JP2000204343A - Antifreezing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifreezing agent composition having high anticorrosion property capable of suppressing the slipping of a vehicle by spraying it on ice surface, snow surface or the like. SOLUTION: This antifreezing agent composition is composed of the first antifreezing agent consisting of a succinic acid salt containing a calcium component and a magnesium component at a ratio of calcium/magnesium = (0.6/1) to (3/1) (molar ratio) and the second antifreezing agent selected from alkali metal succinic acid salts and halides of an alkali metal or alkaline earth metal. The ratio of the first antifreezing agent to the second antifreezing agent is the former/the latter = (50/50) to (95/5) (weight ratio). The first antifreezing agent contains acetic acid calcium/magnesium salt, and the second antifreezing agent is sodium acetate, potassium acetate, sodium chloride, potassium chloride, calcium chloride or magnesium chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifreeze composition capable of suppressing vehicle slippage by spraying on ice or snow.

[0002]

2. Description of the Related Art Alkali metal chlorides and alkalis such as sodium chloride and calcium chloride have conventionally been used as deicing agents (snow-melting agents) on roads (expressways, industrial roads, etc.), sidewalks, bridges, airport runways and the like. Earth metal chlorides are used.

However, since such chlorides are corrosive, they can be used for various protective fences, bridge members, buildings, automobiles,
There is a risk of corroding aircraft and the like. Further, although these chlorides have a quick effect, they are not persistent and cannot maintain the antifreezing property for a long period of time.

Accordingly, calcium magnesium acetate (hereinafter, referred to as a water-freezing agent) having a low corrosive property is known as a water-freezing agent.
(Sometimes referred to as CMA). CMA
Is a report of the Bjorksten Research Laboratory (BRL), "Alternative Highway Deicing Chemicals", 1980, supported by the Federal Highway Administration in the United States.
Mach "has been recognized as an excellent deicing agent. Also, Recent Research on Alternative Deicers
at Chevron, p75-83, TRANSPORTATION RESEARCHRECO
RD 1347 (1992) describes that CMA inhibits metal corrosion because it forms a passivation.

[0005] Regarding CMA, for example, Japanese Patent No. 25075
In Japanese Patent Publication No. 04, CMA having a calcium / magnesium ratio of 3/7 to 4/6 (molar ratio) is produced by mixing dolomite lime, acetic acid and water in a slurry state. Japanese Patent Application Laid-Open No. 9-40935 discloses calcium / magnesium = 1/1 to 3/1 as an antifreezing agent.
A mixture of CMA and calcium acetate (molar ratio) is disclosed.

In Japanese Patent Application Laid-Open No. 9-208955, a CMA composition is produced by mixing calcined dolomite, acetic acid, and, if necessary, quicklime (calcium oxide) or slaked lime (calcium hydroxide). In addition, calcined dolomite and quicklime or slaked lime, the ratio of calcium and magnesium is calcium / magnesium = 1/1 to 1
They are combined so as to be 3/1 (molar ratio).

However, these CMAs and compositions of CMA and calcium acetate are more expensive and economically disadvantageous than conventional alkali metal chlorides and alkaline earth metal chlorides.

On the other hand, a technical information catalog of the CMA anti-icing agent of Cryotech (CRYOTECH CMA DEICER TECHNICAL INF)
ORMATION, CRYOTECH Deicing Technology) discloses that adding CMA to a conventional salt (antifreeze) reduces the corrosiveness of the salt. For example, salt and CM
Assuming that the proportion of CMA in the mixture of A is 20 to 90%,
It is disclosed that the corrosiveness of the salt can be suppressed by about 70 to 80%. However, in the ratio between the salt and CMA, about 20 to 30% of corrosiveness still remains, and the anticorrosion property is insufficient. Further, when the corrosiveness is reduced to 10% or less, the ratio of CMA must be set to about 100%, which is economically disadvantageous. Furthermore, the braking ability against the vehicle passing through the melting ice surface is also insufficient.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antifreeze composition having high anticorrosion properties.

It is another object of the present invention to provide an antifreeze composition having both quick action and long lasting properties. Still another object of the present invention is to provide an antifreeze composition having high damping properties.

