KR100423471B1 - Anti-freeze composition and its manufacturing method - Google Patents

Abstract

It is sprayed onto snow or ice to prevent freezing of the road surface and to suppress slippage of the traveling vehicle.

The cryoprotectant composition containing calcium acetate and calcium acetate in a specific ratio is sprayed onto the snow surface or the ice surface to prevent freezing of the road surface, to suppress slippage, and to shorten the braking distance of the traveling vehicle. The ratio of calcium acetate is about 20 to 250 parts by weight based on 100 parts by weight of calcium magnesium acetate.

Description

Cryoprotectant composition and preparation method thereof

The present invention relates to a cryoprotectant composition capable of suppressing slippage and shortening the braking distance of a traveling vehicle by spraying on frozen ice and snow surfaces.

In cold regions, such as in the northern regions where the cold of winter is severe, it is useful to attach spike tires to the vehicle in order to prevent the vehicle from slipping on the ice snow surface. However, since the use of spike tires has been fully regulated since 1990, very slippery freezing roads have been created in urban areas, increasing skidding and traffic congestion. In particular, since the coefficient of friction decreases and the braking distance of the vehicle becomes long on the ice, a lot of sliding accidents and traffic jams occur.

In order to suppress the sliding of a vehicle, various medicaments for promoting the melting of ice and snow, for example, a melting accelerator such as sodium chloride and calcium chloride are sprayed on the road surface of the road. However, since the snow melt or the melt ice effect is lowered, it is necessary to spray repeatedly, so that the amount of application of the melting accelerator increases. However, when these chemicals are sprayed in large quantities, metals such as automobiles, bridges, and road facilities are corroded. In addition, by dissolving and spilling in water, plant death, groundwater, rivers, water pollution such as lakes and swamps are concerned.

Therefore, calcium acetate (hereinafter sometimes referred to simply as CMA) has been proposed as a cryoprotectant with relatively low adverse effects on the environment. This CMA is a superior antifreeze in the report of the Alternate Highway Deicing Chemicals, 1980, March, of the Bjorksten Research Laboratory (BRL), supported by the US Federal Highway Administration. It is recognized.

Various proposals are made about such a CMA in the manufacturing method and use. For example, Japanese Patent Application Laid-Open No. 62-576 proposes using calcium acetate, magnesium acetate, or calcium magnesium acetate as a snow melt agent for farmland.

Japanese Laid-Open Patent Publication No. 62-267,246 discloses a concentrated acetic acid solution in the reaction vessel while introducing pulverized dolomite lime at a constant rate into the reaction vessel while maintaining the ratio of acid to dolomite lime at a chemical theoretical amount. A method for producing granulated magnesium acetate is disclosed, wherein the molar ratio of the feed amount of water to the feed amount of acetic acid is maintained at 0.75 to 1.15, and the wet granulated product is quantitatively taken out and dried.

Japanese Laid-Open Patent Publication No. 1-502,275 discloses a method for producing an ice making composition by spraying a slurry containing calcium acetate, magnesium acetate or magnesium magnesium magnesium on a support particle in a thin layer and drying. Further, Japanese Patent Laid-Open No. 2-292,385 discloses a non-polluting ice making composition comprising calcium acetate and an organic chelating agent.

Japanese Patent Laid-Open No. 1-502,200 discloses a composition comprising substantially pure magnesium acetate, which is substantially free of crystalline calcium acetate, magnesium acetate and unreacted magnesium base. This document describes that substantially pure magnesium acetate double salt has a high ice-melting effect, as compared to a mixture of calcium acetate and magnesium acetate. In addition, Japanese Patent Laid-Open No. 5-508,617 discloses substantially pure anhydrous crystals of magnesium acetate, having a purity of at least 99.5%, in order to prevent corrosion of aluminum and aluminum alloys.

When such CMA is sprayed on an ice snow surface such as a cold area, it is useful as an antifreezing agent because it promotes melting of ice snow, and can shorten the braking distance of the traveling vehicle. However, CMA alone is still limited in slipping, and it is difficult to further shorten the braking distance.

Accordingly, it is an object of the present invention to provide a freezing or anti-slip agent composition which is useful for suppressing slippage of a traveling vehicle and also a method for producing the same.

