JP3483704B2 - Antifreeze composition 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 antifreeze composition capable of suppressing slippage and shortening a braking distance of a traveling vehicle by spraying on an ice surface, a snow surface, or the like.

[0002]

2. Description of the Related Art In cold regions such as northern countries where winter is severe, it is useful to equip a vehicle with spiked tires in order to prevent the vehicle from slipping on ice and snow. However, since the use of spiked tires has been completely restricted since 1991, a very slippery frozen road surface occurs in cold districts in urban areas, increasing slip accidents and traffic congestion. Especially on an ice plate, slip accidents and traffic jams frequently occur because the friction coefficient decreases and the braking distance of the vehicle becomes long.

Various agents for promoting the melting of ice and snow, for example, melting accelerators such as sodium chloride and calcium chloride are sprayed on the road surface in order to suppress vehicle slip. Moreover, if the effect of melting snow or melting ice is reduced, it is sprayed repeatedly, so the amount of the melting accelerator applied is large.

However, when a large amount of these chemicals are sprayed, they corrode metals such as automobiles, bridges and road facilities. In addition, there is a concern about plant death, groundwater, water pollution of rivers and lakes, etc. due to the dissolution and outflow of water.

Therefore, calcium magnesium acetate (hereinafter sometimes simply referred to as CMA) has been proposed as an antifreezing agent having a relatively small adverse effect on the environment. This CMA is the Federal Highway Administra of the United States.
Bjorksten Research Laboratory supported by tion
(BRL) Report “” Alternative Highway Deicing Chemi
Cals ”, 1980, March”, recognized as a superior antifreeze agent.

For such CMA, various proposals have been made regarding its manufacturing method and use. For example, in JP-A-62-576, calcium acetate,
It has been proposed to use magnesium acetate or calcium magnesium acetate as a snow melting agent for agricultural land.

In Japanese Patent Laid-Open No. 62-267246, a crushed dolomite lime is introduced into a reaction vessel at a constant rate, and at the same time, a concentrated acetic acid aqueous solution is prepared while maintaining the ratio of acid to dolomite lime at a stoichiometric amount. Introduced into the reaction vessel at a constant rate, maintaining the molar ratio of the amount of water supplied to the amount of acetic acid supplied to 0.75 to 1.15, and quantitatively removing the wet granular product and drying. A method of making coarse-grained calcium magnesium acetate is disclosed.

[0008] In JP-A-1-502275, a deicing composition is produced by spraying a slurry containing calcium acetate, magnesium acetate or calcium magnesium acetate in a thin layer on support particles and drying. A method is disclosed. JP-A-2-292385 discloses a non-staining deicing composition containing calcium magnesium acetate and an organic chelating agent.

Japanese Patent Publication No. 1-502200 discloses a composition containing crystalline calcium acetate, magnesium acetate and a substantially pure calcium magnesium magnesium double salt substantially free of unreacted magnesium base. ing. This document describes that substantially pure calcium-magnesium acetate double salt has a higher ice-melting action than a mixture of calcium acetate and magnesium acetate. Further, JP-A-5-508617 discloses a substantially pure anhydrous crystal of calcium magnesium acetate having a purity of at least 99.5% in order to prevent corrosion of aluminum and aluminum alloys. ing.

When such CMA is sprayed on the surface of ice and snow in a cold region or the like, it promotes melting of ice and snow, and is therefore useful as an antifreezing agent, and the braking distance of a traveling vehicle can be shortened. However, with CMA alone, there is still a limit to slip prevention, and it is difficult to further reduce the braking distance.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an antifreezing agent or antislip agent composition useful for suppressing slip of a traveling vehicle and a method for producing the same.

Another object of the present invention is to provide an anti-slip agent composition capable of suppressing freezing of a road surface by spraying on a snowy surface such as a frozen road surface, suppressing slipping of a traveling vehicle, and shortening a braking distance. It is to provide a manufacturing method.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that calcium acetate (hereinafter sometimes simply referred to as CA) is added to CMA at a specific ratio. The inventors have found that the vehicle can be stopped with an extremely short braking distance by suppressing slip even on an ice board, and the present invention has been completed.