[0011]

Means for Solving the Problems As a result of extensive studies to achieve the above object, the present inventor has found that an acetate containing a calcium component and a magnesium component at a predetermined ratio is used as a first antifreezing agent. Combining the first antifreeze with a second antifreeze, such as an alkali metal acetate, an alkali metal or alkaline earth metal halide, can reduce the corrosiveness of the second antifreeze, and The present inventors have found that an antifreeze composition having high antifreeze properties can be obtained and completed the present invention.

That is, the antifreeze composition of the present invention comprises:
A first antifreeze composed of an acetate containing a calcium component and a magnesium component, and a second antifreeze selected from an alkali metal acetate and a halide of an alkali metal or an alkaline earth metal. The ratio of the calcium component and the magnesium component in the first antifreeze is calcium / magnesium = 0.6 / 1 to 3/1 (molar ratio). Also, the first
The ratio of the antifreezing agent to the second antifreezing agent is the former / the latter = 50/50 to 95/5 (weight ratio). The first antifreeze comprises calcium magnesium acetate. The second cryoprotectant can be selected from sodium acetate, potassium acetate, sodium chloride, potassium chloride, calcium chloride and magnesium chloride.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION [First Antifreeze Agent] The acetate constituting the first antifreeze agent has a calcium / magnesium ratio of calcium / magnesium = 0.
About 6/1 to 3/1 (molar ratio), preferably 1/1 to 3
/ 1 (molar ratio), more preferably 1/1 to 2.8.
Calcium Magnesium Acetate (CMA) alone may be used as long as it is about / 1 / (molar ratio), especially about 1.5 / 1 to 2.5 / 1 (molar ratio), such as CMA and calcium acetate, magnesium acetate, etc. And a mixture of magnesium acetate and calcium acetate.

Generally, the ratio of calcium to magnesium in calcium magnesium acetate (crystals such as double salts) is calcium / magnesium = 0.4 / 1 to 0.5 / 1.
(Molar ratio), and the acetate of the present invention containing a calcium component and a magnesium component has a higher calcium component ratio. Therefore, when the first anti-freezing agent is mixed with the alkali metal or alkaline earth metal halide, the conventional CMA (calcium / magnesium = 0.4 / 1 to 0.5 / 1 (molar ratio) ), The corrosiveness of a halide of an alkali metal or an alkaline earth metal can be more effectively reduced as compared with the case where CMA) is mixed. In addition, when the first antifreeze is used, the calcium component is large, the friction coefficient of the sherbet-shaped ice surface can be increased, and the braking distance of the vehicle can be shortened.

The method for producing CMA constituting the first antifreeze is not particularly limited, and a method for precipitating calcium magnesium acetate from a solution containing a calcium component, a magnesium component and acetic acid, for example, described in Japanese Patent No. 2507504 (A stoichiometric amount of 70 to 110 based on an aqueous mixture of calcium magnesium base in a calcium: magnesium ratio of 4: 6 to 3: 7 (molar ratio)).
% Of acetic acid to prepare and ripen an aqueous slurry), a method described in JP-T-5-508617 (a solution containing magnesium and acetate ions in a substantially non-aqueous solvent, A method of mixing a solution containing calcium and acetate ions in a substantially non-aqueous solvent, maintaining the mixture at an appropriate temperature to form crystalline calcium magnesium acetate, , A solution containing calcium and acetate ions, and maintaining the solution at an appropriate temperature to form crystalline calcium magnesium acetate) or a method analogous thereto.

Calcium magnesium acetate can also be produced by reacting (mixing) acetic acid with dolomite lime.
No. 6 (a method in which pulverized dolomite lime and an aqueous solution of acetic acid are introduced into a reaction vessel and the resulting wet granules are dried); Acetic acid and, if necessary, calcium components (quick lime, slaked lime, etc.) are quantitatively supplied, kneaded in a closed reaction system, and the reaction product is extruded and dried) or a method similar thereto. Can be adopted. Particularly, according to the method of kneading the calcined dolomite and acetic acid, and if necessary, the calcium component in a closed reaction system, the calcium component and the magnesium component in the acetate containing the calcium component and the magnesium component can be set in a wide range,
It is convenient.