Another object of the present invention is to provide a non-slip agent composition and a method for manufacturing the same, which can reduce the braking distance by suppressing slippage of a running vehicle while simultaneously suppressing freezing of the road surface by spraying on a frozen snow surface such as a frozen road surface.

The present inventors earnestly examined in order to achieve the above object, and as a result, when calcium acetate (hereinafter sometimes referred to simply as "CA") is added to CMA at a specific ratio, the inventors suppress slippage even on ice and have extremely short braking distances. The present invention has been completed by finding out that the traveling vehicle can be stopped.

That is, the cryoprotectant composition of the present invention contains 20 to 250 parts by weight of calcium acetate (CA) based on 100 parts by weight of calcium magnesium acetate (CMA). This cryoprotectant composition is useful as an antislip agent composition for suppressing slippage on snow or ice surfaces. Therefore, this invention also provides the method of suppressing the slip of a traveling vehicle by spraying the said composition on snow surface or ice surface.

The cryoprotectant composition may be prepared by mixing 20 to 250 parts by weight of calcium acetate (CA) with respect to 100 parts by weight of calcium magnesium acetate (CMA).

In addition, in the present specification, the term “driving vehicle” refers to various vehicles that run in contact with snow or ice, such as bicycles, two-wheeled vehicles, automobiles, railway vehicles, aircrafts, sleds, etc. do.

The present invention is described in detail below.

Calcium magnesium acetate (CMA) may be a hydrate, but is often anhydride. Preferred CMAs include the compositional formula Ca _x Mg _y (C ₂ H ₃ O ₂ ) _{2 (x + y)} (wherein x is 2 to 6, preferably 3 to 4, y is 8 to 4, preferably 7 To 6), especially the crystalline CMA represented by CaMg ₂ (C ₂ H ₃ O ₂ ) ₆ is included. CMA is a salt such as a double salt different from a mixture of calcium acetate and magnesium acetate, and may be used not only as a high-purity magnesium magnesium acetate but also as a reaction product containing calcium acetate, magnesium acetate, unreacted components, and the like. When using the reaction product, the content of CMA is, for example, 95% by weight or more, preferably 98 to 100% by weight, more preferably about 99 to 100% by weight.

The CMA is easily prepared by a general method, for example, by neutralizing acetic acid and dolomite lime, and by precipitation from a solution containing a calcium component, a magnesium component and acetic acid. In the former method, for example, the method described in Japanese Patent Laid-Open No. 62-267,246 (method of introducing pulverized dolomite lime and an acetic acid aqueous solution into a reaction vessel and drying the resulting wet granular material) or The method of conformity is employ | adopted.

In the latter method, for example, the method described in Japanese Patent Laid-Open No. 1-502,200 (70: 110% of the stoichiometric amount with respect to the aqueous mixture of CM bases of calcium: magnesium = 4: 6 to 3: 7). A method of preparing and aging an aqueous slurry by adding acetic acid), the method described in Japanese Patent Laid-Open No. 5-508,617 (1) A solution containing magnesium and acetate ions in a substantially nonaqueous solvent, and a substantially nonaqueous Mixing a solution containing calcium and acetate ions in a solvent and maintaining the mixture at an appropriate temperature to form crystalline magnesium acetate; (2) substantially adding a solution containing magnesium, calcium and acetate ions in a non-aqueous solvent To form crystalline magnesium acetate by maintaining the solution at an appropriate temperature) or the Method and the like can be employed.

A feature of the composition of the present invention is that it comprises a specific ratio of calcium acetate (CA) relative to the CMA. The ratio of CA is 20 to 250 parts by weight (for example 50 to 200 parts by weight), preferably 50 to 250 parts by weight (for example 70 to 240 parts by weight), more preferably 70 to 100 parts by weight of CMA. To 220 parts by weight (for example, 80 to 180 parts by weight). In particular, a composition comprising 80 to 200 parts by weight (for example 100 to 200 parts by weight) of CAMA based on 100 parts by weight of the driving vehicle by spraying on the snow surface by the high anti-slip effect despite the speed of the driving vehicle It is possible to reliably and significantly shorten the traveling distance of the vehicle.

