JP3062008B2 - Antifreeze recovery agent for porous solids and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifreezing / restoring agent for a porous solid, and more particularly to a water-permeable or drainable pavement such as a porous road capable of removing water remaining on a road surface. In addition, the present invention relates to an antifreezing / restoring agent for a porous solid that regenerates a water-permeable function or a drainage function when a pavement is clogged, and a method for producing the same.

[0002]

2. Description of the Related Art Water-permeable and drainable pavements are used from the viewpoint of groundwater recharge in order to prevent flooding of rivers due to a decrease in water retention due to the expansion of urban development, in contrast to currently widely used impermeable asphalt pavements. Is being developed. The permeable pavement has a porous structure obtained by mixing a synthetic resin such as an epoxy resin or a modified asphalt as a binder with an aggregate such as natural stone or ceramic and thermally curing the mixture. In addition, the drainage pavement forms a permeable pavement on top of the impermeable pavement,
This structure drains water that has penetrated the permeable pavement. The water-permeable and drainable pavement can use a high porosity asphalt mixture to infiltrate water and eliminate water remaining on the pavement surface layer. Water that has accumulated on the pavement on paved roads,
Since the tires slide due to the splashing and the hydroplane phenomenon, the water-permeable and drainable pavement road can improve the running safety of the vehicle in rainy weather or the like and reduce the traffic noise.

[0003] However, the water-permeable and drainable pavement in winter or cold regions has a problem in that the drainage and water-permeability in the pores are frozen and clogged, thereby significantly reducing the water-permeability and drainage function of the pavement. In addition, the water-permeable and drainable pavement is clogged by dust or earth and sand entering the pores of the pavement due to long-term use, and the permeation of rainwater into the ground is significantly eliminated. For example, Japanese Patent Publication No. 61-47249 discloses a method of recovering water permeability by spraying pressure water onto the surface of a water-permeable pavement to remove clogged substances. JP 63
JP-A-223206, JP-A-3-137310, JP-A-4-115005, JP-A-4-115
No. 006 discloses a device for recovering the function of a water-permeable or drainable pavement in which high-pressure water is injected and sucked together with a clogging substance. Further, JP-A-6-33428 discloses a water-permeable pavement in which a foaming solution is applied to a water-permeable pavement and particles of the clogging substance in the pores floating on the surface are sucked and collected together with the sprinkled water. 1 shows a cleaning method and a cleaning device.

[0004]

The deterioration of the water-permeability and drainage functions of a water-permeable and drainable pavement in winter or in a cold region is caused by the fact that water accumulated on the road surface freezes to reduce slipping resistance, thereby reducing the safety of vehicle running. Cannot be secured. In order to maintain the water permeation and drainage functions of the pavement, it is necessary to prevent the water permeation and drainage in the pores from freezing. Further, it is necessary to remove clogging substances in the pores to regenerate the water permeation function and the drainage function. A conventional method and apparatus for restoring the function of a water-permeable and drainable pavement is to lift a clogging substance such as dust or earth and sand that has entered the pores with high-pressure water or a foaming solution, and then suction the same together with the water or foaming solution. Collect by device. Therefore, in a pavement in which pores are clogged by permeation and freezing of drainage, the high-pressure water or the foaming solution does not permeate into the pores, and the pavement cannot recover its water permeability and drainage functions. In addition, it is difficult to completely float all the clogging substances such as dust or earth and sand that have entered the pores with high-pressure water or a foaming solution. It is not possible to lift the clogging material with high pressure water or a foaming solution. Furthermore, even if the clogged substance is floated, it cannot be reliably recovered because it returns to the pores along with water permeation before suction.

[0005] Therefore, the present invention is to prevent the permeation and drainage of the pores of the water-permeable and drainage pavement in winter or cold regions, to prevent freezing, and to maintain the water-permeation function and drainage function, and to prevent dust or sediment in the pores. It is an object of the present invention to provide an antifreezing / restoring agent for a porous solid which reliably removes a clogging substance such as a water-permeable function and a drainage function easily and efficiently, and a method for producing the same.

[0006]

The antifreeze and recovery agent for a porous solid according to the present invention is at least 5.0%, preferably at least 10.0%, and at most 30.0%, preferably at most 15%, by weight. 2.0% or less of alcohols and 1.0% or more,
Preferably at least 8.0% and no more than 30.0%, preferably no more than 15.0% of a deliquescent hygroscopic substance, and at least 0.05% and preferably at least 0.1% and no more than 1.0%; Preferably 0.
3% or less carboxylic acid and 0.1% or more, preferably 0.1%.
5% or more and 2.0% or less, preferably 1.0% or less, and 0.1% or more, preferably 1.8% or more and 4.0% or less.
0% or less, preferably 2.5% or less asphalt solvent, and 0.1% or more, preferably 0.8% or more and 2.0%
Or less, preferably 1.5% or less of surfactant and 5.0%
Or more, preferably 7.0% or more and 20.0% or less, preferably 13.0% or less of inorganic acid, and 11.0% or more, preferably 51.7% or more and 88.65% or less; Preferably not more than 71.8% of water.

Alcohols are ethylene glycol, methyl alcohol or glycerin, deliquescent and hygroscopic substances are potassium acetate, calcium chloride or magnesium chloride, carboxylic acids are oxalic acid, malonic acid, crotonic acid or formic acid, reducing agents are gallic acid, sodium sulfide or Trioxyglutaric acid, asphalt solvent is dioxane, ethyl methyl ketone or acetone, surfactant is alkyl polyoxyethylene ether, P-alkylphenyl polyoxyethylene ether, sodium alkyl benzene sulfonate or alkyl pyridinium sulfate, inorganic acid is hydrazine hydrochloride , Carbonic acid or hydrochloric acid.

