JP6501724B2 - Dispersion liquid for filler for concrete structure, method for producing filler for concrete structure, and method for producing concrete structure - Google Patents

Dispersion liquid for filler for concrete structure, method for producing filler for concrete structure, and method for producing concrete structure Download PDF

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JP6501724B2
JP6501724B2 JP2016074285A JP2016074285A JP6501724B2 JP 6501724 B2 JP6501724 B2 JP 6501724B2 JP 2016074285 A JP2016074285 A JP 2016074285A JP 2016074285 A JP2016074285 A JP 2016074285A JP 6501724 B2 JP6501724 B2 JP 6501724B2
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concrete structure
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JP2017186182A (en
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武久　敢
敢 武久
山本　卓司
卓司 山本
松本　高志
高志 松本
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DIC Corp
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/10—Clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/20—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds

Description

本発明は、湿潤面付着性等の各種物性に優れるコンクリート構造体用充填材、コンクリート構造体、及びそれらの製造方法に関する。   The present invention relates to a filler for a concrete structure, which is excellent in various physical properties such as wet surface adhesion, a concrete structure, and a method for producing them.

従来、コンクリート構造物継目やひび割れに対し、各種の充填材が提案されてきた。しかしながら、複雑形状部や湿潤面では付着自体が難しく、また、構造物の季節変動による伸縮に追従できず、剥離、脆性破壊が生じる問題があった。   Heretofore, various fillers have been proposed for concrete structure joints and cracks. However, the adhesion itself is difficult in a complex shape portion or a wet surface, and the expansion and contraction due to the seasonal fluctuation of the structure can not be followed, and there is a problem that peeling and brittle fracture occur.

これらの問題に対し、長期間止水機能を維持し、かつ安価な止水材として、ベントナイト、熱可塑性樹脂、可塑剤、吸水性樹脂を主原料として配合して成形した止水材が提案されている（例えば、特許文献１参照。）。しかしながら、この止水材は湿潤面での付着性が不十分であることから、接着剤を必要とする問題や、複雑形状部への使用には不適である問題があった。   To solve these problems, a water blocking material is proposed which is formed by combining bentonite, a thermoplastic resin, a plasticizer, and a water absorbing resin as main raw materials as a low cost water blocking material that maintains the water blocking function for a long time and is inexpensive. (See, for example, Patent Document 1). However, since the water blocking material has insufficient adhesion on the wet surface, it has problems of requiring an adhesive and being unsuitable for use in a complex shape.

そこで、作業性に優れ、複雑形状や湿潤面においても優れた付着性を発揮し得る充填材が求められていた。   Therefore, there has been a demand for a filler which is excellent in workability and can exhibit excellent adhesion even in complicated shapes and wet surfaces.

特開２００６−５７２７５号公報JP, 2006-57275, A

本発明が解決しようとする課題は、作業性に優れ、難燃性であり、湿潤面付着性、伸縮追従性等の各種物性に優れるコンクリート構造体用充填材、その充填材により間隙を充填されたコンクリート構造体、及びそれらの製造方法を提供することである。   The problem to be solved by the present invention is a filler for a concrete structure, which is excellent in workability, flame retardancy, and excellent in various physical properties such as wet surface adhesion, stretchability, and the like, and the filler is used to fill the gap The present invention provides a concrete structure and a method of manufacturing the same.

本発明者等は、特定の高分子ヒドロゲルを含有するコンクリート構造体用充填材が、作業性に優れ、難燃性であり、湿潤面付着性、伸縮追従性等の各種物性に優れることを見出し、本発明を完成した。   The present inventors have found that a filler for a concrete structure containing a specific polymer hydrogel is excellent in workability, flame retardancy, and excellent in various physical properties such as wet surface adhesion and stretchability. , Completed the present invention.

すなわち、本発明は、水溶性有機モノマーの重合体及び水膨潤性粘土鉱物により形成された三次元網目構造を有する高分子ヒドロゲル（Ａ）を含有することを特徴とするコンクリート構造体用充填材を提供するものである。   That is, the present invention comprises a polymer hydrogel (A) having a three-dimensional network structure formed of a polymer of a water-soluble organic monomer and a water-swellable clay mineral. It is provided.

本発明のコンクリート構造体用充填材は、作業性に優れ、難燃性であり、コンクリート湿潤面への付着性、伸縮追従性等の各種物性に優れることから、トンネル、道路、橋梁、軌道、ビル、護岸、上下水道等のコンクリート構造物の充填材として、また、それらの補修材として用いることができる。   The filler for a concrete structure according to the present invention is excellent in workability, is flame retardant, and is excellent in various physical properties such as adhesion to the wet surface of the concrete and followability to expansion and contraction, tunnels, roads, bridges, tracks, It can be used as a filler for concrete structures such as buildings, revetments, water and sewage, and as a repair material for them.

