KR101867811B1 - Heat insulating color sand and Heat insulating block containing the same - Google Patents

Abstract

The present invention relates to a heat-generating color sand composition, a differential color sand and a differential block, and more particularly, to a heat-sensitive color sand prepared by coloring sand, which is a fine aggregate of a specific resin and a specific pigment, And by introducing such a heat shielding color sand, it is desired to provide a heat shield block excellent in heat resistance and mechanical properties.

Description

[0001] The present invention relates to a differential color sand,

The present invention relates to a block with a heat-shade color sand and an excellent heat-shading property including the same.

In recent years, rapid urban development has led to tropical nights due to the urban heat island phenomenon. In addition to increasing the health damage caused by hot spots, it can act as an urban water pollution and air pollution inducing factors. Therefore, to be.

On the other hand, conventional concrete, a sidewalk plate or an impervious layer block which does not pass water at present occupies most of the inside of the city center. Recently, a permeable block which is used in the market in consideration of environmental problems has been developed, But it is not enough to solve the thermal environment.

In the case of blocks with maintenance performance, which have been recently studied, water is absorbed in the block, and the ambient temperature is lowered by vaporization. However, problems with water absorption period and continuous water absorption in the block, However, there is still a need for an additional device such as a continuous water supply device as a solution to this problem. However, it is still not realized due to practical use and budget shortage, This has many difficulties in management, while manually controlling the timing of water supply and spraying.

In the case of heat-shrinkable packaging, a technology has been developed that can prevent temperature rise while ensuring a lightness over a certain level by mixing the heat-sensitive pigment with cement. However, the block obtained by this method relies on the expensive heat- The mortar paste is wrapped around the aggregate in the surface layer which is the same shape as the surface of the concrete block and becomes a temperature raising factor,

In addition, in the case of heat-shrinkable packaging, patents on manufacturing and application of coating compositions such as the roof of a building and a roadway are disclosed, but most of them are coating technology in the form of a heat-insulating film, and most of them are water- For example, according to the technique disclosed in Korean Patent No. 10-0818489, a water-absorbent polymer and a mineral ceramic fine powder as a water-retaining material are mixed to form a water-retaining cement having a maximum water content of 4.0 to 8.0 l / It is suggested that the water - repellent asphalt pavement layer and the surface - layered asphalt pavement are prepared on the pavement of the asphalt pavement. However, since the chemical water-repellent materials such as the superabsorbent polymer used as the water-retaining material absorbs water by chemical bonding, the effect is good at the beginning, but the irreversible reaction is difficult due to the nature of chemical bonding, And the surface temperature reduction through the latent heat of evaporation of water is not expected to be expected. In particular, maintenance capability can be maintained at the beginning of use, but there is a problem that the ability of the chemical polymer component is reduced over time.

Korea Patent No. 10-0764598 (Published on October 1, 2007) Japanese Unexamined Patent Publication No. 2004-225283 (published on August 12, 2004)

As a result of a specific effort to develop a new heat-shrinkable material for increasing the heat resistance of the heat blocking block, the present invention is excellent in coloring effect of pigments on sand by coloring sand as a fine aggregate with a specific resin and a specific pigment. It has been found that a high heat-shielding effect can be imparted, and thus the present invention has been completed. That is, the present invention provides a heat-shrinkable color sand composition, a heat-shrinkable color sand prepared using the same, and a heat block having the same.

In order to solve the above problems, the present invention relates to a heat-sensitive color sand composition comprising: an acrylic emulsion resin comprising a copolymer aqueous dispersion obtained by copolymerizing an ethylenically unsaturated monomer; A black pigment containing a metal oxide of a spinel structure represented by the composition of Cu (Mn, Fe) ₂ O ₄ , and a heat-sensitive pigment comprising tungsten oxide; And sand.

In one preferred embodiment of the present invention, the heat shade color sand composition of the present invention may comprise 10 to 30 parts by weight of the heat-sensitive pigment and 1,000 to 8,000 parts by weight of the sand, based on 100 parts by weight of the acrylic emulsion resin.

In one preferred embodiment of the present invention, the ethylenically unsaturated monomer is selected from the group consisting of methyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, hexadecyl methacrylate, ethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol methacrylamide, N-methylol acrylamide, glycidyl methacrylate, diacetone acrylamide, acetoxyethylene acrylate, acetoxyethylene methacrylate, and acetic acid Methoxypropyltrimethoxysilane, and ethoxyethyl chlorotonate.

In one preferred embodiment of the present invention, the copolymer is prepared by polymerizing or copolymerizing an ethylenically unsaturated monomer (A) having a Tg of 80 DEG C or higher and an ethylenically unsaturated monomer (B) having a Tg of 30 DEG C or lower at a weight ratio of 1: 2 to 6 As shown in FIG.

In one preferred embodiment of the present invention, the black pigment contains iron and manganese in a molar ratio of 1: 5 to 25, and the molar ratio of copper / (manganese + iron) is 1: 2 to 3.5.

As a preferred embodiment of the present invention, the heat-sensitive color pigment of the differential color sand composition is selected from the group consisting of tin doped indium oxide, antimony doped tin oxide, aluminum doped zinc oxide, indium doped zinc oxide, And an infrared shielding agent containing at least one selected from zinc oxide and silicon-doped zinc oxide.

It is another object of the present invention to provide a differential color sand comprising the various types of differential color sand compositions as described above.

In one preferred embodiment of the present invention, the heat shade color sand of the present invention comprises 25 to 35% by weight of acrylic polyol resin, 25 to 35% by weight of polyester polyol resin, 5 to 15% by weight of toluene, 10 to 20% by weight of xylene, And 10 to 20% by weight of acetate.

Another object of the present invention is to provide a heat block including various types of shell aggregates as described above.

The heat block of the present invention is characterized in that the base layer, the surface layer and the heat shielding-non-slipping structural layer are formed in order, and the heat shielding-non-slipping structural layer includes at least one selected from the heat shading color sand and the shell aggregate, White cement, white quartz, shear color sand, and the shell aggregate, and the base layer may be a water permeable layer or an impermeable layer.