The method for preparing the antifreezing / restoring agent for a porous solid according to the present invention is at least 5.0%, preferably at least 10.0%, and at most 35.0%, preferably at least 15.0%, on a weight basis.
0% or less of alcohols and 1.0% or more, preferably 8.0% or more, and 30.0% or less, preferably 15.0%
With the following deliquescent and hygroscopic substances: 0.05% or more, preferably 0.1% or more and 1.0% or less, preferably 0.3% or less of carboxylic acid, 0.1% or more, preferably 0.3% or more. 5% or more and 2.0% or less, preferably 1.0% or less, and 0.1% or more, preferably 1.8% or more and 4.0% or less, preferably 2.5% or less 60 asphalt solvent
A step of adding 71.0% or more, preferably 81.7% or more, and 94.65% or less, preferably 89.8% or less of water at 80 ° C. and stirring to dissolve the additive uniformly in water. And then 0.1% or more, preferably 0.8% or more and 2.0%
Hereinafter, a step of adding a surfactant of preferably 1.5% or less, stirring and uniformly dissolving, and further, a step of 5.0% or more, preferably 7.0% or more and 20.0% or less, preferably Is 1
Adding 3.0% or less of an inorganic acid and stirring.

[0009]

An aqueous solution of a porous solid freezing / restoring agent is sprayed on the surface of a water-permeable and drainable pavement in winter or cold regions. Since the freezing point (freezing point) of alcohols is 0 ° C. or lower, it is possible to prevent water permeation in pores and freezing of drainage. Since the deliquescent hygroscopic substance associates with water and lowers the freezing point to -10 to -30 ° C, it prevents freezing of permeate and drainage, and also prevents ice that causes permeation and clogging of pores due to freezing of permeate and drainage. Thaw to make water. The clogging substance including dust or earth and sand that has entered the pores is silicon dioxide (Si).
A glass made of a metal compound such as O ₂ ) and iron (Fe);
Sand, Jari. A clogging substance such as silicon dioxide and a metal compound is dissolved with an inorganic acid, a carboxylic acid, a reducing agent and an asphalt solvent, and a complex salt is formed from a metal ion dissolved and released with a carboxylic acid, a reducing agent and an asphalt solvent. Since the complex salt is dispersed in water and becomes colloidal, it can be removed from the pores together with water permeation and drainage. Also,
Due to the synergistic effect of the air-lifting action of hydrogen gas generated from the inorganic acid and the surface-activating action of giving a good wettability to the surface of silicon dioxide and metal compounds with a surfactant, clogging substances such as silicon dioxide and metal compounds are reduced. It moves out of the pores and is discharged out of the pavement by permeation and drainage. Furthermore,
By dissolving the surface of the asphalt with the asphalt solvent to slightly expand the pores, the transfer of clogging substances such as silicon dioxide and metal compounds is facilitated.

The composition ratio of the antifreezing and recovery agent for the porous solid is 5.0% by weight based on the balance of the components.
Above, preferably 10.0% or more, 30.0% or less, preferably 15.0% or less of alcohols, and 1.0% or more, preferably 8.0% or more, 30.0% or less, Preferably 15.0% or less of deliquescent and hygroscopic substance and carboxylic acid is 0.05% or more, preferably 0.1% or more and 1.0% or less, preferably 0.3% or less. The reducing agent is at least 0.1%, preferably at least 0.5% and at most 2.0%, preferably at most 1.0%. The asphalt solvent is at least 0.1%, preferably at least 1.8% and at most 4.0%, preferably at most 2.5%. The surfactant is at least 0.1%, preferably at least 0.8% and at most 2.0%, preferably at 1.5%.
% Or less. Inorganic acid is 5.0% or more, preferably 7.0%
% Or more and 20.0% or less, preferably 13.0% or less. Water is at least 11.0%, preferably at least 51.7% and at most 88.65%, preferably at most 71.8%. If the lower limit of each composition ratio of the alcohols and the deliquescent hygroscopic substance is below the lower limit, the water permeation and the drainage are prevented from freezing, and the ice in the pores generated by the freezing cannot be melted into water.
If the lower limit of each composition ratio of the inorganic acid, carboxylic acid, reducing agent, and asphalt solvent is below the lower limit, silicon dioxide and metal compounds are surely dissolved, metal ions are not released, and complex salts are not formed. Further, even if the mixing exceeds the upper limit of each composition ratio, the effect of restoring the water permeability above the upper limit cannot be obtained, and the soil and groundwater may be contaminated.