本発明のコンクリート構造体用充填材は、水溶性有機モノマーの重合体及び水膨潤性粘土鉱物により形成された三次元網目構造を有する高分子ヒドロゲル（Ａ）を含有するものである。   The filler for a concrete structure of the present invention contains a polymer hydrogel (A) having a three-dimensional network structure formed of a polymer of a water-soluble organic monomer and a water-swellable clay mineral.

前記高分子ヒドロゲル（Ａ）の製造方法としては、簡便に三次元網目構造を有する高分子ヒドロゲルが得られることから、水溶性有機モノマーと、水膨潤性粘土鉱物と、重合開始剤と、水とを含む分散液（ａ）中で、水溶性有機モノマーを重合させる方法が好ましい。得られた水溶性有機モノマーの重合体は水膨潤性粘土鉱物ととともに三次元網目構造を形成し、前記高分子ヒドロゲル（Ａ）の構成要素となる。   As a method for producing the polymer hydrogel (A), a polymer hydrogel having a three-dimensional network structure can be easily obtained, and thus, a water-soluble organic monomer, a water-swellable clay mineral, a polymerization initiator, and water The method of polymerizing the water-soluble organic monomer in the dispersion liquid (a) containing The polymer of the water-soluble organic monomer thus obtained forms a three-dimensional network structure together with the water-swellable clay mineral, and becomes a component of the polymer hydrogel (A).

前記水溶性有機モノマーとしては、特に制限されないが、（メタ）アクリルアミド基を有するモノマー、（メタ）アクリロイルオキシ基を有するモノマー、ヒドロキシル基を有するアクリルモノマー等が挙げられる。   The water-soluble organic monomer is not particularly limited, and examples thereof include a monomer having a (meth) acrylamide group, a monomer having a (meth) acryloyloxy group, and an acrylic monomer having a hydroxyl group.

前記（メタ）アクリルアミド基を有するモノマーとしては、例えば、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−シクロプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピルアクリルアミド、アクリロイルモルフォリン、メタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミド、Ｎ，Ｎ−ジエチルメタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ−シクロプロピルメタクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルメタクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピルメタクリルアミド等が挙げられる。   Examples of the monomer having a (meth) acrylamide group include acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, and N-cyclopropyl acrylamide. N, N-dimethylaminopropyl acrylamide, N, N-diethylaminopropyl acrylamide, acryloyl morpholine, methacrylamide, N, N-dimethyl methacrylamide, N, N-diethyl methacrylamide, N-methyl methacrylamide, N-ethyl methacrylate Methacrylamide, N-isopropyl methacrylamide, N-cyclopropyl methacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminopropionate Methacrylamide, and the like.

前記（メタ）アクリロイルオキシ基を有するモノマーとしては、例えば、メトキシエチルアクリレート、エトキシエチルアクリレート、メトキシエチルメタクリレート、エトキシエチルメタクリレート、メトキシメチルアクリレート、エトキシメチルアクリレート等が挙げられる。   Examples of the monomer having a (meth) acryloyloxy group include methoxyethyl acrylate, ethoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, methoxymethyl acrylate and ethoxymethyl acrylate.

前記ヒドロキシル基を有するアクリルモノマーとしては、例えば、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート等が挙げられる。   Examples of the acrylic monomer having a hydroxyl group include hydroxyethyl acrylate, hydroxyethyl methacrylate and the like.

これらの中でも、溶解性及び得られる高分子ヒドロゲルの物性の観点から、（メタ）アクリルアミド基を有するモノマーを用いることが好ましく、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、アクリロイルモルフォリンを用いることがより好ましく、Ｎ，Ｎ−ジメチルアクリルアミド、アクリロイルモルフォリンを用いることがさらに好ましく、重合が進行しやすい観点から、Ｎ，Ｎ−ジメチルアクリルアミドが特に好ましい。   Among these, in view of solubility and physical properties of the obtained polymer hydrogel, it is preferable to use a monomer having a (meth) acrylamide group, and acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N- It is more preferable to use isopropyl acrylamide and acryloyl morpholine, it is more preferable to use N, N-dimethyl acrylamide and acryloyl morpholine, and N, N-dimethyl acrylamide is particularly preferable from the viewpoint that polymerization easily proceeds.

なお、上述の水溶性有機モノマーは単独で用いても、２種以上を組み合わせて用いてもよい。   The above-mentioned water-soluble organic monomers may be used alone or in combination of two or more.