In one preferred embodiment of the present invention, the surface layer is composed of 120-300 parts by weight of white ruby, 40-250 parts by weight of heat sand, 30-100 parts by weight of shell aggregate, 20-50 parts by weight of water, Layer mortar containing a part of the surface layer.

In one preferred embodiment of the present invention, the impervious base layer may include 300-400 parts by weight of Portland cement and 1,500-2,500 parts by weight of fine aggregate, based on 100 parts by weight of water.

In a preferred embodiment of the present invention, the surface layer may have an average pore size of 12% to 20% and a thickness ratio of the surface layer to the base layer may be 1: 4.5 to 7.

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The heat-shade color sand of the present invention is excellent in long-term tinting strength due to its high bonding force with sand and heat-color pigments, unlike existing heat-shrinkable materials having low coloring power between sand and pigment, and has high light reflection power. It is possible to provide a heat block having an excellent heat insulating property.

1 is a schematic view of a heat block as a preferred embodiment of the present invention.
Fig. 2 is a perspective view showing a schematic view of a preferred embodiment of the heat block of the present invention. Fig.
Fig. 3 is a plan view of the heat block in the direction of the surface layer, which is a preferred embodiment of the heat block of the present invention.
FIG. 4 is a schematic view showing a preferred embodiment in which a heat block having the shape of FIG. 3 is installed.
FIG. 5 shows various embodiments of the joint formed in the heat block of the present invention as a preferred embodiment of the heat block of the present invention.
Fig. 6 is a photograph showing the experiment for measuring heat resistance performed in Experimental Example 2. Fig.
Fig. 7 is a photograph showing a case in which the front troposphere is installed at the time of the measurement of the shading property in Experimental Example 2. Fig.
Figs. 8 and 9 are photographs of the asphalt obtained in the heat resistance evaluation test of Experimental Example 2 and the heat treatment thereof.

Hereinafter, the present invention will be described more specifically.

The heat-shrinkable color sand composition of the present invention comprises an acrylic emulsion resin comprising an aqueous dispersion of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer; Heat pigment; And sand.

The acrylic emulsion resin in the composition of the present invention is an aqueous dispersion of a copolymer obtained by copolymerizing two or more ethylenically unsaturated monomers under a nonionic surfactant.

The nonionic surfactant may be any of those conventionally used in the art and is preferably a polyoxyethylene alkylphenyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene fatty acid ester, a polyoxyethylene polyoxypropylene block polymer, a sorbitan Fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamine ethers, fatty acid diethanolamidoethylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene Ethylene alkylamine ether and fatty acid diethanolamide, preferably at least one selected from polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, poly An oxyethylene sorbitan fatty acid ester, a polyoxyethylene alkylamine ether, and a fatty acid diethanolamide.

The ethylenically unsaturated monomer may be at least one monomer selected from the group consisting of methyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, hexadecyl methacrylate, ethyl acrylate, i-butyl acrylate and 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, N-methylol methacrylamide, N-methylol acrylamide, glycidyl methacrylate, diacetone acrylamide, acetoxyethylene acrylate, acetoxyethylene methacrylate and acetoxyethyl crotonate From the viewpoint of durability and emulsion stability, it is preferable to use a monomer or a monomer having a molecular weight of not less than 100, preferably not less than 100, such as methyl methacrylate, t-butyl methacrylate and i-butyl methacrylate, hexadecyl methacrylate, ethyl acrylate, Unsaturated carboxylic acid esters selected from 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate, Can.

The copolymer which is an aqueous dispersion constituting the acrylic emulsion resin contains an ethylenically unsaturated monomer (A) having a Tg of 80 ° C or higher and an ethylenically unsaturated monomer (B) having a Tg of 30 ° C or lower at a weight ratio of 1: 2 to 6, Preferably from 1: 2.5 to 4 weight ratio. For example, when Tg is 104 ° C when methyl methacrylate (MMA) is singly polymerized, and when Tg is 10 ° C when isobutyl acrylate (IBA) alone is polymerized, MMA and IBA are used in combination as a copolymerizable monomer do. When the Tg of the copolymer of MMA and t-butyl methacrylate (TBMA) is 123 ° C and the Tg of the copolymer of isobutyl methacrylate (IBMA) and IBA is 30 ° C, MMA, TBMA, IBMA and IBA Can be used in combination as a copolymerizable monomer. At this time, if the weight ratio of the ethylenically unsaturated monomer having a Tg of 30 占 폚 or less is less than 2 parts by weight or exceeds 6 parts by weight, the color of the heat-sensitive color sand may be deteriorated.

Among the heat shade color sand compositions of the present invention, the above heat-sensitive pigments include a black pigment and tungsten oxide.

The black pigments in the heat-sensitive pigments include metal oxides of a spinel structure represented by the composition of Cu (Mn, Fe) ₂ O ₄ and have a specific surface area of 20 to 50 m ² / g, preferably 25 to 40 m ² / g Lt; / RTI >

The black pigment contains iron and manganese in a molar ratio of 1: 5 to 25, preferably 1: 7 to 22. At this time, if the molar ratio of manganese exceeds 25, there may be a problem that the coloring power is lowered. If the molar ratio is less than 5 mol, the near infrared absorbability increases and the heat shielding effect may decrease. The molar ratio of copper and (manganese + iron) in the black pigment may be 1: 2 to 3.5, preferably 1: 2.5 to 3.2. When the molar ratio is less than 2.5, the tinting strength may be lowered. There is a problem that the specific surface area of the black pigment becomes small.

Of the heat-generating fuel components, tungsten oxide serves to improve the weatherability of the heat-sensitive pigment, and it is preferable to use 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight based on 100 parts by weight of the black pigment. At this time, if the content of tungsten oxide exceeds 1 part by weight, the heat resistance may be deteriorated.

