JP2008031275A - Waterproofing agent - Google Patents

Waterproofing agent Download PDF

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JP2008031275A
JP2008031275A JP2006205707A JP2006205707A JP2008031275A JP 2008031275 A JP2008031275 A JP 2008031275A JP 2006205707 A JP2006205707 A JP 2006205707A JP 2006205707 A JP2006205707 A JP 2006205707A JP 2008031275 A JP2008031275 A JP 2008031275A
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filler
water absorption
group
silica
silane
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Hiroshi Ota
洋 太田
Toshiki Takizawa
俊樹 滝澤
Yuji Kobayashi
裕二 小林
Hitoshi Kirigatani
仁 桐ヶ谷
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Bridgestone Corp
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Bridgestone 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/65—Water proofers or repellants
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00517—Coating or impregnation materials for masonry

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a waterproofing agent capable of imparting water repellency and a high waterproofing performance to surfaces of building materials such as concrete when applied to the surfaces of the building materials. <P>SOLUTION: The waterproofing agent is obtained by compounding at least one inorganic filler chosen from a silica filler, an alumina filler, a silica-alumina filler and a zeolite filler with an aqueous silane/siloxane emulsion. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は吸水防止材、詳しくはコンクリート等の建材の表面に塗布することにより、建材の内部に浸透し、建材が吸水することを防止する吸水防止材に関する。   The present invention relates to a water absorption preventing material, and more particularly to a water absorption preventing material that penetrates into the building material and prevents the building material from absorbing water by being applied to the surface of the building material such as concrete.

シラン化合物やポリシロキサンなどの有機ケイ素化合物を各種の建材に塗布することで建材表面を疎水化し、建材内部への水の浸透を抑制する方法は従来から知られている。対象となる建材は、コンクリート、モルタル、軽量気泡コンクリート、レンガなどの無機の多孔質建材であり、このような多孔質建材の細孔に有機ケイ素化合物が浸透して表層を疎水化することにより、これら建材の劣化・老朽化が抑制される。さらに、該有機ケイ素化合物によって撥水性も付与されるため、埃の付着やカビの発生が抑制され、汚れが付きにくくなるという効果もある。   A method for making a building material surface hydrophobic by applying an organosilicon compound such as a silane compound or polysiloxane to various building materials and suppressing water permeation into the building material has been conventionally known. The target building material is an inorganic porous building material such as concrete, mortar, lightweight cellular concrete, brick, etc., and the surface of the porous building material penetrates into the pores to make the surface layer hydrophobic, Deterioration and aging of these building materials are suppressed. Further, since the organosilicon compound also imparts water repellency, there is an effect that the adhesion of dust and the generation of mold are suppressed, and dirt is hardly attached.

上記有機ケイ素化合物は、従来は有機溶剤に希釈して用いられていたが、塗布後に揮発する有機溶剤による環境汚染の懸念、作業環境の悪化の観点から、水性のエマルションとして用いることが望ましい。
しかしながら、従来の有機ケイ素化合物の水性エマルションは多数回の塗布を必要としたり、緻密なコンクリートからなる土木構造物に対して用いた場合に、液ダレを起こしたり、浸透性が十分でないという欠点を有していた。 The organosilicon compound has been conventionally diluted with an organic solvent, but is preferably used as an aqueous emulsion from the viewpoint of environmental pollution due to the organic solvent that volatilizes after coating and the deterioration of the working environment.
However, conventional organic silicon compound emulsions have the disadvantages that they need to be applied many times, cause dripping when used for civil engineering structures made of dense concrete, and have insufficient permeability. Had.

そこで、特定の構造のアルキルアルコキシシラン、ポリオルガノシロキサン、乳化剤及び水からなるコンクリートの処理用シラン／シロキサン系エマルションが提案されている（特許文献１、特許請求の範囲参照）。
また、コンクリート材料に撥水性を付与するため、アルコキシシランとポリオルガノシロキサンを有効成分とし、これらの有効成分を水系媒体中に６０質量％以上含有するシラン・シロキサン系の下塗剤が提案されている（特許文献２、特許請求の範囲参照）。 Therefore, a silane / siloxane emulsion for treating concrete comprising an alkylalkoxysilane having a specific structure, a polyorganosiloxane, an emulsifier, and water has been proposed (see Patent Document 1 and Claims).
In order to impart water repellency to a concrete material, a silane / siloxane-based primer containing alkoxysilane and polyorganosiloxane as active ingredients and containing 60% by mass or more of these active ingredients in an aqueous medium has been proposed. (See Patent Document 2 and Claims).