That is, the antifreezing agent composition of the present invention contains 20 to 250 parts by weight of calcium acetate (CA) with respect to 100 parts by weight of calcium magnesium acetate (CMA). This antifreezing agent composition is useful as an antislip agent composition for suppressing a slip on a snow surface or an ice surface. Therefore, the present invention also provides a method of spraying the composition on a snow surface or an ice surface to suppress slipping of a traveling vehicle. The cryoprotectant composition to calcium magnesium acetate (CMA) 100 parts by weight, Ru can be prepared by mixing 20 to 250 parts by weight of calcium acetate (CA).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. Calcium magnesium acetate (CMA) may be a hydrate, but is often an anhydrate. Preferred C
The MA, in the composition formula _{Ca x Mg y (C 2 H} 3 O 2) 2 (x + y) ( wherein, x is 2-6, preferably 3 to 4, y is 8-4, preferably 7 to Crystalline CMA represented by 6), especially CaMg
A crystalline CMA represented by 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 is not only a high-purity calcium magnesium acetate simple substance but also a reaction product containing calcium acetate, magnesium acetate, unreacted components, and the like. May be used. When the reaction product is used, the CMA content is, for example, 95% by weight or more, preferably 98 to 100% by weight, and more preferably 99 to 1% by weight.
It is about 00% by weight.

The CMA can be easily produced by a conventional method, for example, a method of neutralizing acetic acid and dolomite lime, a method of precipitating from a solution containing a calcium component, a magnesium component and acetic acid. In the former method, for example, the method described in JP-A-62-267246 (a method of introducing pulverized dolomite lime and an acetic acid aqueous solution into a reaction vessel and drying the produced wet powder granules) ) Or a method similar thereto can be adopted.
In the latter method, for example, the above-mentioned special table 1-502
200 (Preparation of an aqueous slurry by adding a stoichiometric amount of 70 to 110% acetic acid to an aqueous mixture of CM base of calcium: magnesium = 4: 6 to 3: 7). Method of aging and aging)
No. 508617 (Method of mixing a solution containing magnesium and acetate ions in a substantially non-aqueous solvent and a solution containing calcium and acetate ions in a substantially non-aqueous solvent, and mixing Holding the liquid at a suitable temperature to form crystalline calcium magnesium acetate,
A method of forming a solution containing magnesium, calcium and acetate ions in a substantially non-aqueous solvent, and holding this solution at an appropriate temperature to form crystalline calcium magnesium acetate), a method according to these methods, etc. Can be adopted.

The feature of the composition of the present invention is that it contains a specific ratio of calcium acetate (CA) to the CMA. The ratio of CA is 20 with respect to 100 parts by weight of CMA.
To 250 parts by weight (eg 50 to 200 parts by weight), preferably 50 to 250 parts by weight (eg 70 to 240 parts by weight), more preferably 70 to 220 parts by weight (eg,
80 to 180 parts by weight). In particular, CMA100
80 to 200 parts by weight of CA (eg 10
By spraying a composition containing 0 to 200 parts by weight) on the surface of ice and snow, the travel distance of the traveling vehicle can be reliably and significantly shortened owing to a high anti-slip effect regardless of the speed of the traveling vehicle. If the ratio of CA to 100 parts by weight of CMA is out of the above range, it is difficult to effectively exert a high slip suppressing effect on a traveling vehicle. When CMA is used as a reaction product, the amount of CA in the composition also includes the amount of CA contained as an impurity in the reaction product.

The calcium acetate may be a hydrate such as a monohydrate or a dihydrate, or may be an anhydrate. Calcium acetate can be easily obtained by a conventional method, for example, a reaction between quick lime (calcium oxide) and slaked lime (calcium hydroxide) and acetic acid.