As the heat-sensitive pigment, a metal oxide containing at least one selected from black pigment and tungsten oxide, and at least one selected from calcium and magnesium is further introduced in an amount of about 0.01 to 0.2 part by weight based on 100 parts by weight of the black pigment to obtain a sharper neutral- Or may be made of a pigment.

In order to prevent the temperature rise due to infrared rays, the above-mentioned heat-sensitive coloring pigments may contain tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, tin- And an infrared shielding agent containing at least one selected from silicon-doped zinc oxide. The infrared shielding agent is colorless and does not absorb visible light, does not absorb near infrared rays near 1,500 nm, and has a property of reflecting light in the infrared region. At this time, the amount of the infrared shielding agent used is preferably 0.01 to 0.1 part by weight, preferably 0.03 to 0.1 part by weight based on 100 parts by weight of the black pigment.

The amount of the heat-sensitive pigment in the composition of the present invention may be 10 to 30 parts by weight, preferably 12 to 25 parts by weight, more preferably 15 to 23 parts by weight, based on 100 parts by weight of the acrylic emulsion resin. If the amount of the heat-sensitive pigment is less than 10 parts by weight, the amount of the heat-sensitive pigment to be used may be so small that the coloring effect of the sand may be deteriorated, and the use of more than 30 parts by weight is not economical.

The amount of sand in the composition of the present invention may be 1,000 to 8,000 parts by weight, preferably 2,000 to 7,000 parts by weight based on 100 parts by weight of the acrylic emulsion resin.

Hereinafter, the heat block using the shell aggregate of the present invention described above will be described.

The heat block of the present invention is characterized in that the base layer, the surface layer and the heat shielding-anti-slip structure layer are formed in order, and the heat shielding-anti-slip structure layer comprises a differential thermal color sand, and the surface layer comprises white cement, And the base layer may be a water permeable layer or an impermeable layer. In this case, the differential color sand is as described above.

In addition, the heat shielding-non-skid structure layer and / or the surface layer may further include shell aggregate in addition to the heat shield color sand.

As shown schematically in FIG. 1, the heat block of the present invention is a heat block 10 having a base layer 12, a surface layer 11 and a heat-shroud-anti-slip structure layer 13 formed in order, The present invention will be described in detail.

The heat block of the present invention comprises: preparing each of a surface layer mortar and a base layer mortar; Filling the cavity of the mold with the mortar for the base layer and then performing press vibration forming to form a base layer; Filling the cavity of the mold having the base layer with the mortar for the surface layer, and then performing press vibration forming to mold the block having the surface layer laminated on the upper surface of the base layer; Forming a block-slip preventing structure layer on a top surface of a surface layer by spraying water on the surface of the block after the block is deformed at a predetermined angle after demoulding the block formed from the mold; And curing the block to produce a heat shield block 10 of the type shown schematically in FIG.

The curing may be carried out by natural curing or steam curing. Preferably, the curing is carried out for 40 to 52 hours while maintaining the temperature at 30 to 60 ° C, or for 1 to 5 hours Steam curing can be carried out for a while. At this time, the curing temperature affects the color of the artificial block. The higher the curing temperature, the lower the intensity of the color than the low vapor pressure or the curing in the air. Therefore, in order to realize the optimum color, It is good.

In addition, the method of manufacturing the heat block of the present invention may further include a step of brushing the cured block.

In the present invention, a block formed to have a base layer and a surface layer is tilted at a predetermined angle, and the surface of the block is subjected to a washing treatment with a washing machine, so that one or two of the surface heat- - the anti-slip structure layer (13) is formed and the heat shielding-non-skid structure layer (13) is free of or minimized the cement constituting the surface layer.

In the present invention, the mortar for surface layer comprises 120-300 parts by weight of Baikyosan, 40-250 parts by weight of a heat shade color sand, 30-100 parts by weight of the shell aggregate, and 20-50 parts by weight of water, based on 100 parts by weight of the white cement. And preferably 150 to 270 parts by weight of white tar, 45 to 200 parts by weight of a heat-shrinkable color sand, and 22 to 35 parts by weight of water, based on 100 parts by weight of white cement. Further, it may further comprise 45 to 80 parts by weight of the shell aggregate.

At this time, when the amount of the white sheet is used in an amount of 120 parts by weight, it may be difficult to expose the white series on the appearance of the heat block and may affect the brightness difference. If the amount exceeds 300 parts by weight, And the overall color of the product may become brighter, resulting in increased glare.

If the heat-shielding color sand is less than 40 parts by weight, the heat-shielding effect is lowered. If it is used in excess of 250 parts by weight, the amount of the heat-shielding coloring agent used is too large. have.

If the content of water is less than 20 parts by weight or exceeds 75 parts by weight, it is difficult to maintain proper viscosity of the mortar for surface layer, resulting in poor moldability and workability.

Also, if the amount of the shell aggregate is more than 80 parts by weight, the white color may increase and the glare may be affected.

In the mortar for surface layer, the white cement may be any of those generally used in the art, preferably white cement having a whiteness of 65 or more.

In the heat-shroud-preventing layer and / or the mortar for surface layer, the shell aggregate may be a conventional shell aggregate used in the art, preferably a shell having a heat-treated pressure at 380 to 550 ° C and 1.5 to 3.5 atm Shell aggregate containing crushed shell crumbs can be used. At this time, the pitch angle may include at least one selected from the group consisting of shell shell, scallop shell, abalone shell, oyster shell, sheath shell, lily shell, and carrot shell, preferably scallop shell, abalone shell, oyster shell, And the like.

The shell crushed material is preferably pulverized to have an average particle size of 0.01 mm to 3 mm, preferably 0.5 mm to 3 mm, more preferably 1 mm to 2.5 mm, wherein the average particle size of the crushed shell If it is less than 0.01 mm, the particle size is too small, and the effect of heat shielding may not be exhibited.

The shell aggregate may further comprise at least one selected from the group consisting of stone sludge, anhydrous gypsum, and fine sand in addition to the shell crushed material. Preferably, the shell aggregate contains 20 to 40 parts by weight And 5-20 parts by weight of anhydrous gypsum.