If the ratio of CA to 100 parts by weight of CMA is out of the above range, it is difficult to effectively express a high anti-slip effect on the traveling vehicle. When CMA is used as the reaction product, the amount of CA in the composition also includes the amount of CA contained as impurities in the reaction product.

The calcium acetate may be a hydrate such as monohydrate or dihydrate, or may be anhydride. Calcium acetate can be easily obtained by a general method, for example, by reacting quicklime (calcium oxide), slaked lime (calcium hydroxide) and acetic acid.

The composition containing CMA and CA may contain magnesium acetate (MA). Content of magnesium acetate is 0-10 weight part with respect to 100 weight part of CMA, Preferably it is about 0-5 weight part.

In addition, the quantification of components, such as CMA and CA, can be performed by the following method, for example.

Content of CA A

The content of CA is calculated according to the following formula from the weight loss due to dehydration of the crystal water in CA.½H ₂ O.

Content of CA, 1/2 H ₂ O A (wt%) = W1 × (X / Y) × 100

(W1 represents a weight loss amount (% by weight) according to dehydration of the crystallized water, X represents a molecular weight of 167 of CA.½H ₂ O, and Y represents a molecular weight of 9 of 1/2 H ₂ O.)

Content of MA B

The content of the MA is calculated from the following reference to the peak exothermic heat of MA and 4H ₂ O at 220 to 250 ℃ expression in (Differential Thermal Analysis) DTA.

Content of MA 4H ₂ O B (wt%) =

[(1.576 (μs / mg) × W2 (mg)) / U (μs / mg)) / W2 (mg) × 100

(W2 represents the weight of the sample, and U represents the calorific value 92.2 (Pa · s / mg) per unit weight of MA · 4H ₂ O.)

Content of Unreacted Magnesium Base C

The endothermic peak or weight loss of 320 to 340 ° C. is thought to be due to dehydration of the unreacted magnesium base. [Mg (OH) ₂ → MgO + H ₂ O]. Using this, content of unreacted magnesium base is computed by the following formula.

Content of unreacted magnesium base C (% by weight) = W3 × 58/18

(W3 represents a weight loss amount (% by weight), 58 represents a molecular weight of Mg (OH) ₂ , and 18 represents a molecular weight of water.)

Content of Crystalline and Adsorbed Water in CMA D

In the TG curve of TG (Thermogravimetry) -DTA (Differential Thermal Analysis) analysis, the weight loss amount up to 150 ° C includes the weight loss amount due to dehydration of MA.4H ₂ O in addition to the CMA crystal water and the physical adsorption water. Therefore, the content of crystal water and adsorbed water of CMA is calculated from the following formula.

Content of CMA and Adsorbed Water D (wt%) = W150 (wt%)-WMA (wt%)

(W150 represents a weight reduction amount up to a temperature of 150 ° C., and WMA represents a weight reduction amount due to dehydration of MA.4H ₂ O.)

Content of CMA

Content of CMA is computed by the following formula.

Content of CMA (% by weight) = 100-(A + B + C + D)

Content of Ca and Mg in CMA

The amount of calcium (Ca) T _ca (% by weight) and the amount of magnesium (Mg) T _Mg (% by weight) in the sample are quantitatively analyzed by fluorescence X-ray analysis. Based on this analysis value, Ca content C _{Ca / CMA} and Mg content C _{Mg / CMA} in _CMA are computed according to the following formula.

Ca content in CMA C _{Ca / CMA} (% by weight) = T _Ca -E

Mg content in CMA C _{Mg / CMA} (% by weight) = T _Mg -F-G

(Wherein E is the amount of Ca contained in CA.1 / 2H ₂ O, F is the amount of Mg (% by weight) contained in MA.4H ₂ O, and G is the amount of Mg contained in Mg (OH) ₂ ( Weight percent))

