びＰＥＧモノメタクリレ−ト、及びＰＥＧジアクリレ−ト及びＰＥＧジメタクリレ−トのいずれも使用可能であるが、上述のようにＰＥＧモノメタクリレ−トとＰＥＧジメタクリレ−トの組合せ、即ち両者ともメタクリレ−トを使用することが好ましい。その優位性は前述の効果に加えて、アクリレ−トタイプに比べて得られる組成物の皮膚刺激性が低く、また組成物の長期保存安定性において優れていることが挙げられる。 The PEG mono (meth) acrylate (A) of the general formula (a) and the PEG di (meth) acrylate (B) of the general formula (b) used in the present invention are PEG monoacrylate and PEG. Both monomethacrylate, and PEG diacrylate and PEG dimethacrylate can be used, but as described above, a combination of PEG monomethacrylate and PEG dimethacrylate, i.e. both use methacrylate. preferable. In addition to the above-mentioned effects, the superiority of the composition is lower in skin irritation than the acrylate type, and is excellent in long-term storage stability of the composition.
本発明の止水剤組成物で使用される上記一般式（ａ）のＰＥＧモノ（メタ）アクリレ−トは、例えば（メタ）アクリル酸又はその低級アルコ−ルエステルとアルキレングリコ−ル鎖含有アルコ−ルとのエステル（例えは特開２００２−２９３９１８号公報に記載）であり、酸とアルコ−ルを用いて脱水することにより行う直接エステル化法またはアルコ−ルとエステルを用いて脱アルコ−ルを行うエステル交換法により得られる。 The PEG mono (meth) acrylate of the general formula (a) used in the waterstop composition of the present invention is, for example, (meth) acrylic acid or a lower alcohol ester thereof and an alkylene glycol chain-containing alcohol. An ester with alcohol (for example, described in JP-A-2002-293918), a direct esterification method performed by dehydration using an acid and an alcohol, or a dealcohol using an alcohol and an ester. Obtained by the transesterification method.
上記アルキレングリコ−ル鎖含有アルコ−ルとしては、本発明ではエチレングリコ−ル鎖を有するものであれば何ら限定はない。例えば、ジエチレングリコ−ル、トリエチレングリコ−ル、テトラエチレングリコ−ル、前述の種々のポリエチレングリコ−ルを挙げることができる。その他、２次成分として、プロピレングリコ−ル、ジプロピレングリコ−ル、ブチレングリコ−ル、ドデシレングリコ−ル、オクタデシレングリコ−ル、ネオペンチルグリコ−ルなどの２価のアルコ−ル、グリセリン、ジグリセリン、トリメチロ−ルプロパン等の３価のアルコ−ルも使用して良い。 The alkylene glycol chain-containing alcohol is not particularly limited as long as it has an ethylene glycol chain in the present invention. For example, diethylene glycol, triethylene glycol, tetraethylene glycol, and the various polyethylene glycols described above can be used. Other secondary components include divalent alcohols such as propylene glycol, dipropylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, neopentyl glycol, glycerin, Trivalent alcohols such as diglycerin and trimethylolpropane may also be used.
本発明において、止水剤組成物の必須成分の一つである（Ｂ）上記一般式（ｂ）のＰＥＧジ（メタ）アクリレ−トは、（メタ）クリル酸クロライドと前記記載のアルキレングリコ−ル鎖含有アルコ−ルを塩基の存在下でエステル化反応させることにより得ることができる。（例えば特開２００１−３５４７３１号公報に記載）エステル化反応に用いる塩基としては、第三級アミン及び無機塩基が挙げることができる。これらの例としては、トリエチルアミン、ピリジン、トリプロピルアミン、トリブチルアミン、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム等が挙げることかできる。これらの中では、反応性の高いトリエチルアミン、トリプロピルアミン、トリブチルアミンが好ましい。 In the present invention, (B) the PEG di (meth) acrylate of the general formula (b), which is one of the essential components of the water-stopper composition, includes (meth) acrylic acid chloride and the alkylene glycol described above. It can be obtained by esterifying a ru chain-containing alcohol in the presence of a base. (For example, it describes in Unexamined-Japanese-Patent No. 2001-354731) As a base used for esterification reaction, a tertiary amine and an inorganic base can be mentioned. Examples of these include triethylamine, pyridine, tripropylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Of these, highly reactive triethylamine, tripropylamine, and tributylamine are preferable.
エステル化反応は通常有機溶媒中で行われる。その溶媒の例としては、塩化メチレン、クロロホルムのようなハロゲン系溶媒、ベンゼン、トルエン、エチルベンゼンのような芳香族炭化水素溶媒、ヘキサン等の脂肪族炭化水素溶媒等が挙げることができる。 The esterification reaction is usually performed in an organic solvent. Examples of the solvent include halogen solvents such as methylene chloride and chloroform, aromatic hydrocarbon solvents such as benzene, toluene and ethylbenzene, and aliphatic hydrocarbon solvents such as hexane.
エステル化反応の温度は、一般に−１０〜８０℃、好ましくは０〜６０℃である。必要に応じて重合禁止剤が用いられる。重合禁止剤の例としてはハイドロキノン、メチルハイドロキノンなどのハイドロキノン類、ベンゾキノン、メチル−Ｐ−ベンゾキノンなどのベンゾキノン類、ｔ−ブチルカテコ−ルなどのカテコ−ル類等を挙げることができる。 The temperature of the esterification reaction is generally -10 to 80 ° C, preferably 0 to 60 ° C. A polymerization inhibitor is used as necessary. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-P-benzoquinone, and catechols such as t-butylcatechol.
本発明の止水剤組成物においては、必須成分として（Ｃ）（メタ）アクリロイル基を末端に含む多価金属塩が採用される。（メタ）アクリロイル基を含む多価金属塩の金属としは、例えばアルカリ土類金属塩などの二価以上の多価金属塩であることが好ましい。多価金属塩の例としては、（メタ）アクリル酸マグネシウム、（メタ）アクリル酸カルシウム、（メタ）アクリル酸亜鉛、（メタ）アクリル酸バリウム、（メタ）アクリル酸ストロンチウム、（メタ）アクリル酸鉛、（メタ）アクリル酸ニッケルおよび（メタ）アクリル酸アルミニウム、（メタ）アクリル酸クロム等が挙げることができる。これらの中で、前記組成物の硬化体が高圧縮率でも復元性機能を発揮し再漏水を防止するためには、アクリル酸マグネシウム、アクリル酸アルミニウム及びアクリル酸ストロンチウムを使用することが好ましい。 In the waterstop agent composition of the present invention, a polyvalent metal salt containing a (C) (meth) acryloyl group at the terminal is adopted as an essential component. The metal of the polyvalent metal salt containing a (meth) acryloyl group is preferably a divalent or higher polyvalent metal salt such as an alkaline earth metal salt. Examples of polyvalent metal salts include magnesium (meth) acrylate, calcium (meth) acrylate, zinc (meth) acrylate, barium (meth) acrylate, strontium (meth) acrylate, lead (meth) acrylate , Nickel (meth) acrylate, aluminum (meth) acrylate, chromium (meth) acrylate, and the like. Among these, it is preferable to use magnesium acrylate, aluminum acrylate, and strontium acrylate in order for the cured product of the composition to exhibit a restoring function even at a high compression rate and prevent water leakage.