Further, alcohols, deliquescent and hygroscopic substances, carboxylic acids, reducing agents and asphalt solvents are added, and then a surfactant is added so that each component is uniformly dissolved. The mixture is stirred at a water temperature of ８０80 ° C. for 60 to 80 minutes for tempering. Surfactants hinder the dissolution of alcohols, deliquescent and hygroscopic substances, carboxylic acids, reducing agents and asphalt solvents, so that during the production of the antifreezing / restoring agent for porous solids according to the present invention, these additives are dissolved. And then add. Further, since the inorganic acid hinders the dispersion of the surfactant in the mixture, the surfactant is added and added after stirring.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A 3-10% aqueous solution of an antifreezing and restoring agent for a porous solid according to the present invention is sprayed on a water-permeable and drainable pavement in a winter or cold area at a temperature of -5 to -15 ° C with a sprayer. For 15 to 30 minutes. In order to carry out the present invention, 6.5 m in width, 200 m in length, and 4 cm in depth (thickness) on the existing asphalt pavement with a gradient of 2% from the center of the road to both sides.
Thus, a test section where drainage pavement was constructed using ascon having an open particle size (porosity) having a porosity of 20% was provided. The degree of antifreezing is 110 mm in width and 70 mm in depth containing 250 g of water,
After a sponge body having a height of 30 mm was placed on the road surface for a certain period of time, the weight at which the sponge body peeled off the road surface was measured. At a temperature of -5 to -15 ° C, the sponge body did not peel off from the road surface without spraying the antifreezing / restoring agent according to the present invention, and the degree of antifreezing could not be measured. In addition, by the on-site permeability test method, the elapsed time when the water level in the test device pressed to the road surface in the test section fell to a certain water level was measured, and the water permeability of the drainable pavement was measured. When pavement is applied, water permeability is 1
Although it was 100cc / 15 seconds, it was 1 at 5 tons / vehicle conversion
The amount of water permeation three months after the construction of 000 units / day was reduced to 650 cc / 15 seconds without spraying the anti-freezing / restoring agent according to the present invention.

Example 1 5.0% ethyl alcohol, 1.0% titanium (IV) sulfate, 0.05% trimesic acid, 0.1% trioxyglutaric acid,
0.1% of dioxyacetone was added to 88.65% of water at 80 ° C. and stirred to dissolve uniformly. Next, 0.1% of alkyltrimethylammonium halide was added and stirred to dissolve uniformly. Finally, add 5.0% of hydrazine hydrochloride and add 8%.
The mixture was stirred for 0 minutes to obtain a brown transparent restoring agent for a porous solid.

The obtained 10.0% aqueous solution of the regenerating agent was sprayed at a rate of 5 liters / m ² on a test zone 3 months after the construction of the drainage pavement using a spray truck. It was 9.6 kg when the degree of freezing was measured at an air temperature of -5 ° C. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. Fifteen minutes after the application of the antifreezing / restoring agent, high-pressure washing with 150 liter / m ² was performed at a pressure of 10 kg / cm ² . Then, when the water permeability was measured, the water permeability was 1002 cc / 1.
It improved to 5 seconds (91.1% recovery rate).

Example 2 8.0% ethylene glycol, 9.0% calcium chloride,
0.05% malonic acid, 0.1% sodium sulfide and 0.1% dioxane are added to 72.55% water at 60 ° C. and stirred,
Uniformly dissolved. Next, 0.2% of P-alkylphenyl polyoxyethylene ether was added and stirred to dissolve uniformly. Finally, 10.0% of carbonic acid was added and the mixture was stirred for 80 minutes to obtain an antifreezing / restoring agent for a brown transparent porous solid.

The obtained 3.0% aqueous solution of the antifreezing / restoring agent was sprayed at 5 liters / m ² on the test section 3 months after the construction of the drainage pavement. When the degree of freezing prevention was measured at an air temperature of -5 ° C, it was 8.0 kg. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. Further, 30 minutes after the application of the anti-freezing / restoring agent, high pressure washing with 150 liter / m ² was carried out at a pressure of 10 kg / cm ² , and the water permeability was measured.
It turned out that it recovered in 5 seconds (recovery rate 92.3%).

Example 3 9.0% isopropyl alcohol, sodium hydroxide 1
8.0%, 0.1% of acetic acid, 0.1% of gallic acid and 4.0% of acetone were added to 63.7% of water at 60 ° C., stirred and uniformly dissolved. Next, 0.1% of alkyl polyoxyethylene ether was added and stirred to dissolve uniformly. Finally, 5.0% of hydrochloric acid was added, and the mixture was stirred for 60 minutes to obtain a brown transparent clearing agent for a porous solid.

The obtained 3.0% aqueous solution of the regenerating agent was sprayed at 5 liters / m ² on a test section 3 months after the construction of the drainage pavement using a spray truck. When the degree of freezing prevention was measured at an air temperature of -15 ° C, it was 9.2 kg. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. Further, 30 minutes after the application of the antifreezing / restoring agent, high-pressure washing with 150 liter / m ² was performed at a pressure of 10 kg / cm ² , and the water permeability was measured.
It turned out that it recovered in 5 seconds (recovery rate 91.8%).

EXAMPLE 4 13.0% of ethylene glycol, 10.0% of potassium acetate, 0.1% of oxalic acid, 0.6% of gallic acid and 2.2% of dioxane were added to 62.9% of water at 70 ° C. Stir and dissolve uniformly. Next, alkylpolyoxyethylene ether 2.2%
Was added and stirred to dissolve uniformly. Finally, add hydrochloric acid 5.0
%, And the mixture was stirred for 60 minutes to obtain an antifreezing / restoring agent for a brown transparent porous solid.

A 5.0% aqueous solution of the obtained anti-freezing / restoring agent was sprayed at a rate of 5 liters / m ² on the test section three months after the construction of the drainage pavement. When the degree of freezing was measured at an air temperature of -10 ° C, it was 8.1 kg. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. Fifteen minutes after spraying the anti-freezing / restoring agent, high pressure washing was performed at 150 liter / m ² at a pressure of 10 kg / cm ² , and then the water permeability was measured.
It turned out that it recovered in 5 seconds (recovery rate 93.2%).