前記分散液（ａ）中の水溶性有機モノマーの含有量は、１〜５０質量％であることが好ましく、５〜３０質量％であることがより好ましい。水溶性有機モノマーの含有量が１質量％以上であると、力学物性に優れるヒドロゲルを得ることができることから好ましい。一方、水溶性有機モノマーの含有量が５０質量％以下であると、分散液の調製が容易にできることから好ましい。   The content of the water-soluble organic monomer in the dispersion liquid (a) is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. It is preferable from the ability to obtain a hydrogel excellent in mechanical properties that the content of the water-soluble organic monomer is 1% by mass or more. On the other hand, the content of the water-soluble organic monomer is preferably 50% by mass or less because preparation of the dispersion can be facilitated.

前記水膨潤性粘土鉱物は、上記水溶性有機モノマーの重合体とともに三次元網目構造を形成し、高分子ヒドロゲルの構成要素となる。   The water-swellable clay mineral forms a three-dimensional network structure with the polymer of the water-soluble organic monomer, and becomes a component of a polymer hydrogel.

水膨潤性粘土鉱物としては、特に制限されないが、水膨潤性スメクタイト、水膨潤性雲母等が挙げられる。   The water-swellable clay mineral is not particularly limited, and examples thereof include water-swellable smectite and water-swellable mica.

前記水膨潤性スメクタイトとしては、例えば、水膨潤性ヘクトライト、水膨潤性モンモリロナイト、水膨潤性サポナイト等が挙げられる。   Examples of the water-swellable smectite include water-swellable hectorite, water-swellable montmorillonite, water-swellable saponite and the like.

前記水膨潤性雲母としては、例えば、水膨潤性合成雲母等が挙げられる。   Examples of the water-swellable mica include water-swellable synthetic mica and the like.

これらの中でも、分散液の安定性の観点から、水膨潤性ヘクトライト、水膨潤性モンモリロナイトを用いることが好ましく、水膨潤性ヘクトライトを用いることがより好ましい。   Among these, water-swellable hectorite and water-swellable montmorillonite are preferable from the viewpoint of the stability of the dispersion, and water-swellable hectorite is more preferable.

前記水膨潤性粘土鉱物は、天然由来のもの、合成されたもの、および表面を修飾されたものを用いることもできる。表面を修飾された水膨潤性粘土鉱物としては、例えば、ピロリン酸添加合成ヘクトライト、フッ素変性合成ヘクトライト等が挙げられる。   The water-swellable clay mineral may be of natural origin, synthetic, or surface-modified. Examples of the water-swellable clay mineral whose surface is modified include pyrophosphoric acid-added synthetic hectorite, fluorine-modified synthetic hectorite and the like.

なお、上述の水膨潤性粘土鉱物は単独で用いても、２種以上を組み合わせて用いてもよい。   The above water-swellable clay minerals may be used alone or in combination of two or more.

前記分散液（ａ）中の水膨潤性粘土鉱物の含有量は、１〜２０質量％であることが好ましく、２〜１０質量％であることがより好ましい。水膨潤性粘土鉱物の含有量が１質量％以上であると、力学物性に優れるヒドロゲルを合成できることから好ましい。一方、水膨潤性粘土鉱物の含有量が２０質量％以下であると、分散液の調製が容易にできることから好ましい。   The content of the water-swellable clay mineral in the dispersion (a) is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass. It is preferable from the ability to synthesize a hydrogel excellent in mechanical properties that the content of the water-swellable clay mineral is 1% by mass or more. On the other hand, the content of the water-swellable clay mineral is preferably 20% by mass or less because preparation of the dispersion can be easily performed.

前記重合開始剤としては、特に制限されないが、水溶性の過酸化物、水溶性のアゾ化合物等が挙げられる。   The polymerization initiator is not particularly limited, and examples thereof include water-soluble peroxides and water-soluble azo compounds.

前記水溶性の過酸化物としては、例えば、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸ナトリウム、ｔ−ブチルヒドロペルオキシド等が挙げられる。   Examples of the water-soluble peroxide include potassium peroxodisulfate, ammonium peroxodisulfate, sodium peroxodisulfate, t-butyl hydroperoxide and the like.

前記水溶性のアゾ化合物としては、２，２’−アゾビス（２−メチルプロピオンアミジン）２塩酸塩、４，４’−アゾビス（４−シアノバレリン酸）等が挙げられる。   Examples of the water-soluble azo compound include 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid) and the like.

これらの中でも、水膨潤性粘土鉱物との相互作用の観点から、水溶性の過酸化物を用いることが好ましく、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸ナトリウムを用いることがより好ましく、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸アンモニウムを用いることがさらに好ましい。   Among these, from the viewpoint of interaction with water-swellable clay minerals, it is preferable to use water-soluble peroxides, more preferably potassium peroxodisulfate, ammonium peroxodisulfate and sodium peroxodisulfate, and more preferably peroxo It is more preferable to use potassium disulfate and ammonium peroxodisulfate.