上記（メタ）アクリロイル基を含む多価金属塩は、単独でも、２種類以上を組み合わせて用いてもよい。 The polyvalent metal salt containing the (meth) acryloyl group may be used alone or in combination of two or more.
上記（メタ）アクリロイル基含有多価金属塩類モノマ−の製造方法は、（メタ）アクリル酸とアルカリ土類金属を、公知の製造法である常温よりやや高めの温度で反応させて中和する方法、又は、（メタ）アクリル酸エステルをアルカリ土類金属で鹸化する方法が代表的である。 The method for producing the (meth) acryloyl group-containing polyvalent metal salt monomer is a method of neutralizing (meth) acrylic acid and an alkaline earth metal by reacting them at a temperature slightly higher than room temperature, which is a known production method. Alternatively, a method of saponifying (meth) acrylic acid ester with an alkaline earth metal is typical.
本発明の止水剤組成物は、さらにグリコ−ル類を含むことができる。グリコール類は止水剤組成物の凍結防止剤として機能するたけではなく、室温環境下で長期保存した場合のクラックの発生を防止し、かつ、圧縮応力を負荷したときの耐クラック性も向上させる。グリコ−ル類の例としては、エチレングリコ−ル、プロピレングリコ−ル、ジエチレングリコ−ル、トリエチレングリコ−ル、１、３ブチレングリコ−ル、ヘキシレングリコ−ル、グリセリンなどを挙げることができる。これらの中で、特にエチレングリコ−ル及びプロピレングリコ−ルが好ましい。これらは単独使用又は併用してもよい。これらのグリコ−ル類は止水剤組成物の弾性硬化ゲルは空気中に放置後における寸法及び重量安定性を向上させるため、グリコ−ルの蒸気圧が２５℃で０．１ｍｍＨｇ以下のものが好ましい。前記グリコ−ル類は収縮安定機能の他に凝固点降下機能を有するため、冬期止水剤硬化物の凍結を防止する。 The waterstop agent composition of the present invention can further contain glycols. Glycols not only function as antifreezing agents for water-stopping compositions, but also prevent cracking when stored for a long time in a room temperature environment, and also improve crack resistance when subjected to compressive stress. . Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3 butylene glycol, hexylene glycol, glycerin and the like. . Of these, ethylene glycol and propylene glycol are particularly preferable. These may be used alone or in combination. In these glycols, the elastically cured gel of the water-stopper composition improves the dimensional and weight stability after standing in the air, so that the glycol vapor pressure is 0.1 mmHg or less at 25 ° C. preferable. Since the glycols have a freezing point lowering function in addition to the shrinkage stabilization function, the winter water-stopper cured product is prevented from freezing.
前述のように、本発明において、止水剤組成物の構成成分の（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量部に対して、（Ｄ）グリコ−ル類の添加率は８０〜３５０質量部、好ましくは１００〜３００質量部、より好ましくは１２０〜２８０質量部の範囲で使用することが好ましい。 As described above, in the present invention, the addition rate of (D) glycols is 100 parts by mass of the total amount of the components (A), (B) and (C) of the waterstop agent composition. It is preferable to use in the range of 80 to 350 parts by mass, preferably 100 to 300 parts by mass, more preferably 120 to 280 parts by mass.
１００質量部未満ではゲル化物の空気中での長期放置による減量変化率が大きく、３００質量部を超えるとゲル化物の圧縮負荷変形率が大きくなるため、好ましくない。 If it is less than 100 parts by mass, the rate of change in weight loss due to long-term standing of the gelled product in air is large, and if it exceeds 300 parts by mass, the compressive load deformation rate of the gelled product is increased, which is not preferable.
本発明に用いる重合触媒としては、通常レドックス触媒が使用される。酸化剤としては、例えば、過硫酸ナトリウム、過硫酸アンモニウム、過硫酸カリウム、過酸化水素、過塩素酸のアルカリ金属塩等の無機酸化剤の他、有機過酸化物を使用することができる。止水剤組成物の希釈剤として水を使用する場合は、有機過酸化物よりも無機酸化剤が好ましく、それらの中でも過硫酸ナトリウム、過硫酸アンモニウム、過硫酸カリウム、特に過硫酸アンモニウムが好ましい。酸化剤の使用量は、（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量部に対して、一般に０．５〜１０質量部である。ただし、酸化剤の量は用途によって適宜変更可能であり、止水剤組成物が多量の水等で希釈されるような場合、（Ａ）、（Ｂ）及び（Ｃ）の合計１００質量部に対し、酸化剤を１．５〜３０質量部、好ましくは５〜２０質量部用いることができる。 As the polymerization catalyst used in the present invention, a redox catalyst is usually used. As the oxidizing agent, for example, an organic peroxide can be used in addition to an inorganic oxidizing agent such as sodium persulfate, ammonium persulfate, potassium persulfate, hydrogen peroxide, alkali metal salt of perchloric acid or the like. When water is used as a diluent for the waterstop agent composition, an inorganic oxidizing agent is preferable to an organic peroxide, and among them, sodium persulfate, ammonium persulfate, potassium persulfate, and particularly ammonium persulfate are preferable. Generally the usage-amount of an oxidizing agent is 0.5-10 mass parts with respect to 100 mass parts of total amounts of (A), (B), and (C). However, the amount of the oxidizing agent can be appropriately changed depending on the use. When the waterstop agent composition is diluted with a large amount of water or the like, the total amount of (A), (B) and (C) is 100 parts by mass. On the other hand, the oxidizing agent can be used in an amount of 1.5 to 30 parts by mass, preferably 5 to 20 parts by mass.