Example 5 15.0% propylene glycol, 15.0% cesium acetate
%, 0.3% of oxalic acid, 1.0% of sodium polysulfide and 2.1% of dioxane are added to 52.4% of water at 72 ° C. and stirred.
Uniformly dissolved. Next, sodium alkyl sulfate 1.0
% And stirred to dissolve uniformly. Finally phosphoric acid 1
3.0% was added and the mixture was stirred for 68 minutes to obtain a brown transparent clearing agent for a porous solid.

The obtained 6.0% aqueous solution of the regenerating agent was sprayed at 5 liters / m ² on a test section 3 months after the construction of the drainage pavement with a spray truck. When the degree of freezing prevention was measured at an air temperature of -15 ° C, it was 8.9 kg. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. After spraying the anti-freezing and recovery agent for 20 minutes, high pressure washing with 150 liter / m ² was performed at a pressure of 10 kg / cm ² . Thereafter, when the water permeability was measured, the water permeability was 1030 cc / 1.
It recovered to 5 seconds (recovery rate 93.6%).

EXAMPLE 6 25.0% of methyl alcohol, 2.0% of potassium acetate, 0.5% of crotonic acid, 0.6% of gallic acid and 2.2% of ethyl methyl ketone were added to 64.2% of water at 69.degree. And stirred to dissolve uniformly. Next, 0.5% of sodium alkylbenzenesulfonate was added and stirred to dissolve uniformly. Finally, 5.0% hydrochloric acid was added and the mixture was stirred for 61 minutes to obtain a brown and clear antifreezing / restoring agent.

The obtained 6.0% aqueous solution of the antifreezing / restoring agent was sprayed at 5 liters / m ² on the test section 3 months after the construction of the drainage pavement. When the degree of freezing prevention was measured at an air temperature of -10 ° C, it was 5.2 kg. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. Also, after 20 minutes of spraying the anti-freezing / restoring agent, high pressure washing with 150 liter / m ² was performed at a pressure of 10 kg / cm ² , and then the water permeability was measured.
It recovered to 5 seconds (recovery rate 95.5%).

Example 7 80.0% of glycerin, 30.0% of magnesium chloride, 1.0% of formic acid, 2.0% of gallic acid and 4.0% of acetone
The mixture was added to water (11.0%) at 0 ° C., stirred and uniformly dissolved. Next, 2.0% of alkylpyridinium sulfate was added and stirred to dissolve uniformly. Finally, 20.0% of hydrazine hydrochloride was added, and the mixture was stirred for 75 minutes to obtain a brown transparent porous solid antifreezing / restoring agent.

The 10.0% aqueous solution of the obtained anti-freezing / restoring agent was sprayed at 5 liters / m ² on the test section 3 months after the construction of the drainage pavement. It was 7.7 kg when the degree of freeze prevention was measured at an air temperature of -15 ° C. The sponge body did not exfoliate from the road surface where the antifreezing / restoring agent was not sprayed. Fifteen minutes after spraying the anti-freezing / restoring agent, high-pressure washing with 150 liter / m ² was performed at a pressure of 10 kg / cm ² , and then the water permeability was measured.
It recovered to 5 seconds (recovery rate 99.1%).

In any of the examples, the water permeation and drainage in the pores were not frozen after the antifreezing / restoring agent of the present invention was sprayed. In addition, the amount of water permeability shows almost the amount of water permeation at the time of drainage pavement construction, the water permeability can be restored, even if hot water is sprayed, almost no water permeation, and the water-permeability and drainage pavement that is not drained, when hot water is sprayed Completely permeable and drained. In Example 7, the composition ratio of each additive was set to the upper limit, but there was no significant difference in the effect of restoring the water permeability compared to the other examples.

The anti-freezing and restoring agent for a porous solid according to the present invention comprises an alcohol, a deliquescent and hygroscopic substance, a carboxylic acid, a reducing agent, an asphalt solvent, a surfactant and an inorganic acid, and water. . Since the freezing point (freezing point) of alcohols is 0 ° C. or less, permeation and freezing of drainage can be prevented. The deliquescent hygroscopic substance associates with water.
Since the freezing point is lowered to 30 ° C., the permeation and drainage are prevented from freezing, and the ice that causes the permeation and drainage to freeze and clog the pores is melted into water. A clogging substance such as silicon dioxide and a metal compound is dissolved with an inorganic acid, a carboxylic acid, and a reducing agent, and then a complex salt is formed from a metal ion dissolved and released with a carboxylic acid, a reducing agent, and an asphalt solvent.
When an acetate such as potassium acetate is used as the deliquescent and hygroscopic substance, the clogging substance can also be dissolved with acetic acid to form a complex salt. Since the complex salt is dispersed in water and becomes colloidal, it can be removed from the pores together with water permeation and drainage. In addition, clogging of silicon dioxide and metal compounds is caused by a synergistic effect of an air-lifting action of hydrogen gas generated from the inorganic acid and a surface active action of providing a surfactant with good wettability on the surfaces of silicon dioxide and metal compounds. The material moves out of the pores and is discharged out of the pavement by permeation and drainage. Further, the asphalt solvent dissolves the surface of the asphalt to slightly expand the pores, thereby facilitating the transfer of clogging substances such as silicon dioxide and metal compounds.