なお、上述の重合開始剤は単独で用いても、２種以上を組み合わせて用いてもよい。   The above-mentioned polymerization initiators may be used alone or in combination of two or more.

前記分散液（ａ）中の前記水溶性有機モノマーに対する前記重合開始剤のモル比（重合開始剤／水溶性有機モノマー）は、好ましくは０．０１以上であり、より好ましくは０．０２〜０．１であり、さらに好ましくは０．０４〜０．１である。   The molar ratio (polymerization initiator / water-soluble organic monomer) of the polymerization initiator to the water-soluble organic monomer in the dispersion (a) is preferably 0.01 or more, more preferably 0.02 to 0 .1, and more preferably 0.04 to 0.1.

前記分散液（ａ）中の重合開始剤の含有量は、０．１〜１０質量％であることが好ましく、０．２〜１０質量％であることがより好ましい。重合開始剤の含有量が０．１質量％以上であると、空気雰囲気下でも有機モノマーの重合が可能となることから好ましい。一方、重合開始剤の含有量が１０質量％以下であると、分散液が重合前に凝集せずに使用することができて、取扱性が向上することから好ましい。   The content of the polymerization initiator in the dispersion liquid (a) is preferably 0.1 to 10% by mass, and more preferably 0.2 to 10% by mass. When the content of the polymerization initiator is 0.1% by mass or more, it is preferable because the polymerization of the organic monomer becomes possible even in the air atmosphere. On the other hand, when the content of the polymerization initiator is 10% by mass or less, the dispersion can be used without aggregation before polymerization, which is preferable because the handling property is improved.

前記分散液（ａ）は、水溶性有機モノマー、水膨潤性粘土鉱物、重合開始剤、及び水を含有するが、必要に応じて、有機溶媒、触媒、有機架橋剤、防腐剤、増粘剤等をさらに含んでいてもよい。   The dispersion (a) contains a water-soluble organic monomer, a water-swellable clay mineral, a polymerization initiator, and water, but if necessary, an organic solvent, a catalyst, an organic crosslinking agent, an antiseptic, a thickener And the like may be further included.

前記有機溶媒としては、メタノール、エタノール、プロパノール、イソプロピルアルコール、１−ブタノール等のアルコール化合物；エチルエーテル、エチレングリコールモノエチルエーテル等のエーテル化合物；ジメチルホルムアミド、Ｎ−メチルピロリドン等のアミド化合物；アセトン、メチルエチルケトン等のケトン化合物などが挙げられる。   Examples of the organic solvent include alcohol compounds such as methanol, ethanol, propanol, isopropyl alcohol and 1-butanol; ether compounds such as ethyl ether and ethylene glycol monoethyl ether; and amide compounds such as dimethylformamide and N-methylpyrrolidone; acetone, Ketone compounds such as methyl ethyl ketone and the like can be mentioned.

これらの中でも、水膨潤性粘土鉱物の分散性の観点から、アルコール化合物を用いることが好ましく、メタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコールを用いることがより好ましく、メタノール、エタノールを用いることがさらに好ましい。   Among these, from the viewpoint of dispersibility of water-swellable clay minerals, alcohol compounds are preferably used, methanol, ethanol, n-propyl alcohol and isopropyl alcohol are more preferably used, and methanol and ethanol are further used. preferable.

なお、これらの有機溶媒は単独で用いても、２種以上を組み合わせて用いてもよい。   These organic solvents may be used alone or in combination of two or more.

前記触媒は、水溶性有機モノマーを重合する際に、重合速度を増大させる機能を有する。   The catalyst has a function of increasing the polymerization rate when polymerizing the water-soluble organic monomer.

前記触媒としては、特に制限されないが、３級アミン化合物、チオ硫酸塩、アスコルビン酸類等が挙げられる。   The catalyst is not particularly limited, and examples thereof include tertiary amine compounds, thiosulfates, ascorbic acids and the like.

前記３級アミン化合物としては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、３−ジメチルアミノプロピオニトリル等が挙げられる。   Examples of the tertiary amine compound include N, N, N ', N'-tetramethylethylenediamine, 3-dimethylaminopropionitrile and the like.

前記チオ硫酸塩としては、例えば、チオ硫酸ナトリウム、チオ硫酸アンモニウム等が挙げられる。   Examples of the thiosulfate include sodium thiosulfate, ammonium thiosulfate and the like.

前記アスコルビン酸類としては、例えば、Ｌ−アスコルビン酸、Ｌ−アスコルビン酸ナトリウム等が挙げられる。   Examples of the ascorbic acids include L-ascorbic acid and sodium L-ascorbate.

これらの中でも、分散液の安定性の観点から、３級アミン化合物を用いることが好ましく、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンを用いることがより好ましい。   Among these, from the viewpoint of the stability of the dispersion, it is preferable to use a tertiary amine compound, and it is more preferable to use N, N, N ', N'-tetramethylethylenediamine.

