JPS6337151B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides protection to the surfaces of solid objects such as metals such as iron, copper, and alloys, resins such as synthetic resins, and glass (hereinafter referred to as solid surfaces) for the purpose of preventing moisture from freezing on the surfaces. The present invention relates to a composition for forming a layer (hereinafter referred to as an antifreeze agent), that is, an antifreeze agent. Conventionally, there is no anti-freezing agent as used in the present invention, and water frozen on solid surfaces, such as frost and ice, can be removed using an alcohol-based deicing agent (deicing agent).
However, it is extremely difficult to completely thaw a frozen surface (frozen surface) using an ice-breaker. In addition, glycerin, polyethylene glycol,
Ethylene glycol, lower alcohol, higher alcohol, liquid paraffin, silicone oil, non-drying oil, etc. alone or simply mixed together, or by applying these alone or a mixture of these and water in advance to the solid surface. It is conceivable that it could be used as an antifreeze agent, but in this case, the water-soluble components of these components would be washed away by moisture such as night fog, and as a result, the composition of the applied agent would change completely or remain. It does not perform well as an antifreeze agent. In addition, water-insoluble components whose specific gravity is lighter than water replace water on the solid surface due to displacement action, causing the water to adhere unevenly to the solid surface and partially freeze. . Once frozen, it cannot be easily removed using normal removal methods. Furthermore, the components applied to the solid surface remain on the solid surface even after removal depending on the usual removal method, and the solid object on the solid surface is transparent or similar, usually in the form of a plate. (hereinafter referred to as a transparent solid), it causes diffused reflection and extremely poor transmittance. In view of the above-mentioned drawbacks, the present inventors have conducted extensive research and found that the use of cross-linked polyacrylic acid or its salt not only eliminates all of the above-mentioned drawbacks, but also provides an extremely excellent antifreeze agent. The invention was completed. That is, the present invention is an antifreeze agent containing crosslinked polyacrylic acid or a salt thereof and at least one compound selected from monohydric alcohols, polyhydric alcohols, and ether alcohols, or these and water. The crosslinked polyacrylic acid or its salt according to the present invention is composed of acrylic acid or methacrylic acid, or a mixture thereof, and a polyunsaturated compound having a plurality of polymerizable unsaturated terminal groups, or these and two types thereof. and at least one other monoolefinic unsaturated monomer copolymerizable with the monomer of About 50% by weight, a polyunsaturated compound having a plurality of polymerizable unsaturated end groups is usually used in a small amount, for example about 0.1 to 5% by weight, and usually in the presence of a solvent as necessary, azo type, peroxide type, etc. It is made by polymerizing by a known polymerization method in the presence of a polymerization initiator such as a redox type, or by adding a base to the obtained polymer to form a salt, and is a polyunsaturated compound having multiple polymerizable unsaturated terminal groups. Examples of compounds include hydrocarbons with a large number of unsaturated bonds such as divinylbenzene and divinylnaphthalene, low molecular weight (dissolved) hydrocarbons such as polybutadiene and other acyclic aliphatic conjugated diene polymers polymerized dienes, ethylene glycol diacrylate, ethylene glycol dimethacrylate, glyceryl di- and tri-acrylate, allyl acrylate, meta-allyl methacrylate,
Crotyl acrylate, allyl cinnamate,
diallyl oxalate diallyl phthalate,
monoallyl maleate diallyl maleate,
Di- and polyunsaturated esters such as diallyl malonate, diallyl allyl malonate, di- and tri-allyl citrate and other substances: α-β
-isopropylidenepropionic acid, α-β-(2
- propene) propionic acid and other polyunsaturated acids,
acrylic anhydride, methacrylic anhydride and other polyunsaturated acid anhydrides, divinyl ether, diallyl ether, dimethallyl ether, diallyl ethylene glycol ether, diallyl diethylene glycol ether, diallyl and triallyl glycerol ether, diallyl-
1,2-bropanediol ether, diallyl-3-butene-1,2-diol ether, 1-
diallyl and triallyl ethers of phenyl-1,2,3-propanetriol, diallyl-1,5-naphthalene dimethylol ether, di-tri- and tetra-allyl-1,4,5,8