特開２００４−３３８９８０号公報JP 2004-338980 A 特開２００３−４８７９０号公報JP 2003-48790 A

従来のコンクリート処理用シラン／シロキサン系エマルションは、コンクリート等の建材の表面から深さ方向に１〜５ｍｍ程度の防水層を設けることにより、建材の吸水量を低減させ、建材の長期耐久性を向上させるものであるが、建材の表面は必ずしも撥水性を示すものではなく、むしろ親水性を示すものが多かった。このような、従来の防水層でも建材への水の浸入を防止する効果はあるが、より効果的に吸水を防止するために、建材の表面においても撥水性を示す吸水防止材が望まれていた。
また、従来のタイプの吸水防止材では、建材の表面が親水性であるものが多いため、建材の表面に藻やカビ、苔などが生じやすく、建材の外観が著しく損なわれるという問題もあった。 Conventional silane / siloxane emulsions for concrete treatment reduce the water absorption of building materials and improve the long-term durability of building materials by providing a waterproof layer of about 1-5mm in the depth direction from the surface of building materials such as concrete. However, the surface of the building material does not necessarily exhibit water repellency, but rather exhibits many hydrophilic properties. Such a conventional waterproof layer has an effect of preventing water from entering the building material, but in order to prevent water absorption more effectively, a water absorption preventing material exhibiting water repellency on the surface of the building material is desired. It was.
In addition, since many of the conventional types of water absorption preventing materials have a hydrophilic building material surface, algae, mold, moss and the like are likely to be generated on the surface of the building material, and the appearance of the building material is significantly impaired. .

本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、従来からコンクリート等の吸水防止材として用いられているシラン／シロキサン系エマルションに、特定の充填剤を配合することにより、建材の表面を撥水化することができ、また吸水防止性能が著しく向上することを見出した。本発明はかかる知見に基づいて完成したものである。   As a result of intensive studies to solve the above problems, the present inventors have blended a specific filler with a silane / siloxane emulsion that has been conventionally used as a water absorption preventing material such as concrete, It has been found that the surface of building materials can be made water repellent and the water absorption prevention performance is remarkably improved. The present invention has been completed based on such findings.

すなわち、本発明は、シラン・シロキサン系水性エマルションにシリカ系充填剤、アルミナ系充填剤、シリカ−アルミナ系充填剤、及びゼオライト系充填剤からなる群から選ばれる少なくとも１種の無機充填剤を配合してなる吸水防止材を提供するものである。   That is, in the present invention, at least one inorganic filler selected from the group consisting of a silica-based filler, an alumina-based filler, a silica-alumina-based filler, and a zeolite-based filler is blended with a silane / siloxane-based aqueous emulsion. Thus, a water absorption preventing material is provided.

本発明の吸水防止材によれば、コンクリート等の建材の表面に塗布することにより、該建材の表面を撥水化することができ、著しく高い吸水防止性能を得ることができる。   According to the water absorption preventive material of the present invention, by applying to the surface of building materials such as concrete, the surface of the building material can be made water repellent, and extremely high water absorption preventing performance can be obtained.

本発明の吸水防止材は、シラン・シロキサン系水性エマルションにシリカ系充填剤、アルミナ系充填剤、シリカ−アルミナ系充填剤、及びゼオライト系充填剤からなる群から選ばれる少なくとも１種の無機充填剤を配合することを特徴とする。
シラン・シロキサン系水性エマルションとは、アルキルアルコキシシランとポリオルガノシロキサンを水系媒体中に含有するものをいう。 The water absorption preventive material of the present invention comprises at least one inorganic filler selected from the group consisting of a silane / siloxane aqueous emulsion, a silica filler, an alumina filler, a silica-alumina filler, and a zeolite filler. It is characterized by blending.
The silane / siloxane-based aqueous emulsion refers to an emulsion containing an alkylalkoxysilane and a polyorganosiloxane in an aqueous medium.

アルキルアルコキシシランは、通常、下記一般式（Ｉ）で表されるものである。
Ｒ1 xＳｉ（ＯＲ2）4-x ・・・（Ｉ）
ここで、R1は炭素数１〜２０のアルキル基、Ｒ2は炭素数１〜６のアルキル基又は水素原子、ｘは１又は２の整数である。
Ｒ1の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ドデシル基などのアルキル基；シクロペンチル基、シクロヘキシル基、４−エチルシクロヘキシル基、シクロヘプチル基、ノルボルニル基、メチルシクロヘキシル基のようなシクロアルキル基が挙げられる。これらのうち、特に炭素数４〜１０のアルキル基が好ましい。
なお、複数あるＲ1は分子中で同一であっても異なっていてもよい。 The alkylalkoxysilane is usually represented by the following general formula (I).
R 1 x Si (OR 2 ) 4-x (I)
Here, R 1 is an alkyl group having 1 to 20 carbon atoms, R 2 is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and x is an integer of 1 or 2.
Specific examples of R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. And alkyl groups such as various nonyl groups, various decyl groups and various dodecyl groups; and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, cycloheptyl group, norbornyl group, and methylcyclohexyl group. Among these, an alkyl group having 4 to 10 carbon atoms is particularly preferable.
A plurality of R 1 may be the same or different in the molecule.