To prepare the antifreezing / restoring agent for a porous solid according to the present invention, an alcohol, a deliquescent hygroscopic substance, a carboxylic acid, a reducing agent and an asphalt solvent are heated at 60 to 80 ° C.
Then, the mixture is stirred and added to water, and the additives are uniformly dissolved in water. Then, a surfactant is added and stirred, the mixture is uniformly dissolved, and an inorganic acid is added and stirred for 60 to 80 minutes. Alcohols, deliquescent and hygroscopic substances, carboxylic acids, reducing agents and asphalt solvents are added so that each component is uniformly dissolved, then a surfactant is added, and further an inorganic acid is added, and at a water temperature of 60 to 80 ° C. 6
Stir for 0-80 minutes. Surfactants hinder the dissolution of alcohols, deliquescent and hygroscopic substances, carboxylic acids, reducing agents and asphalt solvents, so that during the production of the antifreezing / restoring agent for porous solids according to the present invention, these additives are dissolved. And then add. Further, since the inorganic acid hinders the dispersion of the surfactant in the mixture, the surfactant is added and added after stirring.

Water-soluble alcohols for preventing permeation and freezing of drainage include methyl alcohol, ethyl alcohol,
Propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, isoamyl alcohol, hexyl alcohol, propargyl alcohol, benzyl alcohol, monohydric alcohol such as furfuryl alcohol, ethylene glycol, propylene glycol, trimethylene glycol, 1,4
-Butanediol, 1,5-pentanediol, 1,6-
It is a dihydric alcohol such as hexanediol and 1,7-heptanediol, and a polyhydric alcohol such as glycerin, tetrit, penchit and hexit.

Water-soluble deliquescent and hygroscopic substances which prevent permeation and drainage of water and melt ice are deliquescent substances such as aluminum chloride / AlCl ₃ of chloride, aluminum bromide / AlBr ₃ of bromide, aluminum iodide / AlI ₃ iodide, aluminum nitrate nonahydrate / Al (NO ₃₎ of nitrates ₃ · 9H ₂ O, barium nitrate / Ba (N
O ₃ ) ₂ , fluorides of beryllium fluoride / BeF ₂ , beryllium chloride / BeCl ₂ , beryllium bromide / BeBr ₂ , beryllium nitrate trihydrate / Be (NO ₃ ) ₂ .3H ₂ O, bismuth chloride / BiCl ₃ , bismuth bromide / BiBr ₃ , calcium chloride / CaCl ₂ , calcium bromide / CaBr ₂ ,
Calcium iodide / CaI ₂ , calcium nitrite monohydrate of nitrite / Ca (NO ₂ ) ₂ .H ₂ O, calcium nitrate tetrahydrate / Ca (NO ₃ ) ₂ .4H ₂ O, cerium chloride (II
I) / CeCl ₃ , cerium (III) nitrate hexahydrate / Ce (N
_{O 3) 3 · 6H 2 O} , ceric ammonium nitrate / Ce (N
H ₄ ) ₂ (NO ₃ ) ₆ , cobalt (II) bromide CoBr ₂ , cobalt (II) iodide / CoI ₂ , cobalt (II) nitrate hexahydrate / C
o (NO ₃ ) ₂ .6H ₂ O, chromium (II) chloride / CrCl ₂ , cesium chloride / CsCl, cesium iodide / CsI, hydroxide cesium hydroxide / CsOH, sulfide cesium sulfide tetrahydrate _{/ Cs 2 S · 4H 2 O} , cesium carbonate carbonate / Cs ₂ CO _3, copper (II) chloride dihydrate / CuCl ₂ · 2
H ₂ O, copper (II) nitrate trihydrate / Cu (NO ₃ ) ₂ .3H ₂ O,
Iron (II) chloride tetrahydrate / FeCl ₂ .4H ₂ O, iron bromide (II
I) / FeBr ₃ , iron (II) iodide / FeI ₂ , iron (III) sulfate
Nonahydrate _{/ Fe 2 (SO 4) 3} · 9H 2 O, iron (III) nitrate nonahydrate _{/ Fe (NO 3) 3 ·} 9H 2 O, iodine trichloride / IC
l ₃ , iodine pentoxide / I ₂ O ₅ , hydroxide potassium hydroxide / KOH, potassium sulfide / K ₂ S, thiosulfate potassium thiosulfate / 3K ₂ S ₂ O ₃ .H ₂ O, potassium nitrite / KNO ₂ , phosphorous acid dipotassium hydrogen phosphate / K ₂ H
PO ₄ , potassium metaborate of metaborate / KB
O ₂ , potassium molybdate of molybdenum oxide / K ₂ M
oO _4, potassium acetate / KCH ₃ COO, magnesium potassium nitrate hexahydrate / KMgCl ₃ · 6H ₂ O chloride, lithium chloride / LiCl, lithium bromide / LiBr, lithium iodide / LiI, lithium sulfide / Li ₂ S, nitrate Lithium / LiNO ₃ , magnesium chloride hexahydrate / MgCl _2.
6H ₂ O, magnesium bromide / MgBr ₂ , magnesium bromide hexahydrate / MgBr ₂ .6H ₂ O, magnesium nitrate hexahydrate / Mg (NO ₃ ) ₂ .6H ₂ O, ammonium chloride magnesium hexahydrate objects _{/ MgNH 4 Cl 3 · 6H 2} O, manganese chloride (II) / MnCl _2, iodide manganese (II) / Mn
I ₂ , manganese (III) sulfate / Mn ₂ (SO ₄ ) ₃ , molybdenum (VI) / MoF ₆ , molybdenum (IV) chloride / MoC
l ₄ , molybdenum (IV) bromide / MoBr ₄ , hydrazinium chloride / N ₂ H ₆ Cl ₂ , ammonium bisulfite / NH ₄ H
SO ₃ , ammonium thiosulfate / (NH ₄ ) ₂ S ₂ O ₃ , ammonium amido sulfate / NH ₄ SO ₃ NH ₂ , ammonium metaborate / NH ₄ BO ₂ .1.25H ₂ O, nickel chloride
(II) ammonium nitrate hexahydrate _{/ NH 4 Cl · NiCl 2 ·} 6
H ₂ O, sodium bromide / NaBr, sodium hydroxide / NaOH, sodium sulfide / Na ₂ S, sodium phosphinate / NaPH ₂ O ₂ .H ₂ O, sodium phosphonate / NaPHO ₃ .5H ₂ O, sodium carbonate Hydrate / NaCO ₃ · H ₂ O, Nickel (II) chloride hexahydrate / Ni
Cl ₂ · 6H ₂ O, nickel bromide / NiBr _2, nickel iodide (II) / NiI _2, nickel (II) nitrate hexahydrate / N
i (NO ₃ ) ₂ .6H ₂ O, antimony (III) chloride / SbCl
_3, antimony sulfate _{(III) / Sb 2 (SO} 4) 3, tin fluoride
(IV) / SnF ₄ , tin (IV) bromide / SnBr ₄ , tin sulfate (I
V) dihydrate _{/ Sn (SO 4) 2 ·} 2H 2 O, vanadium chloride / VCl _3, tungsten chloride (IV) / WCl _4, zinc bromide / ZnBr _2, 18-crown -6 / (CH ₂ CH ₂ O) ₆ ,
Ammonium acetate / NH ₄ CH ₃ CO ₂ , N, N-diethyl urea / (C ₂ H ₆ ) ₂ NCONH ₂ , desoxalic acid / OH—
_{HO 2 CCH-C (CO 2} H) 2 · H 2 O-OH, m- nitrobenzenesulfonate _{/ C 6 H 4 (NO 2} ) (SO 3 H), 4- methylimidazole / C ₄ H ₆ N _2: [72] (CH ₃ ).

