WO2009096147A1 - セメント硬化物用含浸組成物 - Google Patents

セメント硬化物用含浸組成物 Download PDF

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Publication number
WO2009096147A1
WO2009096147A1 PCT/JP2009/000167 JP2009000167W WO2009096147A1 WO 2009096147 A1 WO2009096147 A1 WO 2009096147A1 JP 2009000167 W JP2009000167 W JP 2009000167W WO 2009096147 A1 WO2009096147 A1 WO 2009096147A1
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Prior art keywords
component
aqueous solution
mass
parts
composition according
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PCT/JP2009/000167
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English (en)
French (fr)
Japanese (ja)
Inventor
Naomitsu Tsuyuki
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Co., Ltd. Japan Raw Materials Engineering Laboratory
Tachibana Material Co., Ltd.
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Application filed by Co., Ltd. Japan Raw Materials Engineering Laboratory, Tachibana Material Co., Ltd. filed Critical Co., Ltd. Japan Raw Materials Engineering Laboratory
Publication of WO2009096147A1 publication Critical patent/WO2009096147A1/ja

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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
    • 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
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • 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
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"

Definitions

  • the present invention relates to an impregnated composition for a hardened cement material, and more particularly to a composition for improving the durability of a hardened material by applying and impregnating the hardened cement material such as mortar and concrete.
  • the durability of cement cured products such as mortar and concrete and the peeling of tiles from these cured products are such that moisture adheres to the surfaces of these cured products and moisture enters the interior from the surfaces.
  • the reinforcing bars inside the cured products are corroded and the adhesive bonding the tiles deteriorates.
  • impregnating materials for hardened cement have been used as means for preventing such intrusion of moisture.
  • these impregnating materials for example, an impregnating material mainly composed of a silane / siloxane compound, an impregnating material mainly composed of a silane compound, such as Wetexi S (trademark, manufactured by Phoslock), Nanoconcealer (trademark) , Manufactured by Nissin Japan Co., Ltd.), acrylic resin-based impregnating materials, and the like are known (Non-Patent Document 1).
  • impregnated materials for hardened cement materials have a drawback that they are severely deteriorated by ultraviolet rays and freeze-thawed and have poor durability. Further, these impregnating materials contain highly irritating volatile organic compounds such as petroleum ether solvents, and when applied, the odors emitted from them are strong, and there is a drawback that it significantly harms the health of workers. It was.
  • Patent Document 1 aqueous solution of an alkali metal silicate, for example, sodium silicate, in order to prevent moisture from entering the hardened cement and to repair cracks in the hardened cement.
  • an alkali metal silicate for example, sodium silicate
  • aqueous solutions of alkali metal silicates have a relatively high viscosity. Accordingly, even if the concentration is lowered and injected into the crack, it is difficult to penetrate to the deep part of the crack, and it is only possible to penetrate only a few millimeters from the entrance.
  • the alkali metal may react with the concrete aggregate and expand, destroying the aggregate structure and causing fine cracks again.
  • JP 2006-32267 A Atsushi Shirai and 5 others, “Performance of concrete impregnating material for concrete-Influence of curing period of base on water absorption and water permeability-”, Summary of Annual Conference of Architectural Institute of Japan, (Kanto), September 2006, p . 881-882
  • the present invention provides an impregnated composition for a hardened cement material that is excellent in durability, has low odor when applied, has low viscosity, and does not cause destruction of aggregates.
  • the inventor of the present invention paid attention to the fact that the inner surface of cracks in the hardened cement was carbonated under the influence of carbon dioxide, and mainly calcium carbonate and partially calcium hydroxide.
  • the composition, particularly the component (C) which has penetrated into the hardened cement material , not only does the cement hardened surface chemically bond with the internal tissue to form calcium silicate hydrate, not only exhibit extremely stable and sustainable performance, but also the viscosity of the composition is significantly lower, It was possible to impregnate fine cracks in the hardened cement and easily impregnate to the deep part.
  • the composition was found to have little odor when applied, and the present invention was completed.
  • the present invention (1) (A) 20 to 80 parts by mass of silicone oil, and (B) 80 to 20 parts by mass of an alcohol having 1 to 10 carbon atoms, and a total of 100 parts by mass of components (A) and (B) And (C) an impregnating composition for a hardened cement material, further containing 20 to 500 parts by mass of a silicic acid-containing solution.