Ｒ2の具体例としては、水素原子の他に、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基などが挙げられ、これらのなかでも特に炭素数１又は２のアルキル基が好ましい。
なお、複数あるＲ2は分子中で同一であっても異なっていてもよい。 Specific examples of R 2 include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, tert-pentyl group, n-hexyl group and the like. Among these, an alkyl group having 1 or 2 carbon atoms is particularly preferable.
A plurality of R 2 may be the same or different in the molecule.

次に、ポリオルガノシロキサンは、通常、下記一般式（II）で表されるものである。
Ｒ3 a（ＯＲ4）bＳｉ（ＯＨ）cＯ(4-a-b-c) ・・・（II）
ここで、R3は炭素数１〜２０のアルキル基、Ｒ4は炭素数１〜６のアルキル基、ａ、ｂ及びｃはそれぞれ０．５＜ａ≦２．０、０≦ｂ＜２．０、０≦ｃ＜２、ａ＋ｂ＋ｃ≦３の範囲である。 Next, the polyorganosiloxane is usually represented by the following general formula (II).
R 3 a (OR 4 ) b Si (OH) c O (4-abc) (II)
Here, R 3 is an alkyl group having 1 to 20 carbon atoms, R 4 is an alkyl group having 1 to 6 carbon atoms, and a, b and c are 0.5 <a ≦ 2.0 and 0 ≦ b <2. The ranges are 0, 0 ≦ c <2, and a + b + c ≦ 3.

Ｒ3の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ドデシル基などのアルキル基；シクロペンチル基、シクロヘキシル基、４−エチルシクロヘキシル基、シクロヘプチル基、ノルボルニル基、メチルシクロヘキシル基のようなシクロアルキル基が挙げられる。これらのうち、特に炭素数４〜１０のアルキル基が好ましい。
なお、複数あるＲ3は分子中で同一であっても異なっていてもよい。 Specific examples of R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups. And alkyl groups such as various nonyl groups, various decyl groups and various dodecyl groups; and cycloalkyl groups such as cyclopentyl group, cyclohexyl group, 4-ethylcyclohexyl group, cycloheptyl group, norbornyl group, and methylcyclohexyl group. Among these, an alkyl group having 4 to 10 carbon atoms is particularly preferable.
A plurality of R 3 may be the same or different in the molecule.

Ｒ4の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基などが挙げられ、これらのなかでも特に炭素数１又は２のアルキル基が好ましい。
なお、複数あるＲ4は分子中で同一であっても異なっていてもよい。 Specific examples of R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, and tert-pentyl group. , N-hexyl group and the like. Among these, an alkyl group having 1 or 2 carbon atoms is particularly preferable.
A plurality of R 4 may be the same or different in the molecule.

本発明におけるシラン・シロキサン系水性エマルション中、上記アルキルアルコキシシラン及びポリオルガノシロキサンの合計量（有効成分）は５０〜９０質量％の範囲が好ましい。該合計量（有効成分）が５０質量％以上であると本発明の効果を十分に奏することができ、一方、９０質量％以下であると粘度調整が容易であり、建材等への塗布を容易に行うことができる。以上の観点から、該合計量（有効成分）はさらに６０〜９０質量％の範囲、特には７０〜８５質量％の範囲が好ましい。   In the silane / siloxane-based aqueous emulsion of the present invention, the total amount (active ingredient) of the alkylalkoxysilane and polyorganosiloxane is preferably in the range of 50 to 90% by mass. When the total amount (active ingredient) is 50% by mass or more, the effect of the present invention can be sufficiently achieved. On the other hand, when the total amount (active ingredient) is 90% by mass or less, the viscosity can be easily adjusted and can be easily applied to building materials. Can be done. From the above viewpoint, the total amount (active ingredient) is more preferably in the range of 60 to 90% by mass, and particularly preferably in the range of 70 to 85% by mass.

また、本発明におけるシラン・シロキサン系水性エマルション中のアルキルアルコキシシランとポリオルガノシロキサンの含有量比（アルキルアルコキシシラン／ポリオルガノシロキサン）は、５０／１〜１０／１の範囲が好ましい。この範囲であると多孔質建材への十分な浸透性が得られる。   In addition, the content ratio (alkylalkoxysilane / polyorganosiloxane) of alkylalkoxysilane and polyorganosiloxane in the silane / siloxane-based aqueous emulsion of the present invention is preferably in the range of 50/1 to 10/1. In this range, sufficient permeability to the porous building material can be obtained.