The composition containing CMA and CA may contain magnesium acetate (MA). The content of magnesium acetate is 0 to 1 with respect to 100 parts by weight of CMA.
It is 0 part by weight, preferably about 0 to 5 parts by weight.

The quantification of the components such as CMA and CA can be carried out by the following method, for example. [CA Content A] The CA content is calculated from the following formula based on the weight loss due to dehydration of water of crystallization in CA · 1 / 2H ₂ O. Content of CA · 1 / 2H ₂ O A (% by weight) = W1 × (X /
Y) × 100 (in the formula, W1 is a weight reduction amount (% by weight) due to dehydration of crystal water, X is a molecular weight of CA · 1 / 2H ₂ O of 167, and Y is 1 / 2H ₂ O.
The content of MA is B, and the content of MA is DTA (Differen
It can be calculated by the following formula based on the exothermic peak calorific value of MA.4H ₂ O at 220 to 250 ° C. in tial thermal analysis). MA · 4H ₂ O content B (% by weight) = [(1.576 (μV · s / m
g) × W2 (mg)) / U (μV · s / mg)] / W2 (mg) × 100 (In the formula, W2 is the weight of the sample, and U is the calorific value per unit weight of MA · 4H ₂ O 92.2. (Indicates μV · s / mg) [Content C of unreacted magnesium base] 320 to 340
The endothermic peak at ℃ and the weight loss are thought to be due to dehydration of unreacted magnesium base [Mg (OH) ₂ → MgO +
H ₂ O]. Utilizing this fact, the content of unreacted magnesium base can be calculated by the following formula. Content of unreacted magnesium base C (% by weight) = W3 x
58/18 (In the formula, W3 is the weight reduction amount (% by weight), and 58 is Mg (O
H) ₂ molecular weight, 18 indicates the molecular weight of water) [Content of crystallization water of CMA and adsorbed water D] TG (Thermogr
avimetry) -DTA (Differential thermal analysi)
s) In the TG curve of the analysis, the amount of weight loss up to a temperature of 150 ° C includes MA water in addition to CMA crystallization water and physically adsorbed water.
-Since the weight loss due to dehydration of 4H ₂ O is included, the content of water of crystallization of CMA and adsorbed water is calculated by the following formula. CMA water of crystallization and adsorbed water content D (wt%) = W150
(Wt%)-WMA (wt%) (In the formula, W150 is the weight reduction amount up to a temperature of 150 ° C, WMA
Represents the amount of weight loss due to dehydration of MA.4H ₂ O) [Content of CMA] The content of CMA can be calculated by the following formula. CMA content (% by weight) = 100− (A + B + C +
D) [Contents of Ca and Mg in CMA] Quantitative analysis of calcium (Ca) content T _Ca (wt%) and magnesium (Mg) content T _Mg (wt%) in the sample is carried out by fluorescent X-ray analysis. Based on this analytical value, the Ca content in _CMA C _{Ca / CMA} and M
The g content C _{Mg / CMA} is calculated based on the following formula. Ca content in _CMA C _{Ca / CMA} (wt%) = T _Ca −E Mg content in _CMA C _{Mg / CMA} (wt%) = T _Mg −F−
G (in the formula, E is the amount of Ca contained in CA · 1 / 2H ₂ O, F is M
The amount of Mg contained in A · 4H ₂ O (wt%), G is Mg
(The amount of Mg contained in (OH) ₂ (% by weight) is shown.) The composition of the present invention suppresses slip on a snow surface or an ice surface as compared with CMA and shortens a braking distance of an automobile or the like. It is useful. In particular, the braking distance of the traveling vehicle can be shortened by spraying even on a solid ice plate. This can be considered as follows. That is, C on a solid ice board
When MA is sprayed and a car is run on it, CMA is generated due to the effect of stirring due to the weight of the vehicle body and the rotation of the tire.
Permeates the surface of the ice board, and the ice surface changes into a sherbet. It is believed that this sherbet-like ice surface increases the sliding friction coefficient and shortens the braking distance of the traveling vehicle. On the other hand, the solubility in water at room temperature is about 2 for CMA.
9% (Japanese Patent Laid-Open No. 5-508617), about 25% for calcium acetate, and about 41% for magnesium acetate (tetrahydrate) (Revised 4th edition "Chemical Handbook", Basic Edition, (Nippon Kagaku)) Edited by Maruzen Co., Ltd., published on September 30, 1993,
(P. 177), magnesium acetate has a higher solubility in water than calcium acetate. Therefore, C in CMA
When A is added to increase the calcium content, the coefficient of friction of the sherbet-like ice surface increases, and the braking distance of the vehicle can be further shortened. On the other hand, if the magnesium content is increased, the proportion of the solution is increased, and it is considered that a water film is formed between the ice layer and the lower solid ice disk to reduce the friction coefficient and the braking distance of the vehicle is lengthened. .