  • the component (A) is 30 to 70 parts by mass, the component (B) is 70 to 30 parts by mass, and the component (C) is 50 to 400 parts by mass as described in (1) above Composition
  • the component (A) is 40 to 60 parts by mass, the component (B) is 60 to 40 parts by mass, and the component (C) is 70 to 200 parts by mass as described in (1) above Composition
  • Component (C) is represented by the following formula (I) HO— [Si (OH) 2 —O] n —H (I) (Where n is 1 to 10)
  • the composition according to any one of the above (1) to (4) which is an aqueous solution containing a compound represented by: (6)
  • composition according to any one of (1) to (8) above which is an aqueous solution obtained by dissolving at a ratio of ⁇ 0.7 mol
  • (10) The composition according to the above (9), wherein the alkali metal hydroxide is 0.15 to 0.5 mol and silicon dioxide is 0.35 to 0.6 mol
  • (11) The composition according to the above (9), wherein the alkali metal hydroxide is 0.2 to 0.4 mol and the silicon dioxide is 0.4 to 0.5 mol
  • composition (13) The composition according to any one of (9) to (11) above, wherein the alkali metal hydroxide is sodium hydroxide, (14) The composition according to any one of the above (1) to (13), wherein the component (B) is an alcohol having 1 to 4 carbon atoms, (15) The composition according to any one of (1) to (13) above, wherein the component (B) is methyl alcohol.
  • the impregnated composition for cured cement of the present invention is less deteriorated by ultraviolet rays and freezing and thawing, and therefore can maintain stable performance over a long period of time and has a low odor at the time of application. There is no risk of harm. In addition, because of its low viscosity, it can not only impregnate fine cracks in the hardened cement, but it can be easily impregnated deeper and contains almost no alkali metal, which may destroy the hardened cement. Absent.
  • the impregnated composition for hardened cement material of the present invention comprises component (A) silicone oil, component (B) alcohol having 1 to 10 carbon atoms, and component (C) silicic acid-containing solution.
  • Component (C) of the present invention is a silicic acid-containing solution.
  • the solvent include water, trimethylsiloxane, triethylsiloxane, and the like. Preferably water is used.
  • Component (C) is preferably represented by the following formula (I) HO— [Si (OH) 2 —O] n —H (I) It is an aqueous solution containing the compound shown by these.
  • the compound represented by the formula (I) may be a single substance having a single degree of polymerization, or may be a mixture of a plurality of substances having two or more types of polymerization.
  • n is an average value, and the upper limit is 10, preferably 7, more preferably 5, more preferably 2, and the lower limit is 1. If n exceeds the above upper limit, it is difficult to dissolve in water.
  • the compound represented by the formula (I) is usually present ionized in water.
  • the polymerization degree n can be measured by, for example, a trimethylsilyl (TMS) method.
  • the component (C) silicic acid-containing aqueous solution is, for example, 0.1 to 0.7 mol, preferably 0.15 to 0.5 mol, and more preferably 0.1 to 0.5 mol of alkali metal hydroxide with respect to 1 liter of water. 2 to 0.4 mol, and then silicon dioxide (SiO 2 ) is added in an amount of 0.3 to 0.7 mol, preferably 0.35 to 0.6 mol, more preferably 0.4 to 0.00 mol. It can be further dissolved and produced at a ratio of 5 moles.
  • the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and sodium hydroxide is preferably used.
  • the amount of alkali metal hydroxide exceeds the above upper limit, not only the concentration of alkali metal in the resulting impregnated composition for cement cured product increases and the possibility of destroying the aggregate structure increases, but the composition It also increases the viscosity.
  • silicon dioxide cannot be sufficiently dissolved in water.
  • the amount of silicon dioxide exceeds the above upper limit, the silicon dioxide cannot be sufficiently dissolved in water.
  • the amount of silicon dioxide is less than the above lower limit, the obtained impregnated composition for a cured cement material is used. The effects of the invention cannot be imparted sufficiently.
  • the component (C) silicic acid-containing aqueous solution can also be produced by electrolyzing water glass.