なお、上述の触媒は単独で用いても、２種以上を組み合わせて用いてもよい。   The above-mentioned catalysts may be used alone or in combination of two or more.

触媒を用いる場合における前記分散液（ａ）中の触媒の含有量は、０．０１〜１質量％であることが好ましく、０．０５〜０．５質量％であることがより好ましい。触媒の含有量が０．０１質量％以上であると、得られるヒドロゲルの有機モノマーの合成を効率よく促進できることから好ましい。一方、触媒の含有量が１質量％以下であると、分散液が重合前に凝集せずに使用することができて、取扱性が向上することから好ましい。   When using a catalyst, the content of the catalyst in the dispersion (a) is preferably 0.01 to 1% by mass, and more preferably 0.05 to 0.5% by mass. It is preferable from the ability to accelerate | stimulate synthetic | combination of the organic monomer of the hydrogel obtained as the content of a catalyst is 0.01 mass% or more efficiently. On the other hand, when the content of the catalyst is 1% by mass or less, the dispersion can be used without aggregation before polymerization, which is preferable because the handling property is improved.

前記分散液（ａ）の調製方法としては、例えば、水溶性有機モノマー、水膨潤性粘土鉱物、重合開始剤、水等を一括で混合する方法；水溶性有機モノマーを含有する分散液（ａ１）と重合開始剤を含有する溶液（ａ２）とを別の分散液又は溶液として調製し、使用直前に混合する多液混合方法等が挙げられるが、分散性、保存安定性、粘度制御等の観点から、多液混合方法が好ましい。   As a method of preparing the dispersion (a), for example, a method of mixing a water-soluble organic monomer, a water-swellable clay mineral, a polymerization initiator, water, etc. at one time; a dispersion containing a water-soluble organic monomer (a1) And a solution (a2) containing a polymerization initiator are prepared as a separate dispersion or solution, and a multi-liquid mixing method of mixing immediately before use, etc. may be mentioned, but the viewpoints of dispersibility, storage stability, viscosity control, etc. Therefore, a multi-liquid mixing method is preferred.

前記水溶性有機モノマーを含有する分散液（ａ１）としては、例えば、水溶性有機モノマー及び水膨潤性粘土鉱物を混合した分散液等が挙げられる。   Examples of the dispersion (a1) containing the water-soluble organic monomer include a dispersion in which a water-soluble organic monomer and a water-swellable clay mineral are mixed.

前記重合開始剤を含有する溶液（ａ２）としては、例えば、重合開始剤と水とを混合した水溶液等が挙げられる。   As a solution (a2) containing the said polymerization initiator, the aqueous solution etc. which mixed the polymerization initiator and water are mentioned, for example.

前記高分子ヒドロゲルは、前記分散液（ａ）中で、水溶性有機モノマーを重合させることにより得られるが、重合方法については、特に制限されず、公知の方法によって行うことができる。具体的には、加熱や紫外線照射によるラジカル重合、レドックス反応を利用したラジカル重合等が挙げられる。   The polymer hydrogel is obtained by polymerizing a water-soluble organic monomer in the dispersion (a), but the polymerization method is not particularly limited, and can be performed by a known method. Specifically, radical polymerization by heating or ultraviolet irradiation, radical polymerization utilizing a redox reaction, and the like can be mentioned.

重合温度としては、１０〜８０℃であることが好ましく、２０〜８０℃であることがより好ましい。重合温度が１０℃以上であると、ラジカル反応が連鎖的に進行できることから好ましい。一方、重合温度が８０℃以下であると、分散液中に含まれる水が沸騰せずに重合できることから好ましい。   The polymerization temperature is preferably 10 to 80 ° C., and more preferably 20 to 80 ° C. When the polymerization temperature is 10 ° C. or higher, it is preferable because the radical reaction can proceed in a chain. On the other hand, it is preferable that the polymerization temperature is 80 ° C. or less, because the water contained in the dispersion can be polymerized without boiling.

重合時間としては、重合開始剤や触媒の種類によって異なるが、数十秒〜２４時間の間で実施される。特に、加熱やレドックスを利用するラジカル重合の場合は、１〜２４時間であることが好ましく、５〜２４時間であることがより好ましい。重合時間が１時間以上であると、水膨潤性粘土鉱物と水溶性有機モノマーの重合物が三次元網目を形成できることから好ましい。一方、重合反応は２４時間以内にほぼ完了するので、重合時間は２４時間以下が好ましい。   The polymerization time varies depending on the type of polymerization initiator and catalyst, but is carried out for several tens of seconds to 24 hours. In particular, in the case of radical polymerization using heating or redox, it is preferably 1 to 24 hours, and more preferably 5 to 24 hours. A polymer of a water-swellable clay mineral and a water-soluble organic monomer is preferable because the polymerization time is 1 hour or more because a three-dimensional network can be formed. On the other hand, since the polymerization reaction is almost complete within 24 hours, the polymerization time is preferably 24 hours or less.