As a water-soluble deliquescent hygroscopic substance which prevents permeation and drainage of water and melts ice, those exhibiting hygroscopicity are aluminum iodide hexahydrate / AlI _{3 of} iodide.
・ 6H ₂ O, potassium aluminum sulfate of sulfated oxide / A
lK (SO _{4) 2,} boron triiodide / BI _3, bismuth nitrate nitrates (III) pentahydrate _{/ Bi (NO 3) 3 ·} 5H 2 O, calcium oxide oxide / CaO, calcium nitrate / Ca
(NO ₃ ) ₂ , calcium acetate of vinegar oxide / Ca (CH ₃ CO
O) _2, fluorides of cobalt fluoride (III) / CoF _3, cobalt (II) / CoCl _2, cobalt acetate / Co (CH ₃
COO) ₃ , chromium (III) oxalate of oxalate / Cr _{2
(C 2 O 4) 3 ·} 6H 2 O, cesium fluoride / CsF, disulfide dicesium / Cs ₂ S ₂ sulfide, cesium acetate / Cs
(CH ₃ COO), chloride copper (II) chloride / CuCl ₂ , borate copper (II) tetrafluoroborate tetrahydrate / Cu
[BF ₄ ] ₂ .nH ₂ O, iron (III) sulfate / Fe ₂ (SO ₄ ) ₃ , potassium bromide / KBr, potassium oxide / K ₂ O, potassium carbonate / K ₂ CO ₃ , potassium trithiocarbonate / K ₂ CS _3, potassium tungstate _{/ K 2 WO 4 · 2H 2} O, potassium hexahydrate sodium carbonate (also weathering Yes) / KNaCO ₃ · 6
H ₂ O, lithium dihydrogen phosphate / LiH ₂ PO ₄ , magnesium chloride / MgCl ₂ , magnesium iodide / Mg
I ₂ , manganese (II) dihydrogen phosphate dihydrate / Mn (H ₂ P
_{O 4) 2 · 2H 2 O} , ammonium phosphinate / (NH ₄₎ P
H ₂ O ₂ , ammonium acetate / NH ₄ CH ₃ COO, sodium chloride / NaCl, sodium iodide / NaI, sodium nitrite / NaNO ₂ , sodium nitrate / NaN
O ₃ , sodium aluminum dioxide / NaAlO ₂ , nickel (II) sulfate / NiSO ₄ , platinum (IV) fluoride / Pt
F ₄ , selenium dioxide / SeO ₂ , titanium (IV) sulfate / Ti
(SO ₄ ) ₂ , N, N ′ dimethylhydrazine / (CH ₃ ) ₂ NN
H ₂ , diethyl (R, R ′) tartrate / [CH (OH) CO ₂ C ₂
H ₆ ] ₂ , tetrahydrofurfuryl alcohol / —CH ₂ C
H ₂ —CH ₂ —O— [CHCH ₂ OH] —, 1,2,3,4
- tetrahydro-2-naphthol / C ₁₀ H ₁₂ O, P- nitrobenzenesulfonate _{/ C 6 H 4 (NO 2} ) (SO 3 H), promazine hydrochloride _{/ C 17 H 20 N 2 S} · HCl, 2- bromo Ethanol / BrCH ₂ CH ₂ OH, N-methylhydroxylamine / CH ₃ NHOH, 3-methoxy-1,2-
Propanediol / HOCH ₂ CHCH ₂ OCH ₃ —O
H, 6- methoxyquinoline _{/ C 10 H 9 NO: [} 121] (O
CH ₃ ).