還元剤としては、例えば亜硫酸水素ナトリウム、亜硫酸ナトリウム、亜硫酸カリウム、チオ硫酸ソ−ダ、硫酸第一鉄、トリエチルアミン、トリエタノ−ルアミン、Ｎ−メチルモルフォリン、ニトリロトリスプロピオンアミド、或はナトリウム又はカリウムのメタ重亜硫酸塩等を使用することができる。その使用量は、（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量部に対して、一般に０．５〜５質量部である。ただし、還元剤の量も用途によって適宜変更可能であり、止水剤組成物が多量の水等で希釈されるような場合、（Ａ）、（Ｂ）及び（Ｃ）の合計１００質量部に対し、還元剤を１．５〜３０質量部、好ましくは５〜２０質量部用いることができる。 Examples of the reducing agent include sodium bisulfite, sodium sulfite, potassium sulfite, soda thiosulfate, ferrous sulfate, triethylamine, triethanolamine, N-methylmorpholine, nitrilotrispropionamide, or sodium or potassium. Metabisulfite or the like can be used. The amount used is generally 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of (A), (B) and (C). However, the amount of the reducing agent can also be appropriately changed depending on the use. When the waterstop agent composition is diluted with a large amount of water or the like, the total amount of (A), (B) and (C) is 100 parts by mass. On the other hand, the reducing agent can be used in an amount of 1.5 to 30 parts by mass, preferably 5 to 20 parts by mass.
本発明の止水剤組成物は水硬性セメントをさらに含むことができる。本発明の止水剤組成物に用いられる水硬性セメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、高炉セメント、シリカセメント、フライアッシュセメント、アルミナセメント、超早強セメント、微粒子高炉スラグセメント、エコセメント（普通エコセメント、速硬エコセメントを含む）等を挙げることができる。これらのセメントは１種類のみを単独で用いてもよいし、２種類以上を用いてもよい。 The waterstop composition of the present invention may further contain hydraulic cement. Examples of the hydraulic cement used in the water-stopper composition of the present invention include ordinary Portland cement, early-strength Portland cement, blast furnace cement, silica cement, fly ash cement, alumina cement, ultra-early strong cement, particulate blast furnace slag cement, eco Cement (including ordinary eco-cement and fast-curing eco-cement) can be used. These cements may be used alone or in combination of two or more.
上記水硬性セメントの使用量は、止水剤組成物の止水性、硬化特性、圧縮特性、作業性に応じて決定されるが、一般にその使用量は（Ａ）、（Ｂ）及び（Ｃ）の合計量１００質量部に対して１０〜２００質量部の範囲である。 The usage amount of the hydraulic cement is determined according to the water-stopping property, the curing property, the compression property, and the workability of the water-stopper composition, but the usage amount is generally (A), (B) and (C). It is the range of 10-200 mass parts with respect to the total amount of 100 mass parts.
本発明の止水剤組成物は、止水性、硬化特性、圧縮特性、耐久性等の特性を阻害しない程度にベントナイト、タルク、クレ−、炭酸カルシウムなどのフィラー、顔料、染料等の着色剤など多様な添加剤を使用することができる。 The water-stopper composition of the present invention is a filler such as bentonite, talc, clay and calcium carbonate, a colorant such as pigment and dye, etc. to such an extent that the water-stopping property, curing property, compression property, durability and the like are not impaired. A variety of additives can be used.
本発明の止水剤組成物は、用途に応じて希釈剤で希釈することが可能である。希釈剤としては、有機溶媒、水、有機溶媒と水の混合物等多様なものを使用可能であるが、取扱い性を考慮すると、通常水を用いる。ただし、水希釈率が大きすぎると乾燥収縮率が増大し、乾燥後水浸漬での止水剤組成物ゲル化物の水膨張復元速度が遅くなる。従って、乾燥収縮率を抑える場合には、本発明の止水剤組成物に、水の一部を有機溶媒（エチレングリコ−ル等）に換えて添加することにより、水のみを添加した場合と比較して、乾燥収縮を大幅に低減することができる。すなわち、本発明に適した希釈剤は、水を主成分（５０質量％以上）とし、必要に応じて有機溶媒を含有する。 The waterstop agent composition of the present invention can be diluted with a diluent depending on the application. As the diluent, various solvents such as an organic solvent, water, a mixture of an organic solvent and water can be used, but water is usually used in consideration of handling properties. However, if the water dilution rate is too large, the drying shrinkage rate increases, and the water expansion / restoration speed of the water-stopper composition gelled product in water immersion after drying becomes slow. Therefore, in the case of suppressing the drying shrinkage rate, by adding a part of water to the water-stopper composition of the present invention instead of an organic solvent (ethylene glycol or the like), and adding only water. In comparison, drying shrinkage can be greatly reduced. That is, the diluent suitable for the present invention contains water as a main component (50% by mass or more), and optionally contains an organic solvent.
なお、従来の組成物、すなわち、本発明の止水剤組成物の（Ａ）、（Ｂ）及び（Ｃ）の組成比の範囲外にある組成物では、上記乾燥収縮以外でも優れた特性を維持するためには水希釈倍率が低くする必要があり、このため、止水対象のクラックから大量の漏水が発生するような状況では、水希釈倍率がさらに大きくなり、そのような過剰な水により希釈された止水剤組成物では止水効果を満足させることが困難である。驚くべきことに、本発明の止水性組成物を用いると、大量の水で希釈されるような場合であっても、止水性、硬化性などの特性を維持することが可能である。 In addition, in the conventional composition, that is, the composition outside the range of the composition ratio of (A), (B) and (C) of the water-stopper composition of the present invention, excellent characteristics other than the above-described drying shrinkage are obtained. In order to maintain the water dilution ratio, it is necessary to reduce the water dilution ratio. For this reason, in a situation where a large amount of water leaks from a crack to be stopped, the water dilution ratio is further increased. It is difficult to satisfy the water-stopping effect with the diluted water-stopper composition. Surprisingly, when the water-stopping composition of the present invention is used, it is possible to maintain properties such as water-stopping and curability even when diluted with a large amount of water.
次に、本発明の止水剤組成物を用いた止水工法の具体例について説明する。 Next, the specific example of the water stop construction method using the water stop agent composition of this invention is demonstrated.
本発明の漏水止水工法は、上記本発明の止水剤組成物を用いて、トンネルや下水管路継手部、クラックなどにおける湧水、漏水を止水するため使用され、例えば以下のように行うことができる。本発明の止水剤組成物は、（Ａ）〜（Ｃ）成分及び他の添加剤を予め混合した混合物を用いるか、使用直前に混合する、あるいは混合しながら使用する。好ましくは、少なくとも還元剤を含む成分と少なくとも酸化剤を含む成分とを、止水剤組成物の使用開始直前に混合するか、混合しながら使用（注入、塗布など）する。 The water leakage stop method of the present invention is used to stop springs and water leaks in tunnels, sewer pipe joints, cracks, etc., using the water stop agent composition of the present invention, for example, as follows: It can be carried out. The waterstop agent composition of the present invention uses a mixture in which the components (A) to (C) and other additives are mixed in advance, or is mixed immediately before use or while being mixed. Preferably, a component containing at least a reducing agent and a component containing at least an oxidizing agent are mixed immediately before the start of use of the water-stopper composition or used while being mixed (injection, coating, etc.).