The composition of the present invention may optionally contain various additives such as rubbing aids (eg sand, ground lime, vermiculite, pumice, wood flour, inert granules such as fruit shells). Etc.), a black substance (for example, a black colorant such as charcoal, carbon black, etc.) and the like.

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

The antifreeze composition is prepared by mixing dolomide lime and quick lime (calcium oxide) or slaked lime (calcium hydroxide) according to the ratio of CMA and CA. It can also be obtained by reacting with acetic acid. The amount of quicklime or slaked lime to be used may be, for example, an amount such that CA is in the above ratio with respect to CMA, and can be selected according to the composition of the raw material such as dolomite lime to be used. As for the ratio of dolomite lime and quick lime or slaked lime, the ratio of calcium component and magnesium component is, for example, Ca / Mg = 1/1 to 1 in terms of element ratio.
It is often selected from the range of about 3/1 (molar ratio), preferably about 1.2 / 1 to 2/1 (molar ratio).
It is about 1.3 / 1 to 1.7 / 1 (molar ratio). In addition,
Quick lime and slaked lime may be mixed and used. The acetic acid may be used as an aqueous solution or glacial acetic acid. The amount of acetic acid used is, for example, 75-
It can be selected in the range of about 125%. More specifically, for example, acetic acid of 150 to 2 is added to 100 parts by weight of the mixture.
70 parts by weight (eg 160 to 265 parts by weight), preferably 190 to 230 parts by weight, more preferably 200 to
It is about 230 parts by weight.

The reaction of the mixture with acetic acid is carried out according to
It can be performed by a method similar to the manufacturing method of. The reaction may be carried out in an aqueous system, usually, an acetic acid aqueous solution, a method performed in a reaction system using acetic acid or glacial acetic acid as a solvent, the dolomite lime, quick lime or slaked lime, acetic acid component (acetic acid aqueous solution,
Acetic acid or glacial acetic acid), a method of reacting by mixing while supplying at a constant ratio, the mixture and acetic acid component (acetic acid aqueous solution,
In many cases, it is carried out by a method in which acetic acid or glacial acetic acid) is supplied at a constant ratio and mixed to react. The reaction temperature is usually 50 to 1 including heat generated by the reaction.
The temperature is about 00 ° C (for example, 60 to 90 ° C). After completion of the reaction, a powdery composition may be obtained by crushing the reaction product, if necessary.

The composition of the present invention is usually used in the form of powder. The average particle size of the composition containing CMA and CA can be appropriately selected according to the purpose of use, and is, for example, 10 μm to 1 μm.
It is 0 mm, preferably 50 μm to 5 mm, and more preferably 100 μm to 2.5 mm.

The composition of the present invention is useful as an antifreezing agent for preventing freezing, and a snow melting and deicing agent (snow removing agent or deicing agent) for deicing snow by spraying it on a snow surface or an ice surface. At the same time, it is useful as an anti-slip agent that can reduce the braking distance of a traveling vehicle by spraying it on a frozen surface, a snow surface, an ice surface, or the like.