本発明におけるシラン・シロキサン系水性エマルションは、通常、乳化剤を用いて乳化されるが、乳化剤としては特に制限はなく、各種の公知の乳化剤を使用することができる。具体的には、アルキルスルフェート、アルキルスルホネート、アルキルアリールスルホネート等のアニオン系乳化剤；ポリビニルアルコール、アルキルポリグリコールエーテル、アルキルアミンのエチレンオキシド又はプロピレンオキシドとの付加生成物等の非イオン系乳化剤などが挙げられ、特に非イオン系乳化剤が好ましい。
乳化剤の含有量としては、シラン・シロキサン系水性エマルションに対して、通常０．１〜１０質量％であり、好ましくは０．１〜５質量％である。 The silane / siloxane-based aqueous emulsion in the present invention is usually emulsified using an emulsifier, but the emulsifier is not particularly limited, and various known emulsifiers can be used. Specific examples include anionic emulsifiers such as alkyl sulfates, alkyl sulfonates, and alkyl aryl sulfonates; nonionic emulsifiers such as addition products of polyvinyl alcohol, alkyl polyglycol ethers, and alkylamines with ethylene oxide or propylene oxide. In particular, nonionic emulsifiers are preferred.
The content of the emulsifier is usually 0.1 to 10% by mass, preferably 0.1 to 5% by mass with respect to the silane / siloxane-based aqueous emulsion.

本発明におけるシラン・シロキサン系水性エマルションに用いる水は通常の精製水であればよく、特に制限はない。水の含有量は水性エマルションを構成する有効成分１００質量部に対して、２０００質量部以下の範囲で用いることができるが、水性エマルションの安定性の観点からは、５〜２０００質量部の範囲が好ましい。   The water used in the silane / siloxane-based aqueous emulsion in the present invention may be ordinary purified water, and is not particularly limited. Although water content can be used in 2000 mass parts or less with respect to 100 mass parts of active ingredients which comprise an aqueous emulsion, from a stability viewpoint of aqueous emulsion, the range of 5-2000 mass parts is used. preferable.

次に、本発明で用いる無機充填剤としては、シリカ系充填剤、アルミナ系充填剤、シリカ−アルミナ系充填剤、及びゼオライト系充填剤が挙げられる。これらのうち、その表面が親水性であるものが、シラン・シロキサン系水性エマルション中での安定性が高い点から好ましく、本発明の効果の点から、特にシリカ系充填剤及びアルミナ系充填剤が好ましい。また、無機充填剤は１種を単独で又は２種以上を組み合わせて使用することができる。   Next, examples of the inorganic filler used in the present invention include silica-based fillers, alumina-based fillers, silica-alumina-based fillers, and zeolite-based fillers. Among these, those having a hydrophilic surface are preferable from the viewpoint of high stability in the silane / siloxane-based aqueous emulsion, and from the viewpoint of the effects of the present invention, silica-based fillers and alumina-based fillers are particularly preferable. preferable. Moreover, an inorganic filler can be used individually by 1 type or in combination of 2 or more types.

シリカ系充填剤としては、例えば溶融シリカ、結晶性シリカ、窒化珪素、コロイダルシリカ、シリカエアロゲル、ヒュームドシリカ、焼成シリカ、沈降シリカなどが挙げられ、さらにはこれらの表面を鎖状オルガノポリシロキサン、環状オルガノポリシロキサン、ヘキサメチルジシラザン等によってシラン処理したものが挙げられる。市販品としては、日本アエロジル社製「ＡＥＲＯＳＩＬ２００」などが挙げられる。
該シリカ系充填剤の比表面積については特に制限はないが、通常５０ｍ2／ｇ以上であることが好ましく、より好ましくは１００〜４００ｍ2／ｇの範囲である。 Examples of the silica-based filler include fused silica, crystalline silica, silicon nitride, colloidal silica, silica aerogel, fumed silica, calcined silica, precipitated silica, and the like. Examples include those treated with silane by cyclic organopolysiloxane, hexamethyldisilazane and the like. As a commercial item, Nippon Aerosil Co., Ltd. "AEROSIL200" etc. are mentioned.
No particular limitation is imposed on the specific surface area of the silica-based filler is preferably usually 50 m 2 / g or more, more preferably in the range of 100 to 400 m 2 / g.

アルミナ系充填剤としては、酸性アルミナ、塩基性アルミナ、中性アルミナなどが挙げられる。市販品としては、日本アエロジル社製「Ａｌｕ−Ｃ」などが挙げられる。
また、シリカ系充填剤とアルミナ系充填剤の混合系として、例えば、日本アエロジル社製「ＣＯＫ８４」などが挙げられる。 Examples of the alumina filler include acidic alumina, basic alumina, and neutral alumina. As a commercial item, Nippon Aerosil Co., Ltd. "Alu-C" etc. are mentioned.
Moreover, as a mixed system of a silica-type filler and an alumina-type filler, for example, “COK84” manufactured by Nippon Aerosil Co., Ltd. can be mentioned.

本発明で用いる無機充填剤について、その形状は特に制限されないが、通常は球形のものが好適に用いられる。   The shape of the inorganic filler used in the present invention is not particularly limited, but usually a spherical one is preferably used.