より具体的には、（メタ）アクリレ−ト成分（Ａ、Ｂ及びＣ成分）、還元剤等を含む主剤と、酸化剤、グリコ−ル類等の硬化剤からなり、これらを使用時に混合する。従って、本発明の止水剤組成物は一般に２液混合方式として使用される。漏水量が多くない場合、前記主剤と硬化剤のいずれか一方又は両方に、水などの希釈剤を最大３０質量％添加することができる。注入に用いる装置は特に限定されないが、例えば、主剤と硬化剤を別々に収容する調整容器と、耐圧ホースを介して各調整容器に接続された先端混合室と、先端混合室に接続されたノズルとを有する。主剤及び硬化剤は、それぞれ調整容器から送液ポンプにより耐圧ホ−スを経由して送液される。これら主剤及び硬化剤を先端混合室に４００ｋｇｆ／ｃｍ２以下の圧力で噴射し、均一に混合する。コンクリ−ト構造物の漏水箇所にクラック及びクラックの延長線に沿って構造物の表面から複数削孔した後、これらの削孔箇所にノズルを挿入し、先端混合室で均一に混合された混合液をノズルから注入する。ノズルの先端は、スプリングとボ−ルを装着した逆止弁により均一混合液が逆流しない機能を備えている。この逆止弁は、セラミツクボ−ル及び耐酸ウレタン保護塗膜で保護されていることが、耐久性の点から好ましい。 More specifically, it comprises a main agent containing (meth) acrylate components (A, B and C components), a reducing agent and the like, and a curing agent such as an oxidizing agent and glycols, and these are mixed at the time of use. . Therefore, the waterstop agent composition of the present invention is generally used as a two-liquid mixing system. When the amount of water leakage is not large, a diluent such as water can be added up to 30% by mass in either or both of the main agent and the curing agent. The apparatus used for injection is not particularly limited. For example, an adjustment container that separately accommodates the main agent and the curing agent, a tip mixing chamber connected to each adjustment container via a pressure hose, and a nozzle connected to the tip mixing chamber And have. The main agent and the curing agent are respectively sent from the adjustment container via the pressure hose by the liquid feed pump. These main agent and curing agent are sprayed into the tip mixing chamber at a pressure of 400 kgf / cm 2 or less and mixed uniformly. After a plurality of holes are drilled from the surface of the structure along the cracks and extension lines of the cracks at the water leakage points of the concrete structure, a nozzle is inserted into these holes and mixed uniformly in the tip mixing chamber Liquid is injected from the nozzle. The tip of the nozzle has a function to prevent the uniform mixture from flowing back by a check valve equipped with a spring and a ball. The check valve is preferably protected by a ceramic ball and an acid-resistant urethane protective coating film from the viewpoint of durability.
ノズルから均一混合液を吐出する際の吐出圧は、先端混合室における混合と同様に４００ｋｇｆ／ｃｍ２以下であるが、ヘヤ−クラック幅を対象とした漏水を止水する場合は、２００ｋｇｆ／ｃｍ２以上であることが好ましい。なお、注入ノズルは、注入の際には急結セメントで固定し、注入ノズルの抜去後、削孔空間には無収縮セメントモルタルを充填し、封鎖するのが一般的である。また、止水後、クラツクは無収縮セメントモルタルで幅約２０ｍｍで塗り付けることにより処理することが一般的である。 The discharge pressure at the time of discharging the uniform mixed solution from the nozzle is 400 kgf / cm 2 or less similarly to the mixing in the front end mixing chamber, but 200 kgf / cm when water leakage for the hair crack width is stopped. It is preferable that it is 2 or more. In general, the injection nozzle is fixed with quick setting cement during injection, and after the injection nozzle is removed, the drilling space is filled with non-shrinkage cement mortar and sealed. Further, after the water is stopped, the crack is generally treated by applying a non-shrinkage cement mortar with a width of about 20 mm.
本発明の止水剤組成物の使用方法は上記に限定されない。本発明は土質安定剤として広く使用することが可能であり、例えば、本発明の止水組成物は、人工建造物の他、岩盤等に注入して土質安定剤として使用することもできるし、土壌成分（砂、小石、泥、土等）と混合して該土壌成分を固めることもできる。上述したセメントを添加した本発明の止水性組成物は、いわゆるポリマーセメントとして、通常のセメント材料と同様の使用方法、例えば、塗布、流し込み、充填又は注入して使用することもできる。また、セメントを添加した本発明の止水性組成物としては、砂、砂利、砕砂、砕石、スラグ骨材、その他これらに類似の細骨材を１種以上添加し、いわゆるモルタルとして使用することもできる。 The method for using the waterstop agent composition of the present invention is not limited to the above. The present invention can be widely used as a soil stabilizer, for example, the water-stopping composition of the present invention can be used as a soil stabilizer by being injected into a rock or the like in addition to an artificial building, It can also be solidified by mixing with soil components (sand, pebbles, mud, soil, etc.). The water-stopping composition of the present invention to which the above-mentioned cement is added can also be used as a so-called polymer cement in the same manner of use as a normal cement material, for example, coating, pouring, filling or pouring. In addition, as the water-stopping composition of the present invention to which cement is added, one or more kinds of sand, gravel, crushed sand, crushed stone, slag aggregate, and other fine aggregates similar to these may be added and used as so-called mortar. it can.
［実施例］
次に、本発明の実施例により説明するが、本発明はこれに限定されるものではない。実施例中の「部」は特に断らない限り「質量部」である。
[Example]
Next, although an example of the present invention explains, the present invention is not limited to this. The “parts” in the examples are “parts by mass” unless otherwise specified.
‐ＰＥＧ＃３５０モノメタアクリレ−ト（エチレンオキサイド付加モル数８）（Ａ）
‐ＰＥＧ＃４００ジメタアクリ−ト（エチレンオキサイド付加モル数９）（Ｂ）
‐アクリル酸マグネシウム（固形分換算）（Ｃ）
‐酸化剤・過硫酸アンモニウム
‐還元剤・トリエタノ−ルアミン（５０％濃度水溶液）及び
‐水
を表１の配合比（実施例１−１、１−２、比較例１−３、１−４）で混合して止水剤組成物を得た。
-PEG # 350 monomethacrylate (8 ethylene oxide addition moles) (A)
-PEG # 400 dimethacrylate (ethylene oxide addition mole number 9) (B)
-Magnesium acrylate (solid content conversion) (C)
-Oxidizing agent-Ammonium persulfate-Reducing agent-Triethanolamine (50% strength aqueous solution) and-In the mixing ratios of Table 1 (Examples 1-1, 1-2, Comparative Examples 1-3, 1-4) A water-stopper composition was obtained by mixing.