In the method of producing a block for heat block of the present invention, the base layer may be a water permeable layer or an impervious base layer, and a mortar for the base layer may be a water permeable mortar or an impervious mortar, depending on the base layer characteristics to be produced.

The permeable mortar may include 300-400 parts by weight of Portland cement, 450-650 parts by weight of fine aggregate, and 1,000-1,500 parts by weight of coarse aggregate, preferably 100-300 parts by weight of Portland cement 330 To 390 parts by weight, from 500 to 600 parts by weight of fine aggregate, and from 1,200 to 1,450 parts by weight of coarse aggregate. If the content of the Portland cement is less than 300 parts by weight, the adhesive strength to the fine aggregate and the coarse aggregate may be weak and the strength may be weak. If the amount exceeds 400 parts by weight, the strength may be increased. However, the cement paste may increase the aggregate surface, have.

If the content of the fine aggregate is less than 450 parts by weight, the coarse aggregate content may be relatively increased to improve the water permeability. However, if the content of the fine aggregate exceeds 650 parts by weight, the fine aggregate may fill the void and decrease the permeability.

If the coarse aggregate content is less than 1,000 parts by weight, the permeable porosity may be lowered. If the coarse aggregate content exceeds 1,500 parts by weight, the permeable porosity may be improved, but it may become weak to the strength and the compacting may be difficult.

The impermeable mortar is prepared by blending 300 to 400 parts by weight of Portland cement and 1,500 to 2,500 parts by weight of fine aggregate, preferably 330 to 390 parts by weight of Portland cement and 1,700 to 1,100 parts by weight of Portland cement, If the content of the Portland cement is less than 300 parts by weight, the block bending strength may be affected. If the amount of the Portland cement is more than 400 parts by weight, the CO ₂ emission may be relatively increased regardless of the bending strength

If the content of the fine aggregate is less than 1,500 parts by weight, the amount of aggregate relative to cement is small, which may cause a decrease in strength. If the aggregate exceeds 2,500 parts by weight,

The permeable mortar and / or impervious mortar may further include at least one selected from a water reducing agent and a repairing agent. For example, the water reducing agent may be a lignin-based water reducing agent, and the water-repellent agent may be a magnesium salt of acrylic acid and a dimethylaminoethyl methacrylate copolymer And a polymer compound containing polyethyleneimide can be used.

The surface layer of the heat block of the present invention has an average pore of 12% to 20%, preferably 12% to 16%. At this time, if the average pore size of the surface layer is less than 12%, a capillary phenomenon may occur in the surface layer, and if the average space exceeds 20%, the mechanical properties of the surface layer may be too low.

The thickness ratio of the surface layer to the base layer is preferably about 1: 4.5 to 7, and more preferably about 1: 4.5 to 6.5. If the ratio of the thickness of the base layer to the surface layer is less than 4.5, the thickness of the base layer may become thinner and the bending strength may be a problem. If the thickness ratio of the base layer is more than 7 to the surface layer, the surface layer is reduced so that the heat resistance and / May cause problems.

The heat block of the present invention may have an indentation and the base layer 12 of the heat block may have four sides 51, 52, 53 and 54, Each of them is formed with a row eye 50, a surface layer 11 is formed on an upper end of the base layer, and a joint part is not formed on the surface layer. The joint portion may be formed in the longitudinal axis direction or the lateral axis direction of the block.

That is, the heat block of the present invention has joints as shown in FIGS. 2 to 5 in order to improve the workability when the blocks are laid and to prevent the positions of the blocks from being distorted and to prevent edge breakage and peeling, This line of sight can minimize the amount of filler (sand or sand) between the block and the block, and shorten the block installation time.

3, the heat block 10 of the present invention has a first side 51, a second side 52 in a clockwise direction when viewed from the top surface of the heat shield-anti-slip structure layer, The third side 53 and the fourth side 54 of the first side 51 and the third side 53 of the first side 51 and the third side 53 are arranged in the same position, And in the clockwise direction, the row eye portions 50 of the second side 52 and the fourth side 54 are formed to overlap at the same position.

4, each of the line eyes of the first side, the second side, the third side, and the fourth side is formed so that one of the longitudinal sides of the joint portion coincides with the center line of each side where the joint portion is formed, And the longitudinal sides may be formed spaced apart from the center line of each side.

In addition, in the heat block of the present invention, the sum of the side lengths of the joint portions formed at the respective sides when the joint portions formed on the sides of the first side, the second side, the third side and the fourth side are viewed from the side direction of the block And may be formed to have a length of 20% to 45% with respect to the total length of each side.

In the heat block of the present invention, when viewed from the side direction of the block, the joint portion may have a shape of a transverse length and a length having a length ratio of 1: 1.8 to 2.5.

As shown in Fig. 5, the heat block of the present invention may be a flat surface having a smooth cross-section of a curved rectangle or a curved end when viewed from the lateral direction of the block, The joint can be square, rectangular, trapezoidal or semicircular.

In the conventional heat block, protrusions of about 10 mm in width were formed. After the blocks were installed, the blocks were twisted to each other, so that the joints were likely to be abraded, and when they were worn, the blocks came into contact with each other. Therefore, when viewed from the top surface of the surface layer, the heat block of the present invention is formed such that the thickness of the joint portion is 1.5 mm to 4 mm, preferably 1.5 mm to 3 mm to prevent abrasion of the joint portion and jamming of the line eye portion .

When the automobile or the like passes through the road surface, the blocks are widened to increase the joint width, so that the block is inclined and the surface angle becomes smaller than that of the neighboring block However, according to the present invention, it is possible to minimize breakage of the joint by providing the joint portion with the optimum size, shape, and thickness as described above.

The heat block of the present invention described above satisfies 5.0 MPa or more in the case of an impermeable block and the bending strength of 4.0 MPa or more in a permeable block.