本発明においては、前記無機充填剤は少なくともその表面が親水性であることが好ましい。該無機充填剤が親水性であるとシラン・シロキサン系水性エマルション中での安定性に優れる。   In the present invention, it is preferable that at least the surface of the inorganic filler is hydrophilic. When the inorganic filler is hydrophilic, it is excellent in stability in a silane / siloxane aqueous emulsion.

前記無機充填剤の１次粒子の平均粒子径は５〜５０ｎｍの範囲であることが好ましい。該平均粒子径が５ｎｍ以上であると、溶媒への分散性、取り扱い時のハンドリング性の点で有利であり、一方、５０ｎｍ以下であると、比表面積が高くなるため、溶媒との接触効率が高い点で有利である。以上の観点から、無機充填剤の１次粒子の平均粒子径は７〜２０ｎｍの範囲がさらに好ましい。   The average particle size of the primary particles of the inorganic filler is preferably in the range of 5 to 50 nm. When the average particle size is 5 nm or more, it is advantageous in terms of dispersibility in a solvent and handling properties at the time of handling. It is advantageous in terms of high points. From the above viewpoint, the average particle diameter of the primary particles of the inorganic filler is more preferably in the range of 7 to 20 nm.

前記無機充填剤の配合量は、シラン・シロキサン系水性エマルション中の有効成分１００質量部に対して、０．１〜１０質量部の範囲であることが好ましい。０．１質量部以上であると、エマルションがチクソ性を示し、塗布時の液だれ性を軽減することができ、施工性の点で有利となる。一方１０質量部以下であると、ベース液に対する色相変化が小さく、塗布部の外観が損なわれないという利点がある。以上の観点から、無機充填剤の配合量はシラン・シロキサン系水性エマルション中の有効成分１００質量部に対して１〜９質量部の範囲がさらに好ましく、２〜５質量部の範囲が特に好ましい。   The blending amount of the inorganic filler is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the active ingredient in the silane / siloxane-based aqueous emulsion. When the amount is 0.1 parts by mass or more, the emulsion exhibits thixotropy, can reduce dripping at the time of application, and is advantageous in terms of workability. On the other hand, if it is 10 parts by mass or less, there is an advantage that the hue change with respect to the base liquid is small and the appearance of the coating part is not impaired. From the above viewpoint, the blending amount of the inorganic filler is more preferably in the range of 1 to 9 parts by mass, particularly preferably in the range of 2 to 5 parts by mass with respect to 100 parts by mass of the active ingredient in the silane / siloxane-based aqueous emulsion.

本発明の吸水防止材には、上記成分以外に本発明の効果を損なわない範囲で他の添加剤を含有することができ、例えば、殺カビ剤、殺菌剤、殺藻剤、殺微生物剤、香料、防食剤、消泡剤などを添加することができる。これらの添加剤は、通常、本発明の吸水防止材に対して、０．０１〜２質量％の範囲で添加される。   The water absorption preventing material of the present invention can contain other additives in addition to the above components as long as the effects of the present invention are not impaired, such as fungicides, fungicides, algicides, microbicides, A fragrance | flavor, an anticorrosive, an antifoamer, etc. can be added. These additives are usually added in the range of 0.01 to 2% by mass with respect to the water absorption preventing material of the present invention.

本発明の吸水防止材の粘度は、液温２５℃において、Ｂ型粘度計で測定した値が０．５〜５Ｐａ・ｓの範囲であることが好ましい。この範囲であると液だれがなく、しかも塗布面全体に均一に吸水防止効果を付与することができる。以上の観点から、吸水防止材の粘度はさらに０．８〜４Ｐａ・ｓの範囲が好ましい。
なお、本発明における無機充填剤は、増粘剤としての効果もあるが、吸水防止材の粘度範囲が上記好ましい範囲となるように、無機充填剤以外に増粘剤を配合することもできる。 The viscosity of the water absorption preventing material of the present invention is preferably in the range of 0.5 to 5 Pa · s as measured with a B-type viscometer at a liquid temperature of 25 ° C. Within this range, there is no liquid dripping, and a uniform water absorption preventing effect can be imparted to the entire coated surface. From the above viewpoint, the viscosity of the water absorption preventing material is further preferably in the range of 0.8 to 4 Pa · s.
In addition, although the inorganic filler in this invention also has an effect as a thickener, a thickener can also be mix | blended other than an inorganic filler so that the viscosity range of a water absorption preventive material may turn into the said preferable range.

