JPS6289788A - Anti-freeze - Google Patents

Abstract

PURPOSE:To provide an anti-freeze of specified pH value, for use in motor vehicle engines, etc., consisting mainly of glycol and water, also containing phosphoric acid salt, aromatic polybasic acid, molybdic acis salt, corrosionproof agent and specific copolymer. CONSTITUTION:The objective anti-freeze with a pH 6.5-9 consisting mainly of glycol and water, also containing (A) a phosphoric acid, (B) an aromatic polybasic acid (e.g., phthalic acid), (C) a molybdic acid salt (e.g., sodium molybdate) or tungstic acid salt (e.g., potassium tungstate), (D) a corrosionproof agent (e.g., sodium mercaptobenzothiazole), (E) a copolymer derived from (i) polyalkylene glycol monoaryl ether of formula I (m and n are each 0 or positive integer, m+n=1-100) and (ii) a maleic acid monomer of formula II [X and Y are each (C2H4O)p(C3H6O)qR3 (R3 is H or 1-20C alkyl; p and q are each 0 or positive integer, P+Q=0-100), monovalent metal, divalent metal, ammonium or organic amine].

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antifreeze solution comprising glycols, water and a 11g food suppressant used to prevent freezing of cold 7Jl water of a liquid-cooled internal combustion engine. For more details, see the cold 7 of the car engine.
As a JI liquid, it relates to an antifreeze liquid that is effective in not only preventing freezing, but also preventing rust and preventing cold 11 systems of automatic engines.

(Conventional 1 branch i)) Conventionally, liquid-cooled internal combustion engines, such as the cold f
JL liquid is an antifreeze solution that uses alcohol or glycol as its main ingredient to prevent freezing, and various corrosion inhibitors are added to it to provide both antifreeze and anticorrosion properties.

(Problems to be solved by the invention) Commonly used alcohols include methyl alcohol, nibble alcohol, isopropyl alcohol, etc., and glycols include ethylene glycol, propylene glycol, hexylene glycol, glycerin, etc. Or they are used in combination. Among these, an antifreeze solution containing heptanoethylene glycol as a main ingredient is particularly used as the cold U1 liquid in the cold N1 system of automobile engines.

In the case of 7-ethylene glycol aqueous solution, -
At 15.5°C and 50% suspension, the antifreeze effect up to -37.0°C is 1q.

Alcohols or glycols are oxidized by contact with air, producing acidic alcohol or glycol oxides. The high temperature condition r of 50 to 100° C. further promotes the production of oxides of alcohols or glycols. These acidic alcohols or glycols significantly accelerate the corrosion of various metals constituting the cooling system of an internal combustion engine, especially an automobile engine.

Consumption of various metals constituting the cooling 1.11 system of an internal combustion engine causes a low thermal conductivity due to deposition of corrosion products or blockage of the radiator pipe, causing engine A'-bar heat.

Antifreeze solutions whose main ingredients are alcohols or glycols (11g of anti-corrosion agent are added because alcohols or glycols have no anti-corrosion effect).

As anticorrosive agents, borax, sodium nitrate, phosphoric acid, silicate, sodium benzoate, mercaptobencibuazole thorium salt, benzotriazole, methylbenzotriazole, triethanolamine, jetanolamine, monoethanolamine, At least one member selected from triisopropanolamine, diisopropanolamine, noisobrobanolamine, cyclohexylamine, ethylenediamine, hydrazine, pyridine, morpholine, etc. is added. Typical examples of these include sand, tostanolamine phosphate, sodium benzoate, sodium nitrite, and sodium silicate. Borax has been widely used as an effective anti-corrosion agent for cast iron engines, but in recent years, aluminum parts have been adopted to reduce the weight of 1j + width parts in order to conserve resources and energy. The problem has been that it has some shortcomings.

When an ethylene glycol aqueous solution containing borax is used in the cold IJI system of an automobile engine, it corrodes the aluminum alloy that is the material of the engine's cylinder head and cylinder block, and the corrosion products can clog the radiator. It has been known.

On the other hand, triethanolamine phosphate has excellent corrosion resistance against iron-based and aluminum materials, and is used as an anticorrosion agent in place of borax. It has been reported that the coexistence of amines and Tsukudani M salt should be avoided. In addition, sodium benzoate cannot be expected to be effective enough to replace these anticorrosive agents with Qi