その特性（環境条件別重量変化率、５０％圧縮時復元性、ゲルタイム、５０％圧縮変形時負荷応力）を下記のようにして測定し。評価した。表１に測定結果を示す。 The characteristics (weight change rate according to environmental conditions, 50% compression restoring property, gel time, 50% compressive deformation load stress) were measured as follows. evaluated. Table 1 shows the measurement results.
［評価方法］
１）環境条件別重量変化率;
２００ｍｌポリエチレン容器（直径×高さ＝７０ｍｍ×８０ｍｍ）に、得られた止水剤組成物を１００ｍｌの容量を充填、硬化させた（硬化条件；温度２０℃、相対湿度５０％）。２時間後脱型し、下記環境条件中に７日間放置し、重量変化率を測定した。
[Evaluation method]
1) Weight change rate according to environmental conditions;
A 200 ml polyethylene container (diameter × height = 70 mm × 80 mm) was filled with 100 ml of the obtained water-stopper composition and cured (curing conditions; temperature 20 ° C., relative humidity 50%). After 2 hours, the mold was removed and left for 7 days in the following environmental conditions, and the weight change rate was measured.
重量変化率（％）＝（［Ｗｔ／（Ｗｔ−Ｗ０）］×１００）
［但し、Ｗ０；初期重量（ｇ）、Ｗｔ；７日放置後の重量（ｇ）］
Weight change rate (%) = ([W t / (W t −W 0 )] × 100)
[W 0 ; initial weight (g), W t ; weight after standing for 7 days (g)]
水中：２５℃恒温水槽水中浸漬
気中（大気中）：恒温恒高湿（温度２５℃、湿度５０％）放置
気中→水中：気中恒温恒湿（温度２５℃、湿度５０％）７日放置後、２５℃恒温水
槽中に７日放置後、測定。
Underwater: 25 ° C constant temperature water bath immersion in air (in air): constant temperature and high humidity (temperature 25 ° C, humidity 50%) left in air → water: constant temperature and humidity in air (temperature 25 ° C, humidity 50%) 7 days After standing, measured after standing in a constant temperature water bath at 25 ° C for 7 days.
２）５０％圧縮率後復元性：
内面に離型用ポリエステルフィルム（東レ製マイラ−フィルム、厚み１００μｍ）を巻いた底部密閉二つ割り鋼製モ−ルド（内径×高さ＝３５ｍｍ×５０ｍｍ、モ−ルド厚み５ｍｍ）に各実施例の止水剤組成物を充填し、硬化させた（硬化条件；温度２０℃、相対湿度５０％）。２時間後脱型して供試体とし、圧縮試験機により圧縮速度５ｍｍ／分で圧縮応力を負荷して５０％変形後、圧縮負荷を開放し、初期寸法回復時間を測定した。
2) Restorability after 50% compression ratio:
Stopping of each example on a bottom sealed split steel mold (inner diameter × height = 35 mm × 50 mm, mold thickness 5 mm) with a release polyester film (Toray Mylar film, thickness 100 μm) wound on the inner surface The liquid medicine composition was filled and cured (curing conditions; temperature 20 ° C., relative humidity 50%). After 2 hours, it was demolded to give a specimen, and after applying a compressive stress at a compression rate of 5 mm / min by a compression tester to deform 50%, the compression load was released and the initial dimension recovery time was measured.
３）耐衝撃性・落錘時クラック発生有無：
ＪＩＳ−Ｋ−５４００（塗料一般試験方法）記載の耐衝撃性のデュポン式試験に準拠して実施した。供試体サイズは、φ３５ｍｍ×高さ５０ｍｍの円盤状である。鋼球重量は３００ｇ、落下高さは３００ｍｍとし、供試体の破壊、クラックの有無を観察した。
3) Impact resistance / cracking when falling weight:
The test was carried out in accordance with the DuPont test for impact resistance described in JIS-K-5400 (Paint General Test Method). The specimen size is a disk shape of φ35 mm × height 50 mm. The steel ball weight was 300 g, the drop height was 300 mm, and the presence or absence of cracks and cracks in the specimens were observed.
４）ゲルタイム：
試験管（直径φ２０ｍｍ、高さ１５０ｍｍ）に２０ｍｌ容量の配合物を充填し、２５℃の環境温度で流動性が消失までの時間、すなわち、直径５ｍｍ、長さ２００ｍｍのガラス棒の先端を配合物の表面から５ｍｍの深さに挿入してから、２秒間に１回表面に引き上げ、次いで前記の所定の深さに挿入を繰り返し、ガラス棒の先端から配合物の糸引きが無くなった時間をゲルタイムとした。
4) Gel time:
A test tube (diameter: 20 mm, height: 150 mm) is filled with 20 ml of the composition, and the time until fluidity disappears at an environmental temperature of 25 ° C., that is, the tip of a glass rod having a diameter of 5 mm and a length of 200 mm is formulated. Inserted at a depth of 5 mm from the surface of the glass, pulled up to the surface once every 2 seconds, and then repeated insertion to the predetermined depth, and the time when there was no stringing of the compound from the tip of the glass rod was gel time It was.
５）５０％圧縮率時負荷応力：
実施例１の供試体サイズで、実施例１と同一条件で５０％圧縮率変形まで負荷した時の負荷応力を測定した。
5) Load stress at 50% compressibility:
With the specimen size of Example 1, the load stress was measured when loading up to 50% compressibility deformation under the same conditions as in Example 1.
その測定結果を、表１に示す。 The measurement results are shown in Table 1.
なお、５０％圧縮率時負荷応力の欄中「‐」は、５０％圧縮応力負荷がかかる前にゲル化物が破壊されたことを示す。 In the column of 50% compressive load stress, “-” indicates that the gelled product was broken before 50% compressive stress was applied.