- 2 to 7 or more per molecule made from polyhydric alcohols such as carbohydrates and so-called sugar alcohols, including naphthalene tetrol ether, erythritol, pentaerythritol, arabitol, iodetol, mannitol, sorbitol, inositol, ruffinose, glucose, sucrose, etc. Polyunsaturated ethers such as vinyl, allyl, meta-allyl and crotyl polyethers containing alkenyl ether groups, divinyl ketones, diallyl ketones (di-2-propenyl ketones) and other polyunsaturated ketones and half-ethers, i.e. allyl-β - Partial allyl ethers of polyhydric alcohols such as allyloxypropionate and allylmethacrylic sucrose, half esters i.e. monoallyl maleate triallyl pentaerythritol ether, sulfur such as hexaallyl trimethylene trisulfone containing compounds and other polyunsaturated compounds containing one or more functional groups, including triallyl phosphate, diallyl monohydrogen phosphate, dimethallyl monohydrogen phosphate, diallyl monomethyl phosphate, diallyl monophenyl phosphate, diallyl mono(4- ethyl phenyl) phosphate, diallyl monobenzyl phosphate and the corresponding phosphites, allyl phosphates and phosphites, triallyl phosphates and triallyl phosphites, acrylic acid or methacrylic acid or mixtures thereof, and Examples of at least one other monoolefinic unsaturated monomer that can be copolymerized with the two monomers of the polyunsaturated compound having two polymerizable unsaturated end groups include methacrylic acid, acrylic acid, etc. acids, α,β-unsaturated carboxylic acids such as chloroacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-
Tert-butyl acrylamide, styrene, ethylene, isobutylene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, methyl methacrylate, methyl ethacrylate, vinyl acetate, vinyl propionate,
vinyl butyrate, isopropenyl acetate,
Isopropenyl propionate, isopropenyl butyrate, vinyl benzoate, isopropenyl benzoate, vinyl pyridine, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, methyl vinyl ketone, ethyl vinyl Examples include ketones, methyl isopropenyl ketone, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, etc., which contain acrylic acid or methacrylic acid or a mixture of these acids and a plurality of polymerizable unsaturated end groups. Various synthetic resins are currently known that are crosslinked copolymers with small amounts (e.g., about 0.5 to 2.5% by weight, based on the total copolymerization) of polyunsaturated compounds, such as those described in U.S. Pat. No. 2,798,053. describes crosslinked copolymers of acrylic or methacrylic acid with small amounts of vinyl, allyl or methallyl ethers of polyhydric alcohols having at least 4 carbon atoms and at least 3 alcoholic hydroxyl groups; The patent specification states that preferred polyalkenyl polyether monomers include polyallyl sucrose and polyallyl pentaerythritol (containing an average of at least about 3 allyl groups per molecule of sucrose or pentaerythritol, and where the allyl groups are acros or pentaerythritol, which is more preferably bonded to pentaerythritol through an ether bond), and US Pat. acrylic acid copolymers containing crosslinker monomers which are polymeric and benzene soluble products are described, the polymeric crosslinker monomers containing a large number of 1,2 structure, i.e., a plurality of CH ₂ that can be copolymerized with acrylic acid
= contains a side chain; US Pat. No. 2,958,679 describes a crosslinked copolymer of acrylic acid and polyallyl or polymethallyl trimethylene trisulfone, and US Pat. No. 2,985,631 describes a crosslinked copolymer of acrylic acid and and polyvinyl, polyallyl or polymethallylsilanes or corresponding tin compounds (preferably tetraallyl or tetravinylsilanes or tin compounds) are described. The crosslinked polyacrylic acid or its salt according to the present invention can preferably be easily obtained by polymerizing an olefinic unsaturated carboxylic acid using a crosslinking agent or from the obtained polymer and a base, Examples include, in addition to the above-mentioned examples, known crosslinked polyacrylic acids, preferably crosslinked polyacrylic acids described in Japanese Patent Publication No. 53-5711. That is, the crosslinked polyacrylic acid or its salt according to the present invention is preferably an olefinic unsaturated carboxylic acid having at least one active carbon-carbon olefinic double bond and at least Easily polymerizable acids containing one carboxyl group, in other words, the olefinic double bond is present in the α, β position relative to the carboxyl group in the monomer molecule, or as a terminal methylene group, e.g. , acrylic acid, methacrylic acid, itaconic acid, chloroacrylic acid, cyanoacrylic acid,
Crosslinking of one or a mixture of two or more selected from the group consisting of α-phenylacrylic acid, α-benzylacrylic acid, crotonic acid, maleic acid, fumaric acid, sorbic acid, and other olefinic unsaturated carboxylic acids. General formula as agent (In the formula, R represents hydrogen or a methyl group, l, m,
n represents a number satisfying 0<l+m+n≦500.