本発明のコンクリート構造体用充填材の製造方法としては、複雑形状部等にも容易に充填することができ、土木工事現場や建築工事現場等での作業性がより向上することから、前記分散液（ａ）をコンクリート構造物の間隙に注入し、間隙内で前記高分子ヒドロゲル（Ａ）を生成させる方法が好ましい。

The method for producing a filler for a concrete structure according to the present invention can be easily filled in a complex shape part and the like, and the workability in a civil engineering construction site and a construction site can be further improved. It is preferable to inject the liquid (a) into the gap of the concrete structure to form the polymer hydrogel (A) in the gap.

本発明のコンクリート構造体用充填材は、コンクリートとの親和性により毛細管現象で多孔質に入り密着する。また、湿潤面では、その高い吸水性から濃度勾配を平準化するように多孔質に入り密着すると考えられる。   The filler for a concrete structure of the present invention enters into a porous structure by capillary action and adheres to it by affinity with concrete. On the other hand, it is thought that in the wet side, the high water absorption property causes the porous material to be in intimate contact so as to equalize the concentration gradient.

本発明のコンクリート構造体用充填材は、作業性に優れ、難燃性であり、コンクリート湿潤面への付着性、伸縮追従性等の各種物性に優れることから、トンネル、道路、橋梁、軌道、ビル、護岸、上下水道等のコンクリート構造物の充填材として、また、それらの補修材として用いることができる。   The filler for a concrete structure according to the present invention is excellent in workability, is flame retardant, and is excellent in various physical properties such as adhesion to the wet surface of the concrete and followability to expansion and contraction, tunnels, roads, bridges, tracks, It can be used as a filler for concrete structures such as buildings, revetments, water and sewage, and as a repair material for them.

以下に本発明を具体的な実施例を挙げてより詳細に説明する。   Hereinafter, the present invention will be described in more detail by way of specific examples.

（実施例１：コンクリート構造体用充填材（１）の作製及び評価）
純水１００ｇ中に、Ｎ，Ｎ−ジメチルアクリルアミド（ＫＪケミカルズ株式会社製）１０ｇ、水膨潤性合成ヘクトライト（ビックケミー・ジャパン株式会社製、「ラポナイトＸＬＧ」）１．６ｇを混合攪拌して分散液（ａ１−１）を調製した。また純水１００ｇ中に、ペルオキソ二硫酸カリウム（以下、「ＫＰＳ」と略記する。）５ｇを混合攪拌してＫＰＳ水溶液（ａ２−１）を調製した。
次いで、分散液（ａ１−１）とＫＰＳ水溶液（ａ２−１）との質量比［（ａ１−１）／（ａ１−２）］が１０となるように混合し、分散液（ａ−１）を得た。 Example 1 Preparation and Evaluation of Filler for Concrete Structure (1)
10 g of N, N-dimethyl acrylamide (manufactured by KJ Chemicals, Inc.) and 1.6 g of water-swellable synthetic hectorite ("Laponite XLG", manufactured by BIC Chemie Japan Co., Ltd.) are mixed and stirred in 100 g of pure water to obtain a dispersion. (A1-1) was prepared. In 100 g of pure water, 5 g of potassium peroxodisulfate (hereinafter, abbreviated as "KPS") was mixed and stirred to prepare a KPS aqueous solution (a2-1).
Subsequently, it mixes so that mass ratio [(a1-1) / (a1-2)] of dispersion liquid (a1-1) and KPS aqueous solution (a2-1) may be 10, and dispersion liquid (a-1) I got

［湿潤面付着性の評価］
コンクリート普通平板（ＪＩＳ Ａ ５３７１）６０×３００×３００ｍｍを水に２４時間浸漬し、表面の水滴のみを拭き取った後、上記で得られた分散液（ａ−１）を３ｋｇ／ｍ２塗布し、２３℃、湿度５０％の環境下で１週間養生し、コンクリート構造体用充填材（１）を得た後に、２５ｍｍ幅にコンクリート構造体用充填材（１）をカットし、１８０°の方向に充填材を引っ張った際の充填材の状態により湿潤面付着性を下記の基準に従って評価した。
○：凝集破壊もしくは下地破壊
×：層間剥離 [Evaluation of wet surface adhesion]
Immerse concrete ordinary flat plate (JIS A 5371) 60 × 300 × 300 mm in water for 24 hours and wipe off only water droplets on the surface, then apply 3 kg / m 2 of the dispersion (a-1) obtained above, After curing for 1 week in an environment of 23 ° C and 50% humidity to obtain a filler for a concrete structure (1), cut the filler for a concrete structure (1) to a width of 25 mm, and in the direction of 180 ° The wet surface adhesion was evaluated according to the following criteria depending on the condition of the filler when it was pulled.
○: cohesive failure or base failure ×: delamination