The amount of spray on the snow surface, ice surface, etc.
It can be selected according to the amount of snow, the degree of freezing, the purpose of spraying (freezing prevention, snow melting, ice slip prevention, etc.), for example, 1 to 500 g / m ² , preferably 5 to 250 g / m
² , more preferably about 10 to 100 g / m ² .

[0028]

Since the composition of the present invention contains CMA and CA in a specific ratio, it is useful as an antifreezing agent or an antislip agent for suppressing slip of a traveling vehicle.
Further, by spraying on a snowy or snowy surface such as a frozen road surface, it is possible to suppress the freezing of the road surface, suppress slipping of the traveling vehicle, and shorten the braking distance. Therefore, not only can the road surface be prevented from freezing in cold regions, but also by freezing or spraying on an icy surface, slipping of a traveling vehicle can be prevented, and traffic congestion and traffic accidents can be reduced. In the method of the present invention, the CMA and CA in a simple operation of that match mixed at a specific ratio, the above such composition can be efficiently produced.

[0029]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Examples 1-5 and Comparative Examples 1-3 Calcium magnesium acetate (CMA) double salt (Ca: M
g weight ratio = 1: 1, element molar ratio = 1: 1.7) 100
With respect to parts by weight, the following ratio of magnesium acetate (M
A) or calcium acetate (CA) was mixed to prepare a cryoprotectant composition. In Comparative Example 1, the antifreezing agent composition was not sprayed on the track whose surface was covered with ice. Also,
In order to suppress the physical fluctuation of the friction coefficient, samples of any composition were used in the form of fine powder having a diameter of 0.3 mm or less.

Comparative Example 1: Without spraying the antifreeze 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 = 150/100 (parts by weight) Example 4: CA / CMA = 200 / 100 (parts by weight) Example 5: CA / CMA = 250/100 (parts by weight) Then, the surface is iced under air temperature of -7 ° C to -8 ° C, ice surface temperature of -8 ° C, and cloudy weather conditions. On the covered asphalt pavement (9 runways each having a length of about 50 m and a width of about 5 m), the composition prepared in the comparative example and the example was sprayed at a rate of about 50 g / m ^2.
After spraying the sample on the ice surface for 20 minutes, the test vehicle (FF normal car, weight approximately 12
(00 kg) made 10 round trips on the runway. In addition, in the test of Comparative Example 1, the test vehicle was used to test the runway without spraying the sample.
I made 0 round trips. The test vehicle is approached at a speed of 30 km /
The braking distance was measured as the distance from when the vehicle entered the running road at 40 km / hr and after sudden braking to lock the tires until the vehicle stopped completely. The results are shown in the table and figure.

[0032]

[Table 1] As is clear from the table and the figure, the CM compared to Comparative Example 1
Although the braking distance is shortened by spraying A (Comparative Example 3), the braking distance is increased by using CMA (Comparative Example 2) containing MA. On the other hand, when the composition of the example in which CA is added in a specific ratio, the braking distance of the traveling vehicle can be shortened.

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09K 3/00 102

Claims (5)

(57) [Claims] 1. An antifreeze composition comprising 20 to 250 parts by weight of calcium acetate based on 100 parts by weight of calcium magnesium acetate. 2. The antifreezing agent composition according to claim 1, wherein the proportion of calcium acetate is 50 to 250 parts by weight with respect to 100 parts by weight of calcium magnesium acetate. 3. A composition containing calcium magnesium acetate and calcium acetate for suppressing slippage on snow or ice, wherein the proportion of calcium acetate is 70 parts by weight with respect to 100 parts by weight of calcium magnesium acetate. ~ 2
20 parts by weight of anti-slip agent composition. 4. A method for suppressing slippage of a traveling vehicle by spraying a composition containing 20 to 250 parts by weight of calcium acetate with respect to 100 parts by weight of calcium magnesium acetate on a snow surface or an ice surface. 5. A method for producing an antifreeze composition, which comprises mixing 20 to 250 parts by weight of calcium acetate with 100 parts by weight of calcium magnesium acetate.