本発明の吸水防止材は、コンクリート等の建築部材に塗布することによって、該建築部材の表面に撥水性を付与するものであり、具体的には水の接触角で評価することができる。本発明の吸水防止材は、建築部材の表面に塗布した際に水の接触角が１３０度以上を示し、強い表面撥水性を示すものである。
また、本発明の吸水防止材は接触角の経時変化が小さく、長時間経過した後であっても強い表面撥水性を維持する性質を有する。 The water absorption preventive material of the present invention imparts water repellency to the surface of a building member by applying it to a building member such as concrete, and can be specifically evaluated by the contact angle of water. The water absorption preventive material of the present invention has a water contact angle of 130 degrees or more when applied to the surface of a building member, and exhibits strong surface water repellency.
Further, the water absorption preventing material of the present invention has a property of maintaining a strong surface water repellency even after a long time has passed since the change in contact angle is small.

本発明の吸水防止材は、建築材料、特にコンクリート、モルタル、軽量気泡コンクリート、レンガなどのような無機の多孔質建材に、刷毛塗り又は吹付け塗装により用いることができる。本発明の吸水防止材は、コンクリート等に対して浸透性を有するものである。
また、これら建築材料に対する本発明の吸水防止材の塗布量は、本発明の効果を奏する範囲で特に限定はないが、通常、４００ｇ／ｍ2以下、好ましくは１００〜２５０ｇ／ｍ2である。なお、本発明の吸水防止材は一度の塗装で所要量を塗布することが可能だが、重ね塗りすることもできる。 The water absorption preventive material of the present invention can be used for building materials, particularly inorganic porous building materials such as concrete, mortar, lightweight cellular concrete, bricks, etc. by brush coating or spray coating. The water absorption preventive material of the present invention is permeable to concrete or the like.
The coating amount of the water absorption preventing agent of the present invention for these building materials is not particularly limited within a range that the effect of the present invention, usually, 400 g / m 2 or less, and preferably 100 to 250 g / m 2. The water absorption preventive material of the present invention can be applied in a required amount by a single coating, but can also be applied repeatedly.

次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
（評価方法）
（１）施工性；各実施例及び比較例で得られた吸水防止材を土木学会発行の「表面含浸材の試験方法（案）（ＪＳＣＥ−Ｋ５７１−２００４）に準拠して作製したモルタル板（１００×１００×１００ｍｍ）の裁断面（型枠面以外）の１面が、鉛直方向に平行になるように置き、その面に塗布量が２．０ｇ／面となるように刷毛で塗布して、液だれの有無について評価した。評価は以下の基準に従って行った。
○；液だれが生じず良好に塗布ができた。
△；塗布量が所定量に到達する前後で液だれが生じた。
×；塗布量が所定量に到達する前に液だれが生じた。
（２）塗布面の水の接触角（初期）；吸水防止材を塗布した面にイオン交換水をスポイトで滴下し、生じた水滴の接触角を、協和界面科学（株）製接触角計「ＤｒｏｐＭａｓｔｅｒ ３００」を用いて測定した。測定は５点の位置で行い、その平均値で評価した。
（３）水の接触角の経時変化；上記（２）で生じた水滴の３０分後の接触角を上記（２）に記載の方法と同様の方法で測定した。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Evaluation methods)
(1) Workability: Mortar board (in accordance with “Test method for surface impregnated material (draft) (JSCE-K571-2004)” published by Japan Society of Civil Engineers) 100 × 100 × 100 mm) is placed so that one surface of the cut surface (other than the formwork surface) is parallel to the vertical direction, and the surface is coated with a brush so that the coating amount is 2.0 g / surface. The presence or absence of dripping was evaluated according to the following criteria.
○: Drip did not occur and coating was successful.
Δ: Liquid dripping occurred before and after the coating amount reached the predetermined amount.
X: Drip occurred before the coating amount reached the predetermined amount.
(2) Contact angle of water on the coated surface (initial); Ion exchange water is dropped onto the surface coated with the water absorption prevention material with a dropper, and the contact angle of the resulting water droplet is measured by a contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Measurement was performed using “DropMaster 300”. The measurement was performed at five positions, and the average value was evaluated.
(3) Change with time of contact angle of water; The contact angle after 30 minutes of the water droplet generated in the above (2) was measured by the same method as described in the above (2).