［伸縮追従性の評価］
上記で得られた分散液（ａ−１）を用いて、ＪＩＳ Ａ １４３９の５．１７の「耐久性試験」における目地幅の拡大・縮小を実施した。変形率±２０％、繰返し回数３，６５０回を行い、剥離・破断を確認し、コンクリート構造体用充填材（１）について、下記の基準により伸縮追従性を評価した。
○：剥離・破断なし
×：剥離あり、もしくは破断あり [Evaluation of stretchability]
The joint width was expanded or reduced in the “durability test” of JIS A 1439, 5.17, using the dispersion liquid (a-1) obtained above. The deformation ratio ± 20% and the number of repetitions 3,650 times were performed, peeling and breakage were confirmed, and the following property was evaluated for the filler for a concrete structure (1) according to the following criteria.
○: no peeling or breakage ×: peeling or breakage

［難燃性の評価］
上記で得られた分散液（ａ−１）を厚み１ｍｍの容器に注入して、２０℃で重合を行い、厚み１ｍｍのシート状のコンクリート構造体用充填材（１）を得た。このコンクリート構造体用充填材（１）について、ＵＬ規格のＵＬ９４ＨＢクラスの試験方法に準じ、３０秒間接炎し、下記の基準に従い評価した。
〇：燃焼しなかった
×：燃焼した [Evaluation of flame retardancy]
The dispersion (a-1) obtained above was poured into a container having a thickness of 1 mm, and polymerization was performed at 20 ° C. to obtain a sheet-like filler for a concrete structure (1) having a thickness of 1 mm. About this filler for concrete structures (1), it indirectly flamed for 30 seconds according to the test method of UL94HB class of UL specification, and was evaluated according to the following reference | standard.
○: Not burned ×: Burned

（実施例２：コンクリート構造体用充填材（２）の製造及び評価）
純水１００ｇ中に、Ｎ，Ｎ−ジメチルアクリルアミド（ＫＪケミカルズ株式会社製）１０ｇ、水膨潤性合成ヘクトライト（ビックケミー・ジャパン株式会社製、「ラポナイトＸＬＧ」）４ｇを混合攪拌して分散液（ａ１−２）を調製した。また純水１００ｇ中に、ペルオキソ二硫酸カリウム（ＫＰＳ）５ｇを混合攪拌してＫＰＳ水溶液（（ａ２−２）を調製した。
次いで、分散液（ａ１−２）とＫＰＳ水溶液（ａ２−２）との質量比［（ａ１−２）／（ａ２−２）］が１０となるように混合し、分散液（２）を得た。 Example 2 Production and Evaluation of Filler for Concrete Structure (2)
In 100 g of pure water, 10 g of N, N-dimethyl acrylamide (manufactured by KJ Chemicals, Inc.) and 4 g of water-swellable synthetic hectorite (manufactured by BIC Chemie Japan Ltd., “Laponite XLG”) are mixed and stirred to obtain a dispersion (a1 -2) was prepared. In 100 g of pure water, 5 g of potassium peroxodisulfate (KPS) was mixed and stirred to prepare a KPS aqueous solution ((a2-2).
Next, the dispersion (a1-2) and the KPS aqueous solution (a2-2) are mixed such that the mass ratio [(a1-2) / (a2-2)] is 10, to obtain a dispersion (2). The

実施例１で用いた分散液（ａ−１）を分散液（ａ−２）に変更した以外は、実施例１と同様にコンクリート構造体用充填材（２）を製造し、各評価を行った。   A filler (2) for a concrete structure is manufactured in the same manner as in Example 1 except that the dispersion (a-1) used in Example 1 is changed to the dispersion (a-2), and each evaluation is performed. The

（比較例１）
実施例１で用いた分散液（ａ−１）を、ＪＩＳ Ａ５７５８を満足する２成分系シリコーン系シーリング材（セメダイン株式会社製「ＰＭ７００ＬＭＧ」）に変更した以外は、実施例１と同様に各評価を行った。 (Comparative example 1)
Each evaluation was carried out in the same manner as in Example 1 except that the dispersion (a-1) used in Example 1 was changed to a two-component silicone-based sealing material ("PM700 LMG" manufactured by Cemedine Co., Ltd.) satisfying JIS A 5758. Did.