However, only when R represents hydrogen and n=0,
Exclude numbers that satisfy l+m=1. ), usually in the presence of a solvent and a polymerization initiator such as an azo type, a peroxide type, or a redox type, at a temperature of 30°C to 90°C, or by polymerizing the obtained polymer. It can be easily obtained by adding a base, such as an inorganic base such as sodium hydroxide, ammonium hydroxide, potassium hydroxide, sodium carbonate, or potassium bicarbonate, or an organic base such as triethanolamine, dodecylamine, or triethylamine, to the combination. . In order to obtain the antifreeze agent of the present invention, crosslinked polyacrylic acid or a salt thereof and an antifreeze agent known per se, such as glycerin, polyethylene glycol, ethylene glycol, lower alcohol, higher alcohol, liquid paraffin, silicone oil, non-drying oil, etc. These organic compounds may be used alone or as a mixture, or in some cases, a mixture of these and water may be mixed. The antifreeze to be mixed with these crosslinked polyacrylic acids or salts thereof is at least one compound selected from monohydric alcohols such as lower monohydric alcohols, polyhydric alcohols such as alkylene glycols, and ether alcohols such as ethylene glycol-based ether alcohols. It is preferable to use a mixture containing these and water in some cases. In addition,
The content of crosslinked polyacrylic acid or its salt is usually about 0.01 to 10% by weight of the total. Monohydric alcohols include lower monohydric alcohols such as monohydric alcohols with 1 to 5 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, and polyhydric alcohols include ethylene glycol, propylene glycol, etc. 1,2-glycol, trimethylene glycol, β-butylene glycol,
1,3-glycols such as 2-methyl-2,4-pentanediol, 1,4-glycols such as tetramethylene glycol, γ-pentylene glycol, 1,4-hexanediol, and 1,5-glycols such as pentamethylene glycol. - alkylene glycols such as glycol; other polyhydric alcohols include glycerin, 1,2,3-
Trihydric alcohols such as monoalkylglycerols such as butanetriol and 1,2,3-pentanetriol, alkylglycerols such as dialkylglycerols such as 2-methyl-2,3,4-butanetriol, erythritol, trait, and pentaerythritol. These include tetrahydric alcohols such as adonite, arabite, xyrite, pentahydric alcohols such as adonite, arabite, xyrite, hexahydric alcohols such as aritto, talitz, sorbit, mannitrate, ixite, dulcitrate, heptite, octite, nonite, descitt, etc. Ether alcohols include ethylene. Ethylene glycol monoalkyl ethers such as glycol monomethyl ether and ethylene glycol monoethyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol, diethylene glycol monomethyl ether and diethylene glycol monoethyl alcohol; ethylene glycol-based ether alcohols such as triethylene glycol; glycerin-1
-Methyl ether, glycerin-2-methyl ether, glycerin-1-ethyl ether, glycerin-1-propyl ether, glycerin-1-
Isoamyl ether, glycerin-1,2-dimethyl ether, glycerin-1,3-dimethyl ether, glycerin-1,3-diethyl ether, glycerin-1-ethyl-2-propyl ether, 1,2-methyleneglycerin, 1,3- methylene glycerin, such as methylene glycerin,
ethylidene glycerin such as 1,2-ethylidene glycerin and 1,3-ethylidene glycerin;
1,2-isopropylidene glycerin, 1,3-
Examples include glycerin-based ether alcohols such as isopropylidene glycerin such as isopropylidene glycerin, and glycerin acetals and ketals such as benzylidene glycerin such as 1,2-benzylidene glycerin and 1,3-benzylidene glycerin. The crosslinked polyacrylic acid according to the present invention is usually used as its salt, and its pH
Examples of basic compounds used to adjust the pH are:
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, basic inorganic compounds such as ammonia and hydrazine, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, isopropylamine, diisopropylamine, n-butylamine, n -dibutylamine, n-tributylamine, isobutylamine, diisobutylamine, sec-butylamine, n-amylamine, diamylamine, triamylamine, secondary amylamine, secondary hexylamine, 2-ethylbutylamine, n
-heptylamine, 2-ethylhexylamine,
Dioctylamine, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, aniline, monomethylaniline, dimethylaniline, diethylaniline, N-