[Equation 1]

Flexural strength [MPa (= N / ㎟) ] = (3Pl) / (2bd 2)

In the above equation (1) P is the maximum breaking load (N) of the tester, l is the point-to-point distance (mm), b is the average width in millimeters perpendicular to the point (mm) and d is the average thickness of the block (mm).

In the heat block of the present invention described above, the water permeability coefficient may be 0.1 mm / s or less when measured according to the following equation (2).

&Quot; (2) "

K = (d / h) x {Q / (A x 30s)}

D is the thickness (mm) of the block, h is the water level difference (mm), A is the height of the block (mm), K is the water permeability coefficient (mm / s) (Mm 2), and 30 s is the measurement time (sec).

The water-impermeable block of the present invention as described above has a water absorption rate (moisture absorption rate) of less than 8%, preferably 5.0% to 8.0%, more preferably 5.0% or less, To 7.6%.

&Quot; (3) "

Absorption rate (%) = (m _p -m ₁ ) / m ₁ 100 (%)

In Equation (3), m _p is the weight of the artificial block before water is loaded, m ₁ is It is the weight after the artificial block is carried in water for 6 hours.

The above-described heat block of the present invention has a very high road surface temperature difference of 13 占 폚 or more, preferably 13.5 占 폚 to 15 占 폚 according to the following equation (4).

&Quot; (4) "

T = T1 - T2

In the equation (4), T is the road surface temperature difference (占 폚), T1 is the road surface temperature (占 폚) after three hours irradiation of the specimen of the target block, and T2 is the surface temperature (占 폚) of the comparative specimen after 3 hours irradiation.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention should not be construed to be limited by the following examples.

[ Example ]

Preparation Example 1: Preparation of shell aggregate

Scallop shell, abalone shell and oyster shell were mixed at a weight ratio of 1: 0.35: 0.25.

Next, the shell mixture was thoroughly washed with water, and then supported on an acid solution having a pH of 5.2 to 5.3. After 24 hours, the washed shell was taken out and then sufficiently washed with water and dried naturally.

Next, the dried shell was heat-treated under pressure at 460 ° C and 2.2 atm for 30 minutes. At this time, the pressurization heat treatment was performed while supplying oxygen.

Next, the shell subjected to the heat treatment under pressure was rolled to prepare a crushed shell having an average particle size of 1.2 to 1.3 mm.

Next, the shell aggregate was prepared by mixing 100 parts by weight of the crushed shell, 25 parts by weight of the stone sludge and 8 parts by weight of anhydrous gypsum.

Example  1-1: Differential color of the sand  Produce

(1) Acrylic emulsion  Resin Manufacturing

200 parts of ion-exchanged water as a medium, 0.6 part of trimethylcetylammonium chloride as a surfactant, and 0.1 part of polyoxyethylene lauryl ether (HLB = 1 part) were added to a 1,000 ml four-necked flask equipped with a stirrer, 12) was added thereto, and the interior of the reaction system was purged with nitrogen while stirring. Thereafter, 27 parts of methyl methacrylate, 20 parts of isobutyl acrylate and 1 part of N-methylol acrylamide were added as ethylenically unsaturated monomers, The temperature was raised to 80 ° C, and 0.2 part of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added as a polymerization initiator to initiate polymerization.

After polymerization at this temperature for 30 minutes, the emulsion solution prepared as described below was added dropwise over 2 hours. And 0.2 part of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added in three portions at the time of dropping the emulsion. After completion of the emulsion dropwise addition, the polymerization was completed by aging for 2 hours, and the product was filtered through a 100 mesh metal gauze to remove the coagulum formed during the polymerization process. Thus, a milky white, stable acrylic emulsion resin was obtained.

 (2) Heat pigment  Produce

120 parts of copper sulfate, 130 parts of manganese sulfate and 53.4 parts of iron sulfate were put into water and stirred to prepare a solution. Next, 120 parts of caustic soda was added to the solution, stirred and completely dissolved to prepare 1000 parts of caustic soda aqueous solution.

Next, the above caustic soda aqueous solution was dropped into 1,600 parts of water, stirred, and allowed to stand for 1 hour.

Next, after the pH was adjusted to 12.3 to 12.4, an aqueous hydrogen peroxide solution (concentration: 35%) was added dropwise and subjected to oxidation treatment.

Next, the mixture was heated to 80 DEG C and aged for 2 hours. The reaction product was filtered and purified, and the reaction product was washed with water and then dried at 120 deg.

Next, the dried material was fired at 620 ° C for 1 hour to obtain a fired product, which was pulverized to obtain a black pigment (average diameter 65 nm) having a BET specific surface area of 38.7 2 / g.

The prepared black pigment had a molar ratio of iron and manganese of 1:15, and a molar ratio of copper and (manganese + iron) of 1: 2.8.

Next, 0.12 part by weight of tungsten oxide having an average diameter of 50 nm and 0.05 part by weight of tin-doped indium oxide were mixed with 100 parts by weight of the black pigment to prepare a heat pigment.

(3) 18 parts by weight of the heat-preventive pigment was mixed with 100 parts by weight of the acrylic emulsion resin, and 4,500 parts by weight of sand was added and stirred. The resulting mixture was heat-treated at 170 DEG C for 1 hour and cooled to obtain a gray- A heat sand color sand was prepared.

Example  1-2: Differential color of the sand  Produce

A heat shielding color sand was produced in the same manner as in Example 1-1 except that 15 parts of methyl methacrylate as an ethylenic unsaturated monomer, 12 parts of t-butyl methacrylate, 17 parts of isobutyl acrylate, Acrylic emulsion resin was prepared using 9 parts of butyl methacrylate, and a heat shade color sand was prepared using the emulsion resin.

Comparative Example  One

A heat shade color sand was prepared in the same manner as in Example 1-1 except that 47 parts by weight of methyl methacrylate resin as the ethylenic unsaturated monomer was used as the acrylic resin alone to prepare an acrylic emulsion resin, To prepare a differential color sand.