The CMA thus obtained may be in the form of a powder, and the average particle size is, for example, 0.1 to 10 mm.
Degree, preferably about 0.3 to 7 mm, and more preferably about 0.5 to 5 mm.

[Second Antifreeze] The antifreeze composition of the present invention is characterized by a second antifreeze such as an alkali metal acetate, an alkali metal or alkaline earth metal halide, and the second antifreeze. It is in combination with one antifreezing agent. The second anti-freezing agent has a corrosive property to metals such as iron-based metals (eg, iron, iron-chromium alloy, iron-chromium-nickel alloy) and aluminum-based metals (eg, aluminum alloy). However, in the present invention, the corrosiveness of the second anti-freezing agent can be effectively reduced by using it in combination with the specific first anti-freezing agent.

Among the second antifreezes, alkali metal acetates include, for example, sodium acetate and potassium acetate, and alkali metal or alkaline earth metal halides include, for example, alkali metal chlorides. (Such as sodium chloride and potassium chloride) and chlorides of alkaline earth metals (such as calcium chloride and magnesium chloride).

In particular, as the second antifreeze, chlorides of alkali metals or alkaline earth metals (sodium chloride,
When potassium chloride, calcium chloride, magnesium chloride, and the like, particularly sodium chloride, calcium chloride, and the like, are used alone, they are highly corrosive and can be suitably used in the present invention.

The second deicing agent thus obtained may be in the form of a powder, and the average particle size is, for example, 0.1.
It is about 1 to 20 mm, preferably about 0.2 to 10 mm (for example, about 0.5 to 10 mm).

The ratio of the first antifreeze to the second antifreeze in the antifreeze composition can be selected within a range that can reduce the corrosiveness of the second antifreeze, for example, the former / the latter. =
About 50/50 to 95/5 (weight ratio), preferably 60
/ 40 to 95/5 (weight ratio), more preferably 6
0/40 to 80/20 (weight ratio).
It may be about 5 to 90/10 (weight ratio).

Further, by using a combination of the first antifreezing agent and the second antifreezing agent, the characteristics of the antifreezing agent can be improved in addition to the above-mentioned reduction in corrosiveness. That is, when the first anti-freezing agent is used alone, the anti-freezing property can be maintained for a long period of time (persistence), but after spraying the anti-freezing agent, it takes time for the snow-melting effect to appear ( Delay). On the other hand, when the second anti-freezing agent is used alone, a high snow-melting / melting effect appears from the beginning of the application of the anti-freezing agent (rapid effect), but the anti-freezing property is lost in a short period of time. First
By using a combination of the antifreezing agent and the second antifreezing agent, it is possible to obtain an antifreezing agent composition having both quick-acting and long-lasting properties.

The corrosivity of the antifreeze composition is, for example, S
Corrosion rate test using S400 (rolled steel for general structural use) (National Association of Corrosion Protection Engineers (National Assosiation)
The corrosion rate is about 0 to 0.06 mm / year, preferably about 0 to 0.04 mm / year, and more preferably about 0.03 mm / year. Also, A7075
The corrosion rate of (aluminum alloy) is, for example, 0 to
About 0.015 mm / year, preferably 0 to 0.0
About 1 mm / year, more preferably 0 to 0.00
It is about 5 mm / year. The antifreeze composition of the present invention has a high anticorrosion property comparable to that of the calcium magnesium acetate compound.

The antifreeze composition of the present invention may contain, if necessary, various additives such as friction aids (for example, inert substances such as sand, pulverized lime, vermiculite, pumice, wood flour, fruit husk, etc.). Granular material), a black substance (eg, a black colorant such as charcoal or carbon black), and the like.

The antifreeze composition can be usually used in the form of a powder, and has an average particle size of, for example, about 0.1 to 20 mm, preferably about 0.3 to 7 mm, and more preferably about 0.5 to 7 mm.
It is about 5 mm.

The antifreeze composition can be obtained by mixing the first antifreeze and the second antifreeze. The antifreezing agent composition of the present invention is useful as an antifreezing agent for preventing freezing and a snow melting agent for melting or deicing (snow melting or deicing agent) by spraying on a snow surface or an ice surface. .