（比較例２）
実施例１で用いた分散液（ａ−１）を、加水反応型の一液発泡ウレタン（日本ＴＡＣＣＳ協会「ＴＡＣＣＳ工法 構造物止水用グレードＣＲ−０２０ＮＦ」）に変更した以外は、実施例１と同様に各評価を行った。 (Comparative example 2)
Example 1 except that the dispersion (a-1) used in Example 1 was changed to a hydrolytic reaction type one-component foamed urethane (Japan TACCS Association “TACCS construction method water resistant grade CR-020NF”). Each evaluation was performed similarly to.

（比較例３）
実施例１で用いた分散液（ａ−１）を、ＪＩＳ Ａ６０２４を満足するエポキシ樹脂（コニシ株式会社製「ボンドＥ２０６」）に変更した以外は、実施例１と同様に各評価を行った。 (Comparative example 3)
Each evaluation was performed similarly to Example 1 except having changed the dispersion liquid (a-1) used in Example 1 into the epoxy resin ("bond E206" by Konishi Co., Ltd.) which satisfies JISA6024.

上記で得られた各評価結果を表１に示す。   Each evaluation result obtained above is shown in Table 1.

Figure 0006501724
Figure 0006501724

実施例１及び２の本発明のコンクリート構造体用充填材は、湿潤面付着性、伸縮追従性及び難燃性に優れることが確認された。   It was confirmed that the filler for a concrete structure of the present invention of Examples 1 and 2 is excellent in wet surface adhesion, stretchability, and flame retardancy.

一方、比較例１は充填材として、２成分系シリコーン系シーリング材を使用した例であるが、湿潤面付着性が不十分であり、難燃性に劣ることが確認された。   On the other hand, Comparative Example 1 is an example in which a two-component silicone-based sealing material is used as a filler, but it was confirmed that the adhesion on the wet surface was insufficient and the flame retardancy was inferior.

比較例２は充填材として、加水反応型の一液発泡ウレタンを使用した例であるが、伸縮追従性が不十分であり、難燃性に劣ることが確認された。   Comparative Example 2 is an example in which a hydrolysis reaction type one-component foamed urethane is used as the filler, but it was confirmed that the stretch following property is insufficient and the flame retardancy is inferior.

比較例３は充填材として、エポキシ樹脂を使用した例であるが、伸縮追従性が不十分であり、難燃性に劣ることが確認された。   Although the comparative example 3 is an example which uses an epoxy resin as a filler, it was confirmed that expansion-contraction tracking property is inadequate and it is inferior to a flame retardance.

Claims (4)

水溶性有機モノマーの重合体及び水膨潤性粘土鉱物により形成された三次元網目構造を有する高分子ヒドロゲル（Ａ）を形成するために使用される分散液であって、
前記分散液中の１〜５０質量％の含有量の水溶性有機モノマー、前記分散液中の１〜２０質量％の含有量の水膨潤性粘土鉱物、重合開始剤、及び水を必須原料とするものであることを特徴とするコンクリート構造体用充填材のための分散液。 A dispersion used to form a polymer hydrogel (A) having a three-dimensional network structure formed by a polymer of a water-soluble organic monomer and a water-swellable clay mineral ,
A water-soluble organic monomer having a content of 1 to 50% by mass in the dispersion , a water-swellable clay mineral having a content of 1 to 20% by mass in the dispersion , a polymerization initiator, and water as essential raw materials What is claimed is: 1. A dispersion for a filler for a concrete structure, characterized in that 請求項１に記載のコンクリート構造体用充填材のための分散液において、In the dispersion for a filler for a concrete structure according to claim 1,
前記重合開始剤の含有量が、前記分散液中の０．１〜１０質量％であることを特徴とするコンクリート構造体用充填材のための分散液。Content of the said polymerization initiator is 0.1-10 mass% in the said dispersion liquid. Dispersion liquid for the filler for concrete structures characterized by the above-mentioned. 請求項１又は２に記載の分散液をコンクリート構造体の間隙に注入し、間隙内で前記高分子ヒドロゲル（Ａ）を生成させることを特徴とするコンクリート構造体用充填材の製造方法。 請 Motomeko 1 or 2 dispersion according to and injected into the space of the concrete structure, the manufacturing method of the concrete structure filler, characterized in that to produce the polymer hydrogel (A) in the gap. 請求項１又は２に記載の分散液をコンクリート構造体の間隙に注入し、間隙内で前記高分子ヒドロゲル（Ａ）を生成させて製造されたコンクリート構造体用充填材により、コンクリート構造物の間隙が充填されたコンクリート構造体を得ることを特徴とするコンクリート構造体の製造方法。 The dispersion according to 請 Motomeko 1 or 2 was injected into the gap of the concrete structure, the concrete structure fillers prepared by generating the polymer hydrogel (A) in the gap, of the concrete structure What is claimed is: 1. A method of manufacturing a concrete structure comprising obtaining a concrete structure filled with a gap.
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