実施例１
シラン・シロキサン系水性エマルション（シラン・シロキサン系水性エマルションＡ；旭化成ワッカーシリコーン（株）製「ＢＣ７２５１」、有効成分濃度６８質量％）１００ｇに、シリカ系充填剤（日本アエロジル（株）製「ＡＥＲＯＳＩＬ２００」）１．０ｇを配合し、ミキサーを用いて１０００ｒｐｍの条件で２分間攪拌して吸水防止材を調製した。該吸水防止材をモルタル板（前出と同様の方法で作製、１００×１００×１００ｍｍ）の裁断面（型枠面以外）の１面に塗布量が２．０ｇ／面となるように刷毛で塗布し、２３±２℃、相対湿度５０±５％に調節された室内に１０日間放置し、乾燥させた。このときのモルタル板表面の水分率をｋｅｔｔコンクリート・モルタル水分計「ＨＩ−８００」で測定したところ、１．９％であった。
吸水防止材の施工性、吸水防止材を塗布した面における水の接触角及び該水の接触角の経時変化を上記方法で評価した。その結果を第１表に示す。 Example 1
Silane-siloxane-based aqueous emulsion (Silane-siloxane-based aqueous emulsion A; “BC7251” manufactured by Asahi Kasei Wacker Silicone Co., Ltd., active ingredient concentration: 68% by mass) and silica-based filler (“AEROSIL200” manufactured by Nippon Aerosil Co., Ltd.) ) 1.0 g was blended and stirred for 2 minutes at 1000 rpm using a mixer to prepare a water absorption preventing material. Apply the water absorption preventing material with a brush so that the coating amount is 2.0 g / surface on one surface of the mortar plate (prepared in the same manner as above, 100 × 100 × 100 mm) (other than the mold surface). It was applied and left in a room adjusted to 23 ± 2 ° C. and relative humidity 50 ± 5% for 10 days to dry. The moisture content on the surface of the mortar board at this time was 1.9% when measured with a ket concrete / mortar moisture meter “HI-800”.
The workability of the water absorption preventing material, the contact angle of water on the surface coated with the water absorption preventing material, and the change with time of the water contact angle were evaluated by the above methods. The results are shown in Table 1.

実施例２
シリカ系充填剤の配合量を２．０ｇとしたこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Example 2
A water absorption preventing material was prepared and evaluated in the same manner as in Example 1 except that the amount of the silica-based filler was 2.0 g. The results are shown in Table 1.

実施例３
シリカ系充填剤の配合量を３．０ｇとしたこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Example 3
A water absorption preventing material was prepared and evaluated in the same manner as in Example 1 except that the amount of the silica-based filler was 3.0 g. The results are shown in Table 1.

実施例４
シリカ系充填剤に代えて、アルミナ系充填剤（日本アエロジル（株）製「Ａｌｕ−Ｃ」）２．０ｇを用いたこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Example 4
A water absorption preventing material was prepared in the same manner as in Example 1 except that 2.0 g of an alumina filler (“Alu-C” manufactured by Nippon Aerosil Co., Ltd.) was used instead of the silica filler. evaluated. The results are shown in Table 1.

実施例５
シリカ系充填剤に代えて、シリカ系充填剤（日本アエロジル（株）製「ＡＥＲＯＳＩＬ２００」）１．０ｇとアルミナ系充填剤（日本アエロジル（株）製「Ａｌｕ−Ｃ」）１．０ｇを混合して用いたこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Example 5
Instead of silica filler, 1.0 g of silica filler (“AEROSIL200” manufactured by Nippon Aerosil Co., Ltd.) and 1.0 g of alumina filler (“Alu-C” manufactured by Nippon Aerosil Co., Ltd.) are mixed. A water absorption preventing material was prepared in the same manner as in Example 1 except that it was used. The results are shown in Table 1.

実施例６
シラン・シロキサン系水性エマルションとして、有効成分濃度５０質量％のもの（シラン・シロキサン系水性エマルションＢ；旭化成ワッカーシリコーン（株）製「ＢＣ２１０２」）を用い、シリカ系充填剤の配合量を４．５ｇとしたこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。
なお、モルタル板表面の水分率（ｋｅｔｔコンクリート・モルタル水分計「ＨＩ−８００」で測定）は１．８％であった。 Example 6
As the silane / siloxane aqueous emulsion, an active ingredient concentration of 50% by mass (silane / siloxane aqueous emulsion B; “BC2102” manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) is used, and the amount of silica filler added is 4.5 g. A water absorption preventive material was prepared in the same manner as in Example 1 except that it was evaluated and evaluated in the same manner. The results are shown in Table 1.
The moisture content on the surface of the mortar plate (measured with a ket concrete / mortar moisture meter “HI-800”) was 1.8%.

比較例１
シリカ系充填剤を配合しなかったこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Comparative Example 1
A water absorption preventing material was prepared and evaluated in the same manner as in Example 1 except that no silica-based filler was added. The results are shown in Table 1.

比較例２
シリカ系充填剤に代えて、合成マイカ系充填剤（ズードケミー社製「Ｓ−４８２」）２．０ｇを配合したこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Comparative Example 2
A water absorption preventing material was prepared in the same manner as in Example 1 except that 2.0 g of a synthetic mica-based filler (“S-482” manufactured by Zude Chemie) was used instead of the silica-based filler, and was similarly evaluated. . The results are shown in Table 1.

比較例３
シリカ系充填剤に代えて、合成マイカ系充填剤（ズードケミー社製「Ｓ−４８２」）４．０ｇを配合したこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Comparative Example 3
A water absorption preventing material was prepared in the same manner as in Example 1 except that 4.0 g of a synthetic mica filler (“S-482” manufactured by Zude Chemie) was used instead of the silica filler, and was similarly evaluated. . The results are shown in Table 1.