[0028]

According to the present invention, an antifreeze composition having high anticorrosion properties can be obtained. Since the antifreeze composition has both quick-acting and long-lasting properties, it can maintain a high snow-melting effect over a long period of time from the beginning of spraying. Further, according to the present invention, high anti-freezing agent composition can be imparted with high braking performance.

[0029]

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

Examples 1 to 3 and Comparative Examples 1 to 5 From one end (inlet) of a column-shaped horizontally long kneader, calcined dolomite and acetic acid were respectively 20 kg / hr and 40 kg.
/ Hr. The feed was moved toward the other end (outlet) of the reaction vessel while kneading. During the kneading movement, the reaction exothermically proceeds, and CMA 44% by weight, calcium acetate 46% by weight, magnesium acetate 2% by weight, water 8%
A CMA mixture by weight (calcium component / magnesium component = 1.5 / 1 (molar ratio)) was formed. The product was discharged from the outlet and granulated (first antifreeze).

The first deicing agent and sodium chloride were mixed in the proportions shown in Table 1 to prepare a deicing agent composition. The anticorrosion properties and the quick-acting properties of the antifreeze composition were measured as follows. 1. Corrosion resistance to rolled steel for general structure (SS400) A test piece of SS400 is immersed in a 3% aqueous solution of the antifreeze composition, and air is blown into the aqueous solution at a rate of 25 ° C. at a rate of about two to three times a week. For 500 hours. The corrosion rate of SS400 was calculated by the following equation.

Corrosion rate (mm / year) = (8760)
0 × ΔW) / (A × t × d) (where, ΔW is the weight loss (g) of the test piece, A is the surface area (cm ² ) of the test piece, and t is the test time (h).
r) and d indicates the density (g / cm ³ ) of the test piece.) Corrosion resistance to aluminum alloy (A7075) Measurement was performed in the same manner as above using A7075, except that the test piece was changed to SS400. 3. Immediate effect 60 g of ion-exchanged water was added to a petri dish (8.5 cm in diameter, 1.7 cm in thickness) and frozen by slow freezing. 2.0 g of antifreeze composition was added, and the mixture was added at -5 ° C or -10 ° C.
Amount of water melted after standing for 6 hours or 6 hours (amount of molten water)
(G) was measured.

The results are shown in Table 1.

[0034]

[Table 1]

As is clear from Table 1, the antifreeze compositions of the examples have high anticorrosion properties against both SS400 and A7075, and also have immediate effect.

Claims (7)

[Claims] 1. A first antifreeze comprising an acetate containing a calcium component and a magnesium component, and a second antifreeze selected from an alkali metal acetate and an alkali metal or alkaline earth metal halide. And a ratio of the calcium component and the magnesium component in the first antifreeze is calcium / magnesium = 0.6 / 1 to 3/1 (molar ratio). An antifreeze composition. 2. The method according to claim 1, wherein the ratio of the calcium component to the magnesium component is calcium / magnesium = 1/1 to 3/1.
The antifreeze composition according to claim 1, which is (molar ratio). 3. The antifreeze composition according to claim 1, wherein the ratio of the first antifreeze to the second antifreeze is the former / the latter = 50/50 to 95/5 (weight ratio). . 4. The antifreeze composition according to claim 1, wherein the ratio of the first antifreeze to the second antifreeze is the former / the latter = 60/40 to 95/5 (weight ratio). . 5. The antifreeze composition according to claim 1, wherein the first antifreeze comprises at least calcium magnesium acetate. 6. The method according to claim 1, wherein the second cryoprotectant is sodium acetate,
The antifreeze composition according to claim 1, which is at least one selected from potassium acetate, sodium chloride, potassium chloride, calcium chloride and magnesium chloride. 7. A cryoprotectant composition comprising a first cryoprotectant containing at least calcium magnesium acetate and a second cryoprotectant containing sodium chloride and / or calcium chloride, wherein the first cryoprotectant comprises: The ratio of the calcium component and the magnesium component in the antifreezing agent is calcium / magnesium = 1.5 / 1 to 2.5 / 1 (molar ratio), and the first antifreezing agent and the second antifreezing agent The antifreeze composition according to claim 1, wherein the ratio with the agent is 60/40 to 80/20 (weight ratio).