The composition of the present invention is useful for suppressing slippage on the snow surface or the ice surface and shortening the braking distance of an automobile or the like compared to the CMA. In particular, it is possible to shorten the braking distance of the traveling vehicle by spraying on a hard ice sheet. This is considered as follows. In other words, if the CMA is sprayed on a hard ice sheet and the car is driven on it, the CMA penetrates the surface of the ice sheet due to the stirring effect of the weight of the vehicle body and the rotation of the tire, and the ice surface is shaky. Change to phase. Isha It is thought that the ice surface of the top increases the coefficient of friction to shorten the braking distance of the traveling vehicle. On the other hand, the solubility in water at room temperature was about 29% CMA (Japanese Patent Laid-Open Publication No. 5-508,617), about 25% calcium acetate, and about 41% magnesium acetate (tetrahydrate). "Chemical Handbook" Basic Edition, Nippon Gagakugai, Maruzen, published on September 30, 2015, page 177), Magnesium Acetate has higher solubility in water than calcium acetate. Therefore, when CA is added to CMA to increase calcium content, The coefficient of friction of the ice surface of the bed is increased, which can further shorten the braking distance of the vehicle. On the other hand, it is considered that increasing the magnesium content increases the proportion of the solution, forms a water film between the lower hard ice sheet, lowers the friction coefficient, and lengthens the braking distance of the vehicle.

The composition of the present invention may be formulated with various additives, such as friction aids (e.g., inert particulates such as sand, pulverized lime, vermiculite, pumice, wood meal and fruit husks), black materials (e.g. For example, black coloring agents, such as charcoal and carbon black), etc. may be included.

The cryoprotectant composition of the present invention can be obtained by a simple operation of mixing 20 to 250 parts by weight of calcium acetate with respect to 100 parts by weight of calcium acetate.

In addition, the cryoprotectant composition can be obtained by mixing dolomite lime and quicklime (calcium oxide) or slaked lime (calcium hydroxide) corresponding to the ratio of CMA and CA and reacting the obtained mixture with acetic acid. The amount of quicklime or slaked lime may be, for example, an amount such that the ratio of CA to CMA is the above ratio, and is selected according to the composition of raw materials such as dolomite lime used. The ratio of dolomite lime to quicklime or hydrated lime is such that the ratio of the calcium component to the magnesium component is, for example, Ca / Mg = 1/1 to 3/1 (molar ratio) in terms of elemental ratio, preferably 1.2 / 1 to 2 It is often selected in the range of about / 1 (molar ratio), and is usually about 1.3 / 1 to 1.7 / 1 (molar ratio). Moreover, you may mix and use quicklime and slaked lime. The acetic acid may be used as an aqueous solution or may be used as glacial acetic acid. The amount of acetic acid used is selected in the range of, for example, about 75 to 125% of the theoretical theoretical amount. More specifically, for example, 150 to 270 parts by weight of acetic acid (for example, 160 to 265 parts by weight), preferably 190 to 230 parts by weight, and more preferably 200 to 230 parts by weight, based on 100 parts by weight of the mixture. It is enough.

The reaction of the mixture with acetic acid can be carried out in the same manner as the production method of the CMA. The reaction may be carried out in an aqueous system, usually carried out in a reaction system using an aqueous acetic acid solution, acetic acid and glacial acetic acid as solvents, while supplying the dolomite lime, quicklime or slaked lime and an acetic acid component (aqueous acetic acid solution, acetic acid or glacial acetic acid) at a constant ratio. It is often carried out by a method of mixing and reacting, a method of mixing and reacting the mixture with an acetic acid component (acetic acid aqueous solution, acetic acid or glacial acetic acid) in a fixed ratio. Reaction temperature is about 50-100 degreeC (for example, 60-90 degreeC) normally, including the exotherm produced | generated by reaction. After completion | finish of reaction, a granular composition can also be obtained by crushing a reaction product as needed.

The composition of the present invention is usually used in powder form. The average particle diameter of the composition containing CMA and CA can be suitably selected according to the purpose of use, etc., For example, it is 10 micrometers-10 mm, Preferably it is 50 micrometers-5 mm, More preferably, it is about 100 micrometers-2.5 mm.

The composition of the present invention is useful as an anti-freezing agent that prevents freezing by spraying snow, ice, or the like, and a snow melting or ice-melting agent (snow or ice-making agent) that melts or ices, and is sprayed on a freezing surface, snow, ice, It is also useful as an anti-slip agent that can shorten the braking distance.