‐ＰＥＧ＃３５０モノメタアクリレ−ト（エチレンオキサイド付加モル数８）（Ａ）
‐ＰＥＧ＃６００ジメタアクリレ−ト（エチレンオキサイド付加モル数１４）（Ｂ）
‐アクリル酸マグネシウム（固形分換算）（Ｃ）
‐グリコ−ル類（エチレングリコ−ル）（Ｄ）
‐酸化剤・過硫酸アンモニウム
‐トリエタノ−ルアミン（５０％濃度水溶液）及び
‐水
を、表２の配合比（実施例２−１、２−２、比較例２−３、２−４）で混合して止水剤組成物を得た。
-PEG # 350 monomethacrylate (8 ethylene oxide addition moles) (A)
-PEG # 600 dimethacrylate (ethylene oxide addition mole number 14) (B)
-Magnesium acrylate (solid content conversion) (C)
-Glycols (ethylene glycol) (D)
-Oxidizing agent-Ammonium persulfate-Triethanolamine (50% strength aqueous solution) and-Water were mixed in the mixing ratios shown in Table 2 (Examples 2-1 and 2-2, Comparative Examples 2-3 and 2-4). Thus, a waterstop agent composition was obtained.
得られた止水剤組成物について、浸漬条件別経時重量変化率を測定した。なお、環境条件別重量変化率の評価方法は、水中又は気中に放置する時間を下記表３のように変えた以外は実施例１記載の通り行った。 About the obtained water-stopper composition, the time-dependent weight change rate according to immersion conditions was measured. In addition, the evaluation method of the weight change rate according to environmental conditions was performed as described in Example 1 except that the time for standing in water or in the air was changed as shown in Table 3 below.
測定結果を表３に示す。 Table 3 shows the measurement results.
上記表中の「気中‐水中」は、供試体作成後室温（２０℃）、湿度５５％の気中に７日間放置してから，水中に表３の浸漬時間の放置後の重量変化率である。 “Air-in-water” in the above table is the rate of change in weight after leaving the test piece in room temperature (20 ° C.) and humidity of 55% for 7 days and then leaving it in water for 3 days. It is.
‐ＰＥＧ＃３５０モノメタアクリレ−ト（エチレンオキサイド付加モル数８）（Ａ）
‐ＰＥＧ＃４００ジメタアクリレ−ト（エチレンオキサイド付加モル数９）（Ｂ）
‐アクリル酸アルミニウム（固形分換算）（Ｃ）
‐グリコ−ル類（エチレングリコ−ル、プロピレングリコ−ル）（Ｄ）
‐酸化剤・過硫酸アンモニウム
‐還元剤・トリエタノ−ルアミン（５０％濃度水溶液）及び
‐水
を表４の配合（実施例３−１、３−２、３−３、比較例３−４、３−５、３−６、３−７）で混合して止水剤組成物を得た。
-PEG # 350 monomethacrylate (8 ethylene oxide addition moles) (A)
-PEG # 400 dimethacrylate (ethylene oxide addition mole number 9) (B)
-Aluminum acrylate (solid content conversion) (C)
-Glycols (ethylene glycol, propylene glycol) (D)
-Oxidizing agent-Ammonium persulfate-Reducing agent-Triethanolamine (50% strength aqueous solution) and-Formulation of Table 4 (Examples 3-1, 3-2, 3-3, Comparative Examples 3-4, 3- 5, 3-6, 3-7) to obtain a waterstop agent composition.
得られた止水剤組成物について、実施例１記載と同じ評価方法で５０％圧縮率後復元性、耐衝撃性・落錘時クラック発生有無、ゲルタイムを測定した。 About the obtained water-stopper composition, the same evaluation method as described in Example 1 was used to measure 50% compressibility after restoration, impact resistance, occurrence of cracks when falling weight, and gel time.
測定結果を表４に示す。 Table 4 shows the measurement results.
‐ＰＥＧ＃３５０モノメタアクリレ−ト（エチレンオキサイド付加モル数８）（Ａ）
‐ＰＥＧ＃１０００ジメタアクリレ−ト（エチレンオキサイド付加モル数２３）（Ｂ）
‐アクリル酸マグネシウム（固形分換算）（Ｃ）
‐グリコ−ル類（エチレングリコ−ル、プロピレングリコ−ル）（Ｄ）
‐水硬化性セメント（普通ポルトランドセメント）
‐酸化剤・過硫酸アンモニウム
‐還元剤・トリエタノ−ルアミン（５０％濃度水溶液）及び
‐水
を表５の配合比（実施例４−１、４−２、４−３、４−４、比較例４−５、４−６）で、混合して止水剤組成物を得た。
-PEG # 350 monomethacrylate (8 ethylene oxide addition moles) (A)
-PEG # 1000 dimethacrylate (ethylene oxide addition mole number 23) (B)
-Magnesium acrylate (solid content conversion) (C)
-Glycols (ethylene glycol, propylene glycol) (D)
-Water curable cement (ordinary Portland cement)
-Oxidizing agent / ammonium persulfate-Reducing agent-Triethanolamine (50% strength aqueous solution) and-Mixing ratio of Table 5 (Examples 4-1, 4-2, 4-3, 4-4, Comparative Example 4) -5, 4-6) to obtain a waterstop agent composition.
得られた止水剤組成物について、破壊時圧縮強度、ゲルタイムを測定した。ゲルタイムは実施例１に記載の測定方法と同じである。 About the obtained water-stopper composition, the compressive strength at break and the gel time were measured. The gel time is the same as the measurement method described in Example 1.
［評価方法］
１）破壊時圧縮強度；
二つ割り鋼性モ−ルド（内径×高さ＝５０ｍｍ×１００ｍｍ）に表５の止水剤組成物を充填、硬化させた。（硬化条件；温度２０℃、相対湿度５０％）。２４時間後に脱型し供試体とした。圧縮試験機で圧縮速度５ｍｍ／分で圧縮応力を負荷して、破壊時圧縮強度を測定した。
[Evaluation method]
1) Compressive strength at break;
A split steel composition (inner diameter × height = 50 mm × 100 mm) was filled with the water-stopper composition shown in Table 5 and cured. (Curing conditions; temperature 20 ° C., relative humidity 50%). After 24 hours, the mold was removed to obtain a specimen. A compressive stress was applied at a compression rate of 5 mm / min with a compression tester, and the compressive strength at break was measured.
その測定結果を表５に示す。 The measurement results are shown in Table 5.