Mono-n-butylaniline, N,N-di-n-butylaniline, N-monoamylaniline, P-tertiary amylaniline, N,N-diamylaniline,
N,N-ditertiary amylaniline, o-toluidine, o-chloroaniline, cyclohexylamine, dicyclohexylamine, diethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, ethylmonoethanolamine, n-butylmonoethanolamine ,
Dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, n-butyldiethanolamine, di-n-butylethanolamine, triisopropanolamine, isopropanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, phenylmorpholine, Oxazolidine, N-methyloxazolidine, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2,6-
These include basic organic compounds such as lutidine, quinoline, and isoquinoline. Note that the PH is adjusted to any acidic, neutral, or alkaline PH as necessary. The antifreeze agent of the present invention is extremely excellent as an antifreeze agent, as described below. (1) A protective layer for freezing prevention, usually in the form of a film, can be easily formed, and the formed protective film (hereinafter referred to as the "protective film") remains uniform for a long time. Retained. That is, it can be said that there is virtually no change in the thickness or composition of the protective film, and there is no flow or sagging when the solid surface is vertical. It also has good water resistance and wind resistance, and good adhesion to solid surfaces. (2) The antifreeze effect of the protective layer is effectively maintained even at extremely low temperatures. In other words, moisture such as frost and ice does not freeze on the solid surface even under natural conditions at temperatures below -10°C. Moreover, the smoothness of the protective film is also good. (3) The protective layer can be easily removed from the solid surface by a normal removal method if necessary, and when protecting the surface of a transparent solid, the transparency of the transparent solid after removal must also be maintained. It is very good and does not cause diffused reflection. (4) Highly safe for humans. (5) The solid surfaces to be protected for the purpose of freezing prevention are not particularly limited, and are wide-ranging and have an extremely wide range of applications. That is, the solid may be of any type, such as metal, glass, or resin. (6) The antifreeze agent of the present invention can be used not only in railways, aviation, and ships, but also in hotels, household goods, etc., and can be used in an extremely wide range of fields. Useful. (7) The antifreeze agent of the present invention exhibits particularly excellent effects when used in transparent solid materials such as automobile windshields to ensure visibility of vehicles such as trains, aircraft, ships, and automobiles. do. That is, for example, if the antifreeze agent of the present invention is applied in advance to the windshield of a passenger car, etc.,
Even if the vehicle is parked outdoors for long periods of time during the winter or frost season, atmospheric moisture such as night fog will not freeze on the windshield surface, and it can be easily removed using normal methods such as wiper operation. Not only can it be removed, there is no chemical residue on the windshield after removal, so it has good visibility, and even when it is hit by the lights of an oncoming car, it does not reflect diffusely, ensuring an extremely good visibility through the windshield. Drivers can drive safely. In order to form a protective layer on a solid surface using the antifreeze agent of the present invention, the antifreeze agent is usually applied to the solid surface. It is preferable that the antifreeze agent of the present invention is used as a spray (aerosol) type by being sealed together with a propellant in a closed container. When the antifreeze agent of the present invention is often used in winter or outdoors, it is required to be applied quickly and uniformly to provide antifreeze effect in a short period of time. However, the composition providing the antifreeze agent of the present invention can be applied onto a solid surface such as a windshield by brushing, brushing, cloth, dripping, etc., but it is not easy to apply it uniformly. However, it is necessary to prepare and manage application tools. By aerosolizing the antifreeze agent of the present invention, all of the above-mentioned drawbacks are eliminated, and anyone can easily and uniformly apply the antifreeze agent. Therefore, we considered various conditions for aerosol such as can rust, rubber gaskets, and resin parts, and further,