Comparative Example  2

Except that 47 parts of a copolymer (Tg = 123 ° C) prepared by copolymerizing methyl methacrylate and t-butyl methacrylate at the time of preparing the acrylic emulsion resin was used in the same manner as in Example 1-1 above To prepare an acrylic emulsion, and then a heat shade color sand was prepared using the emulsion.

Comparative Example  3

A heat shade color sand was prepared in the same manner as in Example 1-1 except that a black pigment was prepared such that the molar ratio of iron and manganese was 1: 2 in the preparation of the black pigment.

Example  2-1: For surface layer Mortar  Produce

(100 parts by weight) of white cement having a degree of whiteness of 65 to 70 (manufactured by Union Co., Ltd., trade name: Union white portland cement) in a 1-m3 mixer were mixed with 270 parts by weight of white paper, 54 parts by weight of beige- 54 parts by weight of the shell aggregate and 25 parts by weight of water were mixed to prepare a mortar for surface layer.

Example  2-2 ~ Example  2-3 and Comparative Example  2-1 to 2-4

The mortar for the surface layer was prepared in the same manner as in Example 2-1, except that the shell aggregates of Example 1-1 were replaced with those of Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-4 The mortar for the surface layer was prepared as shown in Table 1 below using the shell aggregate.

division Differential color Shell texture Example 2-1 Example 1-1 - Example 2-2 Examples 1-2 - Example 2-3 Example 1-3 Preparation Example 1 Comparative Example 2-1 Comparative Example 1 - Comparative Example 2-2 Comparative Example 2 - Comparative Example 2-3 Comparative Example 3 -

Example  3: For permeable layer Mortar  Produce

100 parts by weight of water, 367 parts by weight of ordinary Portland cement (Hyundai Cement Co.), 555 parts by weight of sand (fine aggregate) having an average particle size of 4 to 6 mm and 1383 parts by weight of crushed stone (coarse aggregate) To prepare a mortar for a permeable layer.

Example  4 : Impervious  For base layer Mortar  Produce

100 parts by weight of water, 367 parts by weight of ordinary portland cement (Hyundai Cement Co., Ltd.) and 1,938 parts by weight of sand (fine aggregate) having an average particle size of 4 to 6 mm were charged into a 1-m3 mixer and stirred to prepare a mortar for the impervious base layer.

Manufacturing example  One : Of the heat block  Produce

After injecting the mortar for the water permeation layer of Example 3 into the cavity of the mold, the press was lowered to apply pressure to the mold cavity to perform press vibration molding. Next, after the mortar for the surface layer of Example 2 was put in, the press was lowered, pressure was again applied to the mold cavity, and the mold was subjected to press vibration molding to produce a block.

After the plurality of heat block blocks were formed on the upper part of the stage panel, the elevating frame was lowered, and the stage panel was transferred to the washing part while supporting the blocks. Next, when the drive cylinder is operated to push up the operation rod, the stage panel is inclined. When the stage panel is tilted, the nozzle moves along the frame to spray liquid to washig the surface of the heat block, And the surface layer mortar was removed to form a heat-shroud-resistant structure layer in which the heat-shone color sand and a part of the shell aggregate were drawn at the upper surface of the surface layer.

The washing treatment was carried out by primary washing and secondary washing. The primary washing treatment was 90 Hz, the water pressure was 1.50 MPa, the nozzle diameter was 0.30 mm, and the average diameter of water particles sprayed was 180 to 250 占 퐉. The secondary washing treatment had a speed of 85 Hz, a water pressure of 0.50 MPa, a nozzle diameter of 0.30 mm, and an average particle diameter of sprayed water particles of 180 to 250 占 퐉. At this time, after the washing process, when the driving cylinder lowers the operating rod to the original position, the stage panel is placed on the chain conveyor and is discharged from the washing section according to the operation.

Then, the heat block having the base layer / surface layer / heat-shroud-anti-slip structure layer prepared by performing the washing treatment was cured for 48 hours while maintaining the temperature at 45 to 50 ° C.

The thickness ratio of the surface layer and the base layer of the prepared heat blocking block was 1: 5.1, and the thickness of the heat block was 20 cm, 20 cm and 6 cm, respectively.

Manufacturing example  2 ~ Manufacturing example 12 and Comparative Manufacturing Example  1 to 6

A heat block was prepared in the same manner as in Preparation Example 1 except that the surface layer mortar and the base layer mortar were used in combination as shown in Table 2 below.

division Example 3 Example 4 Example 2-1 Production Example 1 Production Example 4 Example 2-2 Production Example 2 - Example 2-3 Production Example 3 - Comparative Example 2-1 Comparative Preparation Example 1 - Comparative Example 2-2 Comparative Production Example 2 - Comparative Example 2-3 Comparative Production Example 3 -

Experimental Example  1: Property evaluation experiment

The bending strength and the water absorption rate (moisture absorption rate) of the heat block prepared in the above-mentioned Production Examples 1 to 4 and Comparative Production Examples 1 to 3 were measured, and the results are shown in Table 3, respectively.

(1) Bending strength measurement

The flexural strength was measured according to KS F 4419: 2001. The flexural test was carried out immediately after the sample was immersed in water for 24 hours and then taken out. The distance between points was taken as 140 mm, and the load was applied at the center between the points. In this case, the pressing speed is applied at a high speed up to about 50% of the breaking load, and the maximum load P shown in the tester is applied by applying a load such that the increase of the maximum bending compressive stress does not exceed 9.8 MPa (= N / And the bending strength is calculated according to the following equation (1). At this time, the flexural strength was measured using a concrete flexural strength tester (C090-07N).

In addition, the heat-insulating concrete impervious block should have a bending strength of at least 4.0 MPa (see Table 3).

[Equation 1]

Flexural strength [MPa (= N / ㎟) ] = (3Pl) / (2bd 2)

In the above equation (1) P is the maximum breaking load (N) of the tester, l is the point-to-point distance (mm), b is the average width in millimeters perpendicular to the point (mm) and d is the average thickness of the block (mm).

(2) Permeability coefficient  Measure

The permeability coefficient is measured by measuring the thickness and cross-sectional area of the block with a vernier caliper, and then fixing the block in the block. At this time, the block is blocked with paraffin or sealing material to prevent water from falling out of the block.