［評価方法］
尚、上記実施例で使用した樹脂濃度（％）は、水硬性セメントを除外した濃度であって、その算出方法は下記の通りである：
樹脂濃度（％）＝〔［（Ａ）+（Ｂ）+（Ｃ）］／［（Ａ）+（Ｂ）+（Ｃ）÷０．３５（０．１）+酸化剤+還元剤+水］〕×１００
[Evaluation method]
The resin concentration (%) used in the above examples is a concentration excluding hydraulic cement, and the calculation method is as follows:
Resin concentration (%) = [[(A) + (B) + (C)] / [(A) + (B) + (C) ÷ 0.35 (0.1) + oxidant + reducing agent + water ] X 100
また、表中の、アクリル酸マグネシウムは３５％濃度水溶液、アクリル酸アルミニウムは１０％濃度水溶液である。そのため、アクリル酸マグネシウムを使用した場合は（Ｃ）成分に０．３を乗じ、アクリル酸アルミニウムを使用した場合は（Ｃ）成分に０．１を乗じて樹脂濃度を算出した。 In the table, magnesium acrylate is a 35% strength aqueous solution, and aluminum acrylate is a 10% strength aqueous solution. Therefore, the resin concentration was calculated by multiplying the component (C) by 0.3 when magnesium acrylate was used, and by multiplying the component (C) by 0.1 when aluminum acrylate was used.
‐ＰＥＧ＃３５０モノメタアクリレ−ト（エチレンオキサイド付加モル数８）（Ａ）
‐ＰＥＧ＃１０００ジメタアクリレ−ト（エチレンオキサイド付加モル数１４）（Ｂ）
‐アクリル酸マグネシウム（固形分換算）（Ｃ）
‐グリコ−ル類（エチレングリコ−ル、プロピレングリコ−ル）（Ｄ）
‐酸化剤・過硫酸アンモニウム
‐還元剤・トリエタノ−ルアミン（５０％濃度水溶液）及び
‐水
を表６の配合比（実施例５−１、５−２、５−３、比較例５−４、５−５）で混合して止水剤組成物を得た。
-PEG # 350 monomethacrylate (8 ethylene oxide addition moles) (A)
-PEG # 1000 dimethacrylate (ethylene oxide addition mole number 14) (B)
-Magnesium acrylate (solid content conversion) (C)
-Glycols (ethylene glycol, propylene glycol) (D)
-Oxidizing agent, ammonium persulfate-Reducing agent, triethanolamine (50% strength aqueous solution) and-Water in the mixing ratios of Table 6 (Examples 5-1, 5-2, 5-3, Comparative Examples 5-4, 5) The water-stopper composition was obtained by mixing in -5).
１００ｍｌ鋼製型枠（直径×高さ＝３５ｍｍ×１００ｍｍ）に、得られ止水剤組成物を５０ｍｌの容量を充填、硬化させた。(硬化条件:温度２０℃、相対湿度５０％)。２時間後脱型し、２５℃恒温水槽水中に７日間及び３６５日間の放置し、実施例４と同じ条件で破壊時圧縮強度を測定し、実施例１と同じ条件で５０％圧縮率後の初期圧縮寸法回復時間を測定した。測定結果を表６に示す。 A 100 ml steel mold (diameter × height = 35 mm × 100 mm) was filled and cured with a volume of 50 ml of the obtained water-stopper composition. (Curing conditions: temperature 20 ° C., relative humidity 50%). After 2 hours, it was demolded, and left in 25 ° C. constant temperature water bath for 7 days and 365 days. The compressive strength at break was measured under the same conditions as in Example 4, and after 50% compression under the same conditions as in Example 1. Initial compression dimension recovery time was measured. Table 6 shows the measurement results.
‐ＰＥＧ＃３５０モノメタアクリレ−ト（エチレンオキサイド付加モル数８）（Ａ）
‐ＰＥＧ＃１０００ジメタアクリレ−ト（エチレンオキサイド付加モル数１４）（Ｂ）
‐アクリル酸マグネシウム（固形分換算）（Ｃ）
‐グリコ−ル類（エチレングリコ−ル）（Ｄ）
‐酸化剤・過硫酸アンモニウム
‐還元剤・トリエタノ−ルアミン（５０％濃度水溶液）及び
‐水
を表７の配合比（実施例６−１、６−２、比較例６−３、６−４）で混合して止水剤組成物を得た。
-PEG # 350 monomethacrylate (8 ethylene oxide addition moles) (A)
-PEG # 1000 dimethacrylate (ethylene oxide addition mole number 14) (B)
-Magnesium acrylate (solid content conversion) (C)
-Glycols (ethylene glycol) (D)
-Oxidizing agent, ammonium persulfate-Reducing agent, triethanolamine (50% strength aqueous solution) and-Water in the mixing ratios shown in Table 7 (Examples 6-1 and 6-2, Comparative Examples 6-3 and 6-4) A water-stopper composition was obtained by mixing.
鋼製２つ割りモ−ルド（直径×高さ＝１００ｍｍ×５００ｍｍ）の垂直方向に、上端から１００ｍｍ、上端から下端に向けて４００ｍｍの各箇所に金網と多孔板の二層構成体を設置し、上記二層構成体の間の長さ３００ｍｍに川砂（６０％径１．８０ｍｍ、３０％径１．０ｍｍ、１０％径０．６５ｍｍ、均等係数２．７７、比重２．６７）を充填し、これに一定水頭、すなわち一定水圧（水頭差）の水を送り、モ−ルド下部の流量調節コックを操作して上部から下部への一定流速の動水状態を作り出し、その中に止水剤組成物１５０ｍｌ、注入圧力０．０１〜０．０２ＭＰａ、注入時間１分で注入管（内径５ｍｍ、外径７ｍｍの注入管を上端から１５０ｍｍの位置を先端開口にして注入した。 A two-layer structure consisting of a metal mesh and a perforated plate is installed at each position of 100 mm from the upper end and 400 mm from the upper end to the lower end in the vertical direction of the steel split mold (diameter x height = 100 mm x 500 mm). In addition, river sand (60% diameter 1.80 mm, 30% diameter 1.0 mm, 10% diameter 0.65 mm, uniformity coefficient 2.77, specific gravity 2.67) is filled into a length of 300 mm between the two-layer structure. A constant water head, that is, water with a constant water pressure (water head difference) is sent to this, and a flow control cock at the bottom of the mold is operated to create a hydrodynamic state with a constant flow rate from the upper part to the lower part. 150 ml of the composition, an injection pressure of 0.01 to 0.02 MPa, and an injection time of 1 minute were injected into an injection tube (inner tube with an inner diameter of 5 mm and an outer diameter of 7 mm, with the position 150 mm from the upper end being the tip opening).
主剤液と硬化剤液を等量比で二液一工程方式で注入した。実施例６−１〜６−２は川砂層間流速が２ｃｍ／秒でも有効固結率１００％を維持したが、比較例６−３〜６−４では流速が０．５ｃｍ／秒で有効固結率５０％以下の動水固結特性の測定結果であった。 The main agent solution and the curing agent solution were injected in an equal ratio by a two-component one-step method. In Examples 6-1 to 6-2, the effective consolidation rate was maintained at 100% even when the river sand interlayer flow rate was 2 cm / second, but in Comparative Examples 6-3 to 6-4, the effective flow rate was 0.5 cm / second. It was a measurement result of the dynamic water consolidation characteristics with a rate of 50% or less.