By selecting the propellant used, a stable aerosol position was achieved. In addition, the antifreeze agent of the present invention exhibits extremely excellent effects even when used as it is as an ice melting agent (deicing agent) or an oil film removing agent. That is, when the antifreeze agent of the present invention is used for these purposes, it is extremely effective in removing oil from the solid surface, such as organic compounds (e.g., alcoholic solvents) contained in the deicing agent. Since it can be completely removed, for example, when used to thaw water frozen on the surface of a transparent solid, the transparent solid after removal has extremely good transparency and no diffused reflection occurs. Examples are shown below. Example 1 200 parts of methanol, 100 parts of ethylene glycol,
Mix and dissolve 150 parts of propylene glycol, add 2 parts of cross-linked polyacrylic acid resin (Hibis Wako 103, manufactured by Wako Pure Chemical Industries, Ltd.), stir thoroughly with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and then add 2 parts of triethylamine. In addition, a homogeneous and thick stock solution was obtained. The viscosity of the obtained stock solution was determined to be 14,000 cps using a Bruckfield rotational viscometer at 20 rpm. Example 2 In the same manner as in Example 1, 1 part of Hiviswako 105 (crosslinked polyacrylic acid resin manufactured by Wako Pure Chemical Industries, Ltd.) was added to a homogeneous solution of 100 parts of ethanol, 200 parts of ethylene glycol, and 150 parts of hexylene glycol, and laurylamine was added. Neutralization was performed with 3 parts to obtain a concentrated stock solution with a viscosity of 6900 cps. Example 3 Similarly to Example 1, Carbopol was added to a homogeneous solution of 150 parts of ethanol and 100 parts each of ethylene glycol, diethylene glycol, and hexylene glycol.
Add 3 parts of 934 (cross-linked polyacrylic acid resin manufactured by Gutudoritsu, USA) and neutralize with 3 parts of morpholine to reduce the viscosity.
A concentrated stock solution of 7300 cps was obtained. Example 4 Same as Example 1, add Carbopol 940 to 150 parts each of methanol, ethanol, and propylene glycol.
Add 2 parts of cross-linked polyacrylic acid resin (manufactured by Gutudoritsu, USA) and neutralize with 2 parts of morpholine to reduce the viscosity.
A concentrated stock solution of 12500 cps was obtained. Example 5 In the same manner as in Example 1, 250 parts of methanol, 50 parts of ethylene glycol, 100 parts of hexylene glycol, 4.5 parts of Hiviswako 105 (crosslinked polyacrylic acid resin manufactured by Wako Pure Chemical Industries, Ltd.) were added to 50 parts of water, and a homomixer was added. After thorough stirring, 18 parts of 10% sodium hydroxide solution was added to neutralize the mixture to obtain a concentrated stock solution with a pH of 7.5 and a viscosity of 9800 cps. Example 6 As in Example 1, 200 parts of ethanol, 50 parts of propylene glycol, 50 parts of diethylene glycol,
Add 3 parts of Hibis Wako 104 (crosslinked polyacrylic acid resin manufactured by Wako Pure Chemical Industries, Ltd.) to 50 parts of hexylene glycol and 100 parts of water and neutralize with 3.5 parts of triethylamine to obtain a concentrated stock solution with a pH of 7.8 and a viscosity of 7200 cps. I got it. Example 7 Same as Example 1, 100 parts of ethanol, 50 parts of ethylene glycol, 30 parts of propylene glycol, 120 parts of diethylene glycol, 2-methyl-2,3,
To 50 parts of 4-butanetriol and 100 parts of water, 4.5 parts of Hibis Wako 103 (crosslinked polyacrylic acid resin manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 7 parts of triethanolamine was added.