Next, water was filled into the overflow tanks of the permeable permeability testing device, and the blocks in the water side tamping block were caught. Then, the water level was kept constant until the water overflowed from the overflow portion of the tamping portion.

Next, the flow amount Q (㎣) for 30 seconds was measured with a measuring cylinder while waiting for the displacement amount to become constant in the overflow water tank. At the same time, the water level difference between the overflow tank water level and the water level surface water level drained for 30 seconds was measured.

The permeability coefficient was measured by three samples at intervals of one minute or more, and each value was calculated by the following equation (2) and expressed as an average value. If the permeability coefficient is 0.1 mm / s or more, the acceptance is evaluated. If the permeability coefficient is less than 0.1 mm / s, the evaluation is rejected.

&Quot; (2) "

K = (d / h) x {Q / (A x 30s)}

In the above equation (2). K is the water permeability coefficient (mm / s), Q is the drainage amount (㎣) to be drained, d is the thickness of the block (mm), h is the water level difference (mm), A is the cross- And 30s is the measurement time (sec).

(3) Absorption rate measurement

The absorption rate After the bending strength test, two specimens were taken from one specimen and the required mass and the specimen mass of the specimen were determined, and the absorptivity was calculated according to the following equation (3).

&Quot; (3) "

Absorption rate (%) = (m _p -m ₁ ) / m ₁ 100 (%)

In Equation (3), m _p is the weight of the artificial block before water is loaded, m ₁ is It is the weight after the artificial block is carried in water for 6 hours.

(4) Measurement of impact resistance

The impact resistance was evaluated by evaluating the number of falls at the time of dropping by dropping a 3 kg steel ball on the artificial block. The results are shown in Table 4 below. At this time, when the number of times of the dropping is 1, it is usually poor. When the number of times of dropping is 2 to 3 times, it is usually excellent, and when it is 4 to 5 times, it is excellent. : Poor).

division Flexural strength
(MPa = N / mm < 2 >) Absorption rate
(%) Permeability coefficient
(Mm / sec) Is separation of colored layer occurred? For Press Car theft Individual Average Plain block
(Impervious) 5.0 or higher below 10 7 or less - If there is a colored layer, the thickness should be at least 8 mm from the surface and the separation of the colored layer should not occur after the bending strength test. Permeable block 4.0 or higher 5.0 or higher - - 0.1 or more
pass

division Flexural strength (MPa) Permeability coefficient
(mm / sec) Absorption Rate (%) Impact resistance Colored layer
Is separation occurring? Production Example 1 5.1 pass - ◎ Occurrence × Production Example 2 4.7 pass - ◎ Occurrence × Production Example 3 4.9 pass - ◎ Occurrence × Production Example 4 5.3 - 5.1 ◎ Occurrence × Comparative Preparation Example 1 4.6 pass - ◎ Occurrence × Comparative Production Example 2 4.7 pass - ◎ Occurrence × Comparative Production Example 3 4.6 pass - ◎ Occurrence ×

In all of Production Examples 1 to 4 and Comparative Production Examples 1 to 3, physical properties such as bending strength, permeability coefficient and impact resistance were excellent.

However, in Comparative Production Example 1 in which acid treatment was not performed and Comparative Production Example 2 in which acid treatment was performed in an acid solution of pH 6.5, odor was generated during storage of shell aggregate and block production due to the presence of organic matter remaining after pressure- There was a problem.

Further, in the case of the shell aggregates of Comparative Production Examples 1-3 and 1-4, there was a problem that the angular portions of the shell aggregate had some angled portions, resulting in poor work stability.

Experimental Example  2 : Chaos  Evaluation experiment

The heat shrinkability evaluation test of the heat block prepared in the above Production Examples and Comparative Production Examples was carried out, and the results are shown in Table 5 below.

Then, in order to evaluate the tinting strength of the heat-shielding color block of the above-mentioned heat block, after immersing in brine for 12 hours in the direction of the surface layer of the heat block, washing with water under strong pressure was carried out to evaluate heat resistance in the following manner.

The evaluation of the heat resistance was carried out in accordance with the evaluation standard on the road surface reduction block similar to that of the Japan Interlocking Block Pavement Technology Association (JIPEA), and was measured based on the following measuring devices and methods.

1. Measuring equipment

 (1) Application specimen specification

100 mm x 60 mm (the concrete block was formed into a circumferential shape of 100 mm (core cut) (see Fig. 8).

(2) Survey lamps

A xenon lamp (dose: 850 w / m ² ) was used to uniformly irradiate the surface of the specimen to be applied.

(3) Lamp holders

As shown in FIG. 6, the lamp was fixed at the center of the specimen and the height and direction of the lamp were adjustable.

(4) Thermocouple

The thermocouple measurement range was 0 to 100 and the accuracy was 0.1.

(5) Data logger

 The accuracy of the data logger was 0.1.

(6) Insulation

Foamed styrofoam (insulation material) having a thickness of about 50 mm was provided on the bottom and side surfaces of the specimen in order to prevent heat dissipation on the specimen (see FIG. 9).

2. Test method

(1) Preparation of Comparative Specimen

The comparative specimens were made of asphalt concrete of the same specification as the target block (see Fig. 8).

(2) Pre-Tropical Installation Method

As shown in Fig. 7, the front troposphere was installed on the specimen. The total installation point of the troposphere was set to three points with a radius of 20 mm in the circumference centered on the specimen. In addition, the front surface of the specimen was fixed with adhesive and attached to the temperature detector with silver paper of 1cm × 1cm or less. The fixation by the adhesive was also carried out not only on the connection part but also on the covering part.

(3) Constant temperature and humidity setting and specimen curing

Temperature in a constant temperature and humidity room Set the temperature at 30 ° C (± 1 ° C). The specimens were cured for more than 5 hours in the constant temperature and humidity chamber, and the relative humidity of the temperature and humidity chamber was 50 (± 5) RH%.