The amount of spraying on snow, ice, etc. may be selected according to the air temperature, the amount of snow, the degree of freezing, the purpose of the application (freezing prevention, snow melting, non-slip, etc.), for example, 1 to 500 g / ㎡, preferably 5 to 250 g / m 2, more preferably about 10 to 100 g / m 2.

Since the composition of this invention contains CMA and CA in a specific ratio, it is useful as an antifreezing agent or antislip agent which suppresses the slip of a traveling vehicle. In addition, by spraying on a frozen snow surface such as a frozen road surface, the freezing of the road surface can be suppressed, the sliding of the traveling vehicle can be suppressed, and the braking distance can be shortened. For this reason, not only freezing of the road surface in the cold region can be prevented, but also by spraying on the freezing or freezing surface, slippage of the traveling vehicle can be prevented, and traffic congestion and occurrence of a traffic accident can be reduced.

In the method of the present invention, a simple operation of mixing CMA and CA at a specific ratio allows the composition as described above to be efficiently produced.

Example

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited to these Examples.

Examples 1 to 5 and Comparative Examples 1 to 3

Magnesium acetate (CMA) double salt (Ca: Mg weight ratio = 1: 1, element molar ratio = 1: 1.7) Magnesium acetate (MA) or calcium acetate (CA) was mixed and frozen at the following ratio with respect to 100 parts by weight of An inhibitor composition was prepared. In Comparative Example 1, the cryoprotectant composition was not sprayed on the running path covered with ice. In addition, in order to suppress the physical friction coefficient fluctuation, the samples of all the compositions were used in the fine powder of 0.3 mm or less in diameter.

Comparative Example 1: No application of cryoprotectant composition

Comparative Example 2: MA / CMA = 10/100 (parts by weight)

Comparative Example 3: CA / CMA = 0/100 (parts by weight)

Example 1 CA / CMA = 50/100 (parts by weight)

Example 2 CA / CMA = 80/100 (parts by weight)

Example 3 CA / CMA = l50 / 100 (parts by weight)

Example 4 CA / CMA = 200/100 (parts by weight)

Example 5 CA / CMA = 250/100 (parts by weight)

Then, on an asphalt pavement (about 50 m in length and 9 running paths of about 5 m in width) covered with ice under a temperature of -7 ° C to -8 ° C, an ice surface temperature of -8 ° C, and cloudy weather conditions, The composition prepared in Comparative Examples and Examples was sprayed with a spraying amount of about 50 g / m 2, and then allowed to stand for 20 minutes, and a test vehicle (FF ordinary car, weight of about 1,200 kg) was used to infiltrate and stir each sample onto the ice surface. 10 round trips were made. In the test of Comparative Example 1, the test vehicle was reciprocated to the traveling path 10 times without spraying with a sample. Thus, the test vehicle enters the driveway at the entry speeds of 30 km / hr and 40 km / hr, and the distance from the brake to the complete stop of the vehicle with the rapid brake is measured as the braking distance. It was. The results are shown in Table 1 below and in FIG.

TABLE 1

As clearly shown in Table 1 and the accompanying FIG. 1, the braking distance is shortened by spraying of CMA (Comparative Example 3) compared to Comparative Example 1, but when using CMA (Comparative Example 2) to which MA is added, the braking distance is achieved. Lengthens. On the other hand, the composition of the embodiments in which CA is added in a specific ratio can shorten the braking distance of the traveling vehicle.

1 is a graph showing the results in Examples and Comparative Examples.

Claims (5)

A cryoprotectant composition comprising 20 to 250 parts by weight of calcium acetate based on 100 parts by weight of calcium acetate. The cryoprotectant composition according to claim 1, wherein the ratio of calcium acetate is 50 to 250 parts by weight based on 100 parts by weight of calcium magnesium acetate. An anti-slip agent composition comprising calcium acetate and calcium acetate, wherein the ratio of calcium acetate is 70 to 220 parts by weight relative to 100 parts by weight of calcium magnesium acetate. A method of spraying a composition comprising 20 to 250 parts by weight of calcium acetate with respect to 100 parts by weight of calcium acetate on snow or ice to suppress slippage of a traveling vehicle. A method for producing a cryoprotectant composition, comprising mixing 20 to 250 parts by weight of calcium acetate with respect to 100 parts by weight of calcium acetate.