比較例４
シリカ系充填剤に代えて、有機系充填剤（ズードケミー社製「ＴＶＳ」）２．０ｇを配合したこと以外は実施例１と同様にして吸水防止材を調製し、同様に評価した。その結果を第１表に示す。 Comparative Example 4
A water absorption preventing material was prepared and evaluated in the same manner as in Example 1 except that 2.0 g of an organic filler (“TVS” manufactured by Zude Chemie) was blended in place of the silica filler. The results are shown in Table 1.

比較例５
市販されているコンクリート浸透性吸水防止材（鹿島リノベイト社製「マジカルリペラー」）を吸水防止材として用いて実施例１と同様の評価を行った。その結果を第１表に示す。 Comparative Example 5
The same evaluation as in Example 1 was performed using a commercially available concrete-permeable water-absorbing preventive material (“Magical Repeller” manufactured by Kashima Renovate) as the water-absorbing preventive material. The results are shown in Table 1.

Figure 2008031275
Figure 2008031275

本発明の吸水防止材によれば、コンクリート等の建材の表面に塗布することにより、該建材の表面を撥水化することができ、著しく高い吸水防止性能を得ることができる。また、建材の表面においても撥水性を示すため、建材の表面に藻やカビ、苔などが生じにくく、長期間にわたって建材の外観を維持することができる。   According to the water absorption preventive material of the present invention, by applying to the surface of building materials such as concrete, the surface of the building material can be made water repellent, and extremely high water absorption preventing performance can be obtained. In addition, since the surface of the building material exhibits water repellency, algae, mold, moss and the like are hardly generated on the surface of the building material, and the appearance of the building material can be maintained over a long period of time.

Claims (5)

シラン・シロキサン系水性エマルションにシリカ系充填剤、アルミナ系充填剤、シリカ−アルミナ系充填剤及びゼオライト系充填剤からなる群から選ばれる少なくとも１種の無機充填剤を配合してなる吸水防止材。   A water absorption preventing material comprising a silane / siloxane aqueous emulsion and at least one inorganic filler selected from the group consisting of a silica filler, an alumina filler, a silica-alumina filler, and a zeolite filler. 前記無機充填剤が親水性である請求項１に記載の吸水防止材。   The water absorption preventing material according to claim 1, wherein the inorganic filler is hydrophilic. 前記無機充填剤の配合量がシラン・シロキサン系水性エマルション中の有効成分１００質量部に対して、０．１〜１０質量部である請求項１又は２に記載の吸水防止材。   The water absorption preventive material according to claim 1 or 2, wherein the amount of the inorganic filler is 0.1 to 10 parts by mass with respect to 100 parts by mass of the active ingredient in the silane / siloxane-based aqueous emulsion. 前記無機充填剤の１次粒子の平均粒子径が５〜５０ｎｍの範囲である請求項１〜３のいずれかに記載の吸水防止材。 The water absorption preventing material according to any one of claims 1 to 3, wherein an average particle diameter of primary particles of the inorganic filler is in a range of 5 to 50 nm. コンクリートに対して浸透性を有する請求項１〜４のいずれかに記載の吸水防止材。 The water absorption preventive material according to any one of claims 1 to 4, which has permeability to concrete.
JP2006205707A 2006-07-28 2006-07-28 Waterproofing agent Pending JP2008031275A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009000614A1 (en) 2009-02-04 2010-08-05 Evonik Degussa Gmbh Fluorine-free composition for water-repellent coating of surfaces with improved beading properties
KR100973984B1 (en) * 2008-05-30 2010-08-05 진도화성주식회사 Waterproofing Composition Having Permeation Mechanism
JP5701441B1 (en) * 2014-09-01 2015-04-15 エムケイテック株式会社 Water repellent composition
KR102345422B1 (en) * 2021-03-16 2021-12-29 한양대학교 에리카산학협력단 Admixture of water-repellent impregnated natural zeolite and method for preparing the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100973984B1 (en) * 2008-05-30 2010-08-05 진도화성주식회사 Waterproofing Composition Having Permeation Mechanism
DE102009000614A1 (en) 2009-02-04 2010-08-05 Evonik Degussa Gmbh Fluorine-free composition for water-repellent coating of surfaces with improved beading properties
WO2010089166A1 (en) 2009-02-04 2010-08-12 Evonik Degussa Gmbh Fluorine-free composition for water-repellent coating of surfaces having improved beading properties
JP5701441B1 (en) * 2014-09-01 2015-04-15 エムケイテック株式会社 Water repellent composition
JP2016050271A (en) * 2014-09-01 2016-04-11 エムケイテック株式会社 Water repellent composition
KR102345422B1 (en) * 2021-03-16 2021-12-29 한양대학교 에리카산학협력단 Admixture of water-repellent impregnated natural zeolite and method for preparing the same

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