  • silicone oil A conventionally well-known various silicone oil can be used.
  • silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil. These silicone oils may be used alone or in combination of two or more.
  • the upper limit of the viscosity (25 ° C.) of the silicone oil is preferably 1,000 mPa ⁇ s, more preferably 500 mPa ⁇ s, still more preferably 100 mPa ⁇ s, and the lower limit is preferably 1 mPa ⁇ s, more preferably 5 mPa ⁇ s. s.
  • Exceeding the upper limit is not preferable because the viscosity of the impregnated composition for a hardened cement product increases.
  • limiting in particular in the measuring method of this viscosity It can measure using well-known viscometers, such as a B-type viscosity meter, an E-type viscosity meter, and a rheometer.
  • a commercial item can be used as this silicone oil.
  • Commercially available products include, for example, dimethyl silicone oil KF series (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., methyl phenyl silicone oil KF series (trademark) manufactured by Shin-Etsu Chemical Co., Ltd., methyl hydrogen silicone oil KF manufactured by Shin-Etsu Chemical Co., Ltd. Series (trademark), modified silicone oil BY series (trademark) manufactured by Toray Dow Corning Co., Ltd., dimethyl silicone oil SH series (trademark) manufactured by Toray Dow Corning Co., Ltd., and the like.
  • the upper limit of the carbon number of the component (B) alcohol is 10, preferably 6, and more preferably 4, and the lower limit is 1.
  • the alcohol include monohydric alcohols and polyhydric alcohols such as dihydric alcohols and trihydric alcohols.
  • Component (A) and component (B) are blended in an amount of 20 to 80 parts by mass of component (A) and 80 to 20 parts by mass of component (B) out of a total of 100 parts by mass of component (A) and component (B).
  • the component (A) is preferably 30 to 70 parts by mass and the component (B) is 70 to 30 parts by mass, and more preferably the component (A) is 40 to 60 parts by mass and the component (B) is 60 to 40 parts by mass.
  • component (B) is less than the lower limit and component (A) exceeds the upper limit, the components are separated and the composition becomes non-uniform, and component (B) exceeds the upper limit and component (A) is the lower limit. If it is less than this, the water repellency of the composition will be poor.
  • the upper limit of the compounding amount of the component (C) is 500 parts by weight, preferably 400 parts by weight, more preferably 200 parts by weight, and the lower limit is 100 parts by weight in total of the component (A) and the component (B). 20 parts by mass, preferably 30 parts by mass, more preferably 40 parts by mass.
  • the component (C) exceeds the above upper limit or less than the above lower limit, the water repellency of the composition is lowered, and the effects of the present invention cannot be exhibited sufficiently.
  • the cement cured product in which the composition of the present invention is used preferably refers to a cement alone or a cured composition containing cement and aggregate, and examples thereof include concrete and mortar.
  • the cement is preferably a hydraulic cement, for example, ordinary Portland cement, moderately hot Portland cement, early strength Portland cement, low sulfate Portland cement, white Portland cement and other Portland cement, hydraulic lime, Roman cement Natural cement, alumina cement, blast furnace cement, silica cement, expanded cement, colored cement and the like.
  • the aggregate include sand, gravel, silica fume, artificial lightweight aggregate, pearlite, and granulated slag.
  • additives such as stabilizers, pigments, surfactants and various chemical admixtures for concrete can be blended as long as the effects of the present invention are not impaired. .
  • the impregnation composition for hardened cement material of the present invention can be produced, for example, by mixing the component (A), the component (B), and the component (C) at room temperature.
  • Component (C) Silicic acid-containing solution was prepared as follows.
  • ⁇ Comparison impregnating agent> As a comparative impregnating agent, an impregnating material (MC Fine, trademark, manufactured by EMD Corporation) containing a silane compound as a main component was used.
  • Evaluation items and evaluation methods for each impregnation composition and comparative impregnation material are as follows.
  • ⁇ Neutralization depth test> It conformed to JSCE-K571-2005.