測定結果を表７に示す。 Table 7 shows the measurement results.
［評価方法］
尚、上記実施例で使用された有効固結率は、静水状態での止水剤組成物注入後の固結率を１００％として、動水状態での注入後の固結容積を測定し、前者対比で有効固結率を測定した。
[Evaluation method]
In addition, the effective consolidation rate used in the above-mentioned examples is to set the consolidation rate after injection of the water-stopper composition in the still water state as 100%, and measure the consolidation volume after injection in the hydrodynamic state, The effective consolidation rate was measured in comparison with the former.
以上の結果より、本発明の止水剤組成物は、そのゲル化生成物の、水中、空気中、及び空気中放置後の水中における重量変化率が良好であり、圧縮復元性及び長期圧縮復元性、動水固結性、耐衝撃性にも優れている。またこのような良好な特性が、ポリエチレングリコ−ル（ＰＥＧ）モノ（メタ）アクリレ−ト及びポリエチレングリコ−ル（ＰＥＧ）ジ（メタ）アクリレ−ト並びに末端（メタ）アクリロイル基含有多価金属塩を本発明の特定範囲の臨界的意義も明らかである。さらに、表５から水硬性セメントなどのセメントとの使用にも支障がないことも分かる。 From the above results, the water-stopper composition of the present invention has a good rate of weight change of the gelled product in water, air, and water after standing in the air, compression recovery and long-term compression recovery. Excellent in water resistance, dynamic water consolidation, and impact resistance. In addition, such good characteristics are obtained by using polyethylene glycol (PEG) mono (meth) acrylate and polyethylene glycol (PEG) di (meth) acrylate and terminal (meth) acryloyl group-containing polyvalent metal salt. The critical significance of the specific range of the present invention is also clear. Furthermore, it can be seen from Table 5 that there is no hindrance to use with cement such as hydraulic cement.
Claims (6)
（式中、Ｒ１は水素原子又はメチル基でｎは２以上で５０以下の整数）
で表される化合物の単独もしくは混合物からなる成分１０質量部〜４０質量部と、
（Ｂ）一般式（ｂ）
（式中、Ｒ２、Ｒ３はそれぞれ水素原子又はメチル基でｍが２以上で５０以下の整数）で表される化合物の単独もしくは混合物からなる成分２０質量部〜５０質量部と、
（Ｃ）末端（メタ）アクリロイル基含有多価金属塩からなる成分１５〜５０質量部と、を含有し、
（Ａ）、（Ｂ）及び（Ｃ）成分の合計が１００質量部であり、かつ、
（Ｂ）成分の質量が、（Ａ）成分の質量と同じかそれよりも多い止水剤組成物。 (A) General formula (a)
(Wherein R 1 is a hydrogen atom or a methyl group, and n is an integer of 2 to 50)
10 to 40 parts by mass of a component consisting of a single compound or a mixture of
(B) General formula (b)
(C) 15 to 50 parts by mass of a component consisting of a terminal (meth) acryloyl group-containing polyvalent metal salt,
The sum of (A), (B) and (C) components is 100 parts by weight, and
(B) The water-stopping agent composition whose mass of a component is the same as that of the mass of (A) component, or more.
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| JP2019203094A (en) * | 2018-05-24 | 2019-11-28 | 東亞合成株式会社 | Soil improver composition and use thereof |
| JP2022035626A (en) * | 2020-08-21 | 2022-03-04 | 株式会社エヌ・エス・テック | Water stop agent composition and elastic water stop material as cured product thereof |
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|---|---|---|---|---|
| JPS5319615A (en) * | 1976-08-06 | 1978-02-23 | Mitsui Toatsu Chemicals | Water stopping agent |
| JPS58206680A (en) * | 1982-05-26 | 1983-12-01 | Mitsui Toatsu Chem Inc | Water-stopping agent |
| JPS61221281A (en) * | 1985-03-27 | 1986-10-01 | Nitto Chem Ind Co Ltd | Water stopping agent |
| JPS61231081A (en) * | 1985-04-06 | 1986-10-15 | Mitsui Toatsu Chem Inc | Waterproofing agent |
| JPS6234977A (en) * | 1985-08-08 | 1987-02-14 | Mitsui Toatsu Chem Inc | Water stopping agent |
| JP3082966B2 (en) * | 1991-07-08 | 2000-09-04 | 第一工業製薬株式会社 | Water stopping agent |
| JPH0517773A (en) * | 1991-07-15 | 1993-01-26 | Dai Ichi Kogyo Seiyaku Co Ltd | Water stopping agent |
| JP3970604B2 (en) * | 2001-12-26 | 2007-09-05 | 三菱レイヨン株式会社 | Water-stop agent and water-stop method |
| JP2004124063A (en) * | 2002-08-02 | 2004-04-22 | Toagosei Co Ltd | Aqueous solution of water-stop material |
| JP2004115646A (en) * | 2002-09-26 | 2004-04-15 | Aqua Guard:Kk | Water sealant |
| JP4916695B2 (en) * | 2005-10-05 | 2012-04-18 | 吉佳株式会社 | Waterstop composition |
| JP6284812B2 (en) * | 2014-04-18 | 2018-02-28 | ライト工業株式会社 | Water-stopping composition and water-stopping method |
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2015
- 2015-11-26 JP JP2015230303A patent/JP6074484B1/en active Active
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| JP2019203094A (en) * | 2018-05-24 | 2019-11-28 | 東亞合成株式会社 | Soil improver composition and use thereof |
| JP7063114B2 (en) | 2018-05-24 | 2022-05-09 | 東亞合成株式会社 | Ground improver composition and its use |
| CN109265603A (en) * | 2018-08-28 | 2019-01-25 | 南通职业大学 | A kind of salinized soil solidification acrylate copolymer emulsion, preparation method and application |
| CN109265603B (en) * | 2018-08-28 | 2021-01-26 | 南通职业大学 | Acrylate copolymer emulsion for curing saline soil, preparation method and application |
| JP2022035626A (en) * | 2020-08-21 | 2022-03-04 | 株式会社エヌ・エス・テック | Water stop agent composition and elastic water stop material as cured product thereof |
| JP7440847B2 (en) | 2020-08-21 | 2024-02-29 | 株式会社エヌ・エス・テック | Water stop agent composition and elastic water stop material as its cured product |
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