Examples of water-soluble carboxylic acids that dissolve silicon dioxide and intermetallic compounds contained in glass, sand and jali include formic acid, acetic acid, propionic acid, butyric acid, valeric acid,
Monocarboxylic acids such as acrylic acid, crotonic acid, isocrotonic acid, propiolic acid, oxalic acid, malonic acid, succinic acid,
Dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, and maleic acid, and tricarboxylic acids such as tricalibaric acid and trimesic acid can be used.

The water-soluble reducing agent includes sodium sulfide, sodium polysulfide, gallic acid, trioxyglutaric acid, hydrazine and the like.

Preferred water-soluble asphalt solvents which slightly dissolve asphalt include acetone, dioxyacetone, dioxane, ethyl methyl ketone and the like.

The water-soluble inorganic acid that dissolves silicon dioxide and intermetallic compounds is, for example, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, carbonic acid, hydrazine hydrochloride and the like.

Examples of water-soluble surfactants for improving the surface wetting of silicon dioxide and intermetallic compounds include sodium alkyl sulfate, sodium alkyl bezensulfonate, N
-Anionic surfactants such as sodium acylamino acid, sodium alkylnaphthalenesulfonate and dialkylsodium 2-sulfosuccinate; cationic surfactants such as N-ethylalkanamidoammonium halide, alkylpyridinium sulfate and alkyltrimethylammonium halide; Adekanol B4001 (nonionic) as alkyl polyoxyethylene ether,
Nonionic surfactants such as alkylcarbonyloxypolyoxyethylene, P-alkylphenylpolyoxyethylene ether, fatty acid polyhydric alcohol ester, fatty acid polyhydric alcohol polyoxyethylene, fatty acid sucrose ester, and alkyl betaine, alkyldiethylenetriaminoacetic acid, etc. Is an amphoteric surfactant.

[0038]

According to the present invention, the permeable and drainable pavement is reliably prevented from freezing in the winter or cold region, and the clogging material in the clogged pores is reliably removed. The ability to easily and efficiently regenerate the body's water permeation or drainage function prevents traffic accidents caused by slips and splashes on paved roads, improves vehicle driving safety, reduces traffic noise, and reduces ground noise. It is possible to prevent inundation disasters due to river flooding without reducing the amount of rainwater returned to the river.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-305096 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09K 3/00 102 C09K 3/18 E01H 10 / 00 E01H 1/00 E01C 11/24 CA (STN)

Claims (20)