  • the impregnation composition and the comparative impregnation material in accordance with JIS A 1153, under conditions of a temperature of 20 ⁇ 2 ° C., a relative humidity of 60 ⁇ 5%, and a carbon dioxide concentration of 5 ⁇ 0.2%, A 28-day accelerated neutralization test was conducted. Then, based on JIS A1152, the test body was split so that the impregnation surface of a test body was divided into two, and the neutralization depth from the impregnation surface of the split surface was measured.
  • ⁇ Chlorine ion penetration depth test> It conformed to JSCE-K571-2005. Immerse in water at a temperature of 23 ⁇ 2 ° C. so that the impregnation surface of each test specimen impregnated with the impregnation composition and the comparative impregnation material is the side surface, and the upper surface of the test specimen is 20 mm or more below the water surface, A chloride ion penetration test was performed. The test specimen was taken out 63 days after the start of immersion. Then, based on 7.8 of JIS A 1171, the test body was split so that the impregnation surface of the test body was divided into two, and the chloride ion penetration depth from the impregnation surface of the split surface was measured.
  • ⁇ Freeze-thaw test> It conformed to JIS A 1148 (freezing and thawing test method of concrete).
  • Each test specimen impregnated with the impregnation composition and the comparative impregnation material was subjected to a total of 300 cycles at a freezing temperature of ⁇ 18 ° C., a melting temperature of + 20 ° C., and a cycle of 5 to 6 hours.
  • the relative kinematic modulus and mass reduction rate of each test specimen were measured.
  • the relative kinematic modulus is calculated by measuring the primary resonance frequency of the flexural vibration for each test specimen for each cycle and using the following equation.
  • Relative kinematic modulus (%) F n 2 / F 0 2 ⁇ 100 (Where F 0 is the primary resonance frequency of the flexural vibration of the specimen before the start of the test, and F n is the primary resonant frequency of the flexural vibration of the n-cycle specimen.)
  • the mass reduction rate was measured by measuring the mass of the test specimen before the start of the freeze-thaw test and the mass of the test specimen in each cycle, and indicated the percentage of the reduced mass with respect to the mass of the test specimen before the start of the freeze-thaw test.
  • the obtained mortar was molded into dimensions of 100 mm ⁇ 100 mm ⁇ 400 mm. This was kept in air at 20 ° C. and 90% (RH) for 1 day and then in water at 20 ° C. for 6 days.
  • the molded body thus obtained was cut into dimensions of 100 mm ⁇ 100 mm ⁇ 100 mm. This was dried in air at 20 ° C. and 60% (RH) for 25 days, and then specified in JIS K 5664 (tar epoxy resin paint) on each surface except the surface coated with the impregnating material and the surface opposite to the surface.
  • An epoxy resin paint (Unitac, trademark, Taiheiyo Material Co., Ltd.) was applied and further dried under the same conditions for 3 days.
  • impregnation composition and a comparative impregnation material were applied to the obtained molded body, and dried in air at 20 ° C. and 60% (RH) for 14 days. This was used as a specimen for appearance observation, impregnation depth test, water permeability test, water absorption rate test, neutralization depth test, and chloride ion penetration depth test.
  • the mortar was molded into dimensions of 40 mm ⁇ 40 mm ⁇ 160 mm. This was kept in air at 20 ° C. and 90% (RH) for 1 day and then in water at 20 ° C. for 6 days. The molded body thus obtained was dried in air at 20 ° C. and 60% (RH) for 25 days, and then JIS K 5664 was formed on each surface excluding the impregnated material coated surface and the surface facing the surface.
  • An epoxy resin paint (Unitac, trademark, Taiheiyo Material Co., Ltd.) specified in (Tar epoxy resin paint) was applied and further dried under the same conditions for 3 days.
  • the obtained molded body was impregnated with the impregnation composition and the comparative impregnation material, and dried in air at 20 ° C. and 60% (RH) for 14 days. This was used as a specimen for a freeze-thaw test.
  • Example 1 (A) 50 parts by mass of silicone oil, (B) 50 parts by mass of methyl alcohol, and (C) 100 parts by mass of silicic acid-containing aqueous solution (I) were stirred at room temperature to produce an impregnated composition for a cement cured product. Various tests were conducted using the composition.
  • Table 4 shows the results of the impregnation depth test, water permeability test, water absorption rate test, neutralization depth test, and chloride ion penetration depth test.