(5) Setting the lamp height

In the field test, the lamp height was adjusted so that the surface temperature of the comparative specimen (wheat grain asphalt concrete) rose to 60 ° C for about 3 hours.

(6) Specimen setting

The weight was installed at the center of the lamp just below the center of the lamp.

(7) Start of test

Connect the entire troposphere to the data logger, turn on the lamp and start the irradiation test. In addition, since it takes about 10 minutes until the irradiation amount becomes constant immediately after the irradiation, the switch is turned on before the start of the test so as not to directly touch the specimen. Also, the room temperature and the surface temperature of the specimen were measured every 10 minutes, and the test was terminated after 3 hours of irradiation.

(8) Calculation method of the road surface temperature difference

The road surface temperature difference was calculated by the following equation (4).

&Quot; (4) "

T = T1 - T2

In the equation (4), T is the road surface temperature difference (占 폚), T1 is the road surface temperature (占 폚) after three hours irradiation of the specimen of the target block, and T2 is the surface temperature (占 폚) of the comparative specimen after 3 hours irradiation.

division T1 (° C) T2 (占 폚) T (占 폚) Production Example 1 46.2 60.3 13.1 Production Example 2 45.5 60.4 13.6 Production Example 3 46.0 60.3 14.1 Production Example 4 46.4 60.2 13.5 Comparative Preparation Example 1 46.9 60.4 9.8 Comparative Production Example 2 47.1 60.1 10.2 Comparative Production Example 3 50.6 60.4 12.5

As a result of the test results of Table 5, it can be seen that the heat block of Production Examples 1 to 4 and Comparative Production Examples 1 to 3 had significantly lower surface temperature over time than the block made of asphalt.

In this connection, Comparative Example 1 in which methyl methacrylate alone was used and Tg in the case of using the acrylic emulsion resin of Comparative Example 2, which was copolymerized only with monomers having a Tg of more than 120 ° C., , The coloring power of the heat-sensitive pigment to the sand was not good, and the pigment was partially peeled off from the sand, resulting in a low surface temperature difference.

In Comparative Production Example 3, although the road surface temperature difference was high, there was a problem that the chromaticity of the surface of the heat block was inferior.

As a result, it was confirmed that the heat block of the present invention has excellent mechanical properties. It was also confirmed that the heat block of the present invention has a very high road surface temperature difference of 13 캜, preferably 13.5 캜 to 15 캜.

10: heat block 10a: drainage groove 11: surface layer
12: base layer 13: heat shielding-non-slip structure layer 20: chain conveyor
50: line eye 51: first side (or first side) 52: second side (or second side)
53: third side (or third side) 54: fourth side (or fourth side)

Claims (14)

An acrylic emulsion resin containing an aqueous dispersion of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer;
A black pigment containing a metal oxide of a spinel structure represented by the composition of Cu (Mn, Fe) ₂ O ₄ , and a heat-sensitive pigment comprising tungsten oxide; And
Wherein the copolymer comprises an ethylenically unsaturated monomer (A) having a Tg of 80 ° C or higher and an ethylenically unsaturated monomer (B) having a Tg of 30 ° C or lower at a weight ratio of 1: 2 to 6 Heat sand color sand composition.
The heat-shrinkable color sand composition according to claim 1, which comprises 10 to 30 parts by weight of the heat-sensitive pigment and 1,000 to 8,000 parts by weight of the sand, based on 100 parts by weight of the acrylic emulsion resin.
The method of claim 1, wherein the ethylenically unsaturated monomer is selected from the group consisting of methyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, hexadecyl methacrylate, ethyl acrylate, Hydroxyethyl methacrylate, N-methylol methacrylamide, N-methylol acrylamide, glycidyl methacrylate, diacetone acrylamide, acetoxyethylene acrylate, acetoxyethylene methacrylate, Wherein the coloring composition comprises at least two selected from the group consisting of sodium carbonate and sodium carbonate.
delete The heat-shrinkable color sand composition according to claim 1, wherein the black pigment comprises iron and manganese in a molar ratio of 1: 5 to 25, and the molar ratio of copper / (manganese + iron) is 1: 2 to 3.5 molar ratio.
The method of claim 1, wherein the heat-sensitive pigment is selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, tin-doped zinc oxide, Zinc, and an infrared shielding agent comprising at least one selected from the group consisting of zinc and zinc.
A heat-shrunk color sand comprising the composition of claim 1.
The method of claim 7, wherein the differential color sand is selected from the group consisting of 25-35 wt.% Acrylic polyol resin, 25-35 wt.% Polyester polyol resin, 5-15 wt.% Toluene, 10-20 wt.% Xylene, 10-20 wt. % ≪ / RTI > by weight of the composition.
A base layer, a surface layer and a heat shielding-non-slip structure layer are formed in order,
Wherein the heat-shroud-resistant structural layer comprises the heat-set color sand and shell aggregate of claim 7,
Wherein the surface layer comprises white cement, white quartz, the heat shade color sand, and shell aggregate,
The base layer is a water-permeable layer or an impermeable layer,
The surface layer is formed of a surface layer mortar containing 100 to 300 parts by weight of white cement, 40 to 250 parts by weight of a heat shade color sand, 30 to 100 parts by weight of a shell aggregate, and 20 to 50 parts by weight of water Features a differential block.
delete [10] The method of claim 9, wherein the water permeable layer is formed of a permeable mortar containing 300 to 400 parts by weight of Portland cement, 450 to 650 parts by weight of fine aggregate, and 1,000 to 1,500 parts by weight of coarse aggregate with respect to 100 parts by weight of water, .
The heat block according to claim 9, wherein the impervious base layer is formed of an impermeable mortar containing 300 to 400 parts by weight of Portland cement and 1,500 to 2,500 parts by weight of fine aggregate, based on 100 parts by weight of water.
10. The method of claim 9, wherein the surface layer has an average void of 12% to 20%
Wherein the thickness ratio of the surface layer to the base layer is 1: 4.5 to 7.
delete

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