(57) [Claims] 1. An alcohol, based on weight, of 5.0 to 30.
0%, deliquescent and hygroscopic substance 1.0 to 30.0%, carboxylic acid 0.05 to 1.0%, reducing agent 0.1 to 2.0%, and asphalt solvent 0.1 to 4.0. 0% and surfactants 0.1 to 2.
0%, inorganic acid 5.0 to 20.0%, and water 11.0 to 88.0.
An antifreezing and restoring agent for a porous solid, comprising 65%. 2. The alcohols are ethylene glycol, the deliquescent and hygroscopic substance is potassium acetate, the carboxylic acid is oxalic acid, the reducing agent is gallic acid, the asphalt solvent is dioxane, the surfactant is alkylpolyoxyethylene ether, and the inorganic acid is hydrazine hydrochloride. The antifreezing / restoring agent for a porous solid according to claim 1, which is 3. Alcohols are 10.0 to 15.0%, deliquescent and hygroscopic substances are 8.0 to 15.0%, and carboxylic acids are 0.1.
~ 0.3%, reducing agent 0.5 ~ 1.0%, asphalt solvent 1.8 ~ 2.5%, surfactant 0.8 ~ 1.5%, inorganic acid 7.0 ~. The antifreezing / restoring agent for a porous solid according to claim 1, wherein 13.0% and water are 51.7 to 71.8%. 4. The alcohol is ethylene glycol, the deliquescent and hygroscopic substance is potassium acetate, the carboxylic acid is oxalic acid, the reducing agent is gallic acid, the asphalt solvent is dioxane, the surfactant is alkylpolyoxyethylene ether, and the inorganic acid is hydrazine hydrochloride. The antifreezing / restoring agent for a porous solid according to claim 3, which is 5. Alcohols: 8.0%, deliquescent and hygroscopic substances: 9.0%, carboxylic acids: 0.05%, reducing agents: 0.1%.
%, Asphalt solvent is 0.1%, surfactant is 0.2
%, Inorganic acid is 10.0%, and water is 72.55%. 6. The alcohols are ethylene glycol, the deliquescent and hygroscopic substance is calcium chloride, the carboxylic acid is malonic acid, the reducing agent is sodium sulfide, the asphalt solvent is dioxane, the surfactant is P-alkylphenyl polyoxyethylene ether, The antifreezing / restoring agent for a porous solid according to claim 5, wherein the acid is carbonic acid. 7. Alcohols: 25.0%, deliquescent and hygroscopic substances: 2.0%, carboxylic acids: 0.5%, reducing agents: 0.6%.
%, Asphalt solvent 2.2%, surfactant 0.5%
%, Inorganic acid is 5.0%, and water is 64.2%. 8. The alcohols are methyl alcohol, the deliquescent and hygroscopic substance is potassium acetate, the carboxylic acid is crotonic acid, the reducing agent is gallic acid, the asphalt solvent is ethyl methyl ketone, the surfactant is sodium alkylbenzene sulfonate, and the inorganic acid is The antifreezing / restoring agent for a porous solid according to claim 7, which is hydrochloric acid. 9. Alcohols: 30.0%, deliquescent and hygroscopic substances: 30.0%, carboxylic acids: 1.0%, reducing agents: 2.0%.
0%, asphalt solvent 4.0%, surfactant 2.0
%, Inorganic acid is 20.0%, and water is 11.0%.
4. The antifreezing / restoring agent for a porous solid according to item 1. 10. The alcohol is glycerin, the deliquescent and hygroscopic substance is magnesium chloride, the carboxylic acid is formic acid, the reducing agent is gallic acid, the asphalt solvent is acetone, the surfactant is alkylpyridinium sulfate, and the inorganic acid is hydrazine hydrochloride. An antifreezing / restoring agent for a porous solid according to claim 9. 11. Alcohols 5.0 to 3 on a weight basis.
0.0%, deliquescent hygroscopic substance 1.0-30.0%, carboxylic acid 0.05-1.0%, reducing agent 0.1-2.0% and asphalt solvent 0.1-4.0% With 11.0 water at 60-80 ° C.
To 88.65% and stirring to dissolve the additive uniformly in water; and to add 0.1 to 2.0% of the surfactant and stirring to dissolve uniformly. And a step of adding 5.0 to 20.0% of an inorganic acid and stirring the mixture. 12. The alcohols are ethylene glycol,
The porous solid according to claim 11, wherein the deliquescent and hygroscopic substance is potassium acetate, the carboxylic acid is oxalic acid, the reducing agent is gallic acid, the asphalt solvent is dioxane, the surfactant is alkylpolyoxyethylene ether, and the inorganic acid is hydrazine hydrochloride. Preparation of antifreeze recovery agent. 13. Alcohols 10.0 to 15.0%, deliquescent and hygroscopic substances 8.0 to 15.0%, carboxylic acids 0.1 to 0.1.
3%, reducing agent 0.5-1.0% and asphalt solvent 1.
Adding 8 to 2.5% to 51.7 to 71.8% of water at 60 to 80 ° C. and stirring to dissolve the additive uniformly in water; The freeze prevention of a porous solid according to claim 11, further comprising a step of adding 1.5%, stirring and uniformly dissolving, and a step of further adding 7.0 to 13.0% of an inorganic acid and stirring. Formulation of recovery agent. 14. The alcohol is ethylene glycol,
The porous solid according to claim 13, wherein the deliquescent and hygroscopic substance is potassium acetate, the carboxylic acid is oxalic acid, the reducing agent is gallic acid, the asphalt solvent is dioxane, the surfactant is alkylpolyoxyethylene ether, and the inorganic acid is hydrazine hydrochloride. Preparation of antifreeze recovery agent. 15. Alcohols 8.0%, deliquescent and hygroscopic substances 9.0%, carboxylic acid 0.05%, reducing agent 0.1% and asphalt solvent 0.1% 72.55% water at 60 ° C. , And a step of dissolving the additive uniformly in water by stirring, and a step of adding 0.2% of a surfactant, stirring and uniformly dissolving, and further adding 10.0% of an inorganic acid. And stirring the mixture. 12. The method of claim 11, further comprising the step of: 16. The alcohol is ethylene glycol,
The deliquescent and hygroscopic substance is calcium chloride, the carboxylic acid is malonic acid, the reducing agent is sodium sulfide, the asphalt solvent is dioxane, the surfactant is P-alkylphenyl polyoxyethylene ether, and the inorganic acid is carbonic acid. An antifreeze and recovery agent for porous solids. 17. 25.0% of alcohols, 2.0% of deliquescent and hygroscopic substance, 0.5% of carboxylic acid, 0.6% of reducing agent and 2.2% of asphalt solvent are mixed with 64.2% of water at 69 ° C. , And a step of dissolving the additive uniformly in water by stirring with water, a step of adding 0.5% of a surfactant and stirring to uniformly dissolve the additive, and a step of adding 5.0% of inorganic acid. And stirring the mixture. 12. The method of claim 11, further comprising the step of: 18. The alcohol is methyl alcohol, the deliquescent and hygroscopic substance is potassium acetate, the carboxylic acid is crotonic acid, the reducing agent is gallic acid, the asphalt solvent is ethyl methyl ketone, the surfactant is sodium alkylbenzene sulfonate, and the inorganic acid is The method for producing a freeze-protecting / restoring agent for a porous solid according to claim 17, which is hydrochloric acid. 19. An alcohol (30.0%), a deliquescent and hygroscopic substance (30.0%), a carboxylic acid (1.0%), a reducing agent (2.0%) and an asphalt solvent (4.0%) in 80 ° C. water (11.0%). , And a step of uniformly dissolving the additive in water, and then, a step of adding 2.0% of a surfactant and stirring to uniformly dissolve the same. Further, 20.0% of an inorganic acid And stirring the mixture. 12. The method of claim 11, further comprising the step of: 20. Alcohols are glycerin, deliquescent and hygroscopic substance are magnesium chloride, carboxylic acid is formic acid, reducing agent is gallic acid, asphalt solvent is acetone, surfactant is alkylpyridinium sulfate, and inorganic acid is hydrazine hydrochloride. 20. A method for producing the antifreezing / restoring agent for a porous solid according to claim 19.