  • Example 2 (A) Silicone oil, (B) methyl alcohol, and (C) silicic acid-containing aqueous solution were stirred at room temperature at the blending amounts shown in Table 6 to produce impregnated compositions for each hardened cement material. Various tests were conducted using the composition. The test results are shown in Table 6.
  • Examples 2 and 3 are obtained by increasing and decreasing the content of the component (C) with respect to Example 1, respectively.
  • Examples 4 and 5 are different from Example 1 in that component (A) is increased and component (B) is decreased, and component (A) is decreased and component (B) is increased, respectively. It is a thing.
  • the component (C) silicic acid-containing aqueous solution (I) was converted into a silicic acid-containing aqueous solution (II) having a high silicic acid content and a silicic acid-containing aqueous solution (III) having a low silicic acid content, respectively. Instead of. In any of the examples, good results were obtained.
  • Comparative Examples 1 and 2 are obtained by increasing and decreasing the content of the component (C) out of the scope of the present invention with respect to Example 1, respectively.
  • Comparative Examples 3 and 4 the component (A) is increased and the component (B) is decreased outside the scope of the present invention, and the component (A) is outside the scope of the present invention.
  • component (B) are increased.
  • Comparative Examples 1 and 2 the neutralization depth deteriorated.
  • Comparative Example 3 each component in the impregnation composition was separated and could not be used as an impregnation material.
  • Comparative Example 4 the water permeability and the neutralization depth deteriorated.
  • Example 5 It implemented like Example 1 except having replaced with the component (C) silicic acid containing aqueous solution (I) and using a comparative impregnating agent (MC fine, a trademark, the product made from EM Co., Ltd.).
  • MC fine a trademark, the product made from EM Co., Ltd.
  • Table 8 shows the results of the impregnation depth test, the water permeability test, the water absorption rate test, and the neutralization depth test.
  • the impregnating composition for cured cement of the present invention is better than the comparative impregnating agent in any of the impregnation depth, water permeability, water absorption rate, and neutralization depth. I found out.
  • the impregnated composition for hardened cement according to the present invention is applied to hardened cement such as concrete and mortar to prevent moisture from entering the hardened cement and avoid corrosion of reinforcing bars and falling off of tiles. These durability can be remarkably improved. In addition, it can be used for repairing a hardened cement by injecting it into cracks of the hardened cement. Moreover, the impregnating composition for hardened cement material of the present invention can impart water repellency to wood by applying it to wood, thereby enhancing its durability.

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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)
PCT/JP2009/000167 2008-01-28 2009-01-20 セメント硬化物用含浸組成物 WO2009096147A1 (ja)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7243982B2 (ja) * 2018-03-26 2023-03-22 国立大学法人山口大学 コンクリート補修剤

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63310781A (ja) * 1987-06-12 1988-12-19 Kikusui Kagaku Kogyo Kk 旧劣化表面の強化化粧方法
JPH10310768A (ja) * 1997-03-10 1998-11-24 Inter Seputo Kk 紫外線カット型超撥水剤、それを塗工してなる改質セメント系成形体およびそれで後加工してなる改質編織布
JPH10316937A (ja) * 1997-03-14 1998-12-02 Matsushita Electric Works Ltd 防汚性シリコーンエマルジョンコーティング材組成物とその製造方法およびそれを用いた防汚性塗装品
JP2005015727A (ja) * 2003-06-30 2005-01-20 Kansai Paint Co Ltd 撥水性被膜形成組成物及びそれを用いた塗装方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63310781A (ja) * 1987-06-12 1988-12-19 Kikusui Kagaku Kogyo Kk 旧劣化表面の強化化粧方法
JPH10310768A (ja) * 1997-03-10 1998-11-24 Inter Seputo Kk 紫外線カット型超撥水剤、それを塗工してなる改質セメント系成形体およびそれで後加工してなる改質編織布
JPH10316937A (ja) * 1997-03-14 1998-12-02 Matsushita Electric Works Ltd 防汚性シリコーンエマルジョンコーティング材組成物とその製造方法およびそれを用いた防汚性塗装品
JP2005015727A (ja) * 2003-06-30 2005-01-20 Kansai Paint Co Ltd 撥水性被膜形成組成物及びそれを用いた塗装方法

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