A concentrated stock solution with pH 8.3 and viscosity 11,500 cps was obtained. Example 8 The concentrated stock solutions obtained in Examples 1 to 7 were filled into aerosol cans, and then various propellants were filled in a conventional manner to prepare aerosol compositions. This is sprayed onto the windshield of a car and left outdoors at night in the cold (minimum temperature -12°C). Table 1 shows the results of comparing the transparency of the glass after wiping.

[Table] The undiluted solution was evenly applied to the areas coated with this antifreeze agent, and a film was formed even after being left overnight, and no frost adhesion (freezing) was observed. The wipeability was good and the visibility of the windshield after wiping was also good. Frost adhered to the entire surface of the area to which this antifreeze agent was not applied, and it was difficult to wipe it off with a wiper or scrape it off with a piece of plastic. Furthermore, "Hibis Wako" is a registered trademark of Wako Pure Chemical Industries, Ltd. Comparative example: 200 parts of methanol, 100 parts of ethylene glycol,
A homogeneous solution of 150 parts of propylene glycol60
After filling an aerosol can with 40 parts of chlorofluorocarbon gas, an aerosol composition liquid was prepared and applied to the windshield of a car in the same manner as in Example 8 to examine the anti-freezing effect. As with the areas to which no composition was applied, frost adhered to the entire surface, and it was difficult to wipe it off with a wiper or scrape it off with a piece of plastic. Experimental example 1 100ml of the antifreeze stock solution used in Example 5 was added to 200ml
The mixture was placed in a beaker and 50 ml of distilled water was slowly layered on top of it, taking care not to disturb the interface. After leaving it at room temperature for 20 hours, the height of the resulting mixed layer of the antifreeze stock solution and distilled water (the layer that appears cloudy) was measured. For comparison, a commercially available linear polyacrylic acid (average molecular weight: 90,000) was used in place of Hivis Wako 105 in Example 5, and the other conditions were as follows.
The same operations as above were performed using the same reagents as in Example 5 and those prepared by the same operations. As a result, when using the cross-linked polyacrylic acid according to the present invention, the mixed layer formed was about 7% of the total (undiluted solution layer + mixed layer + water layer), but when using the linear polyacrylic acid, If used, 33-35%
A mixed layer of . As is clear from this, antifreeze agents prepared using cross-linked polyacrylic acid have stronger thixotropic properties than those prepared using linear polyacrylic acid, and are easily soluble in water. It turns out that they are not miscible. Experimental Example 2 An appropriate amount of the antifreeze stock solution used in Example 6 was spread on a glass plate to form a 10 cm ² gel plate with a thickness of 1.5 mm. The glass plate was tilted at 50°, and water in an amount three times the weight of the gel was sprayed onto the gel plate in the form of a mist to avoid irritating the gel plate. After that, the glass plate was left to stand for 5 minutes.
The residual rate of gel on the glass plate was determined. For comparison, commercially available linear polyacrylic acid (average molecular weight: 90,000) was used in place of Hiviswako 104 in Example 6, and the other
The same operations as those described above were performed using the same reagents as in Example 6 and those prepared by the same operations. As a result, when the cross-linked polyacrylic acid according to the present invention was used, the gel residual rate was 75 to 85%, but when linear polyacrylic acid was used, it was 15 to 25%. The gel residual rate was high. As is clear from this, antifreeze agents prepared using cross-linked polyacrylic acid have stronger thixotropic properties and are more water resistant than those prepared using linear polyacrylic acid. I understand that.

Claims (1)

[Scope of Claims] 1. An antifreeze agent containing crosslinked polyacrylic acid or a salt thereof and at least one compound selected from monohydric alcohols, polyhydric alcohols, and ether alcohols, or these and water. 2. The antifreeze agent according to claim 1, which is sealed in a closed container together with a propellant to form a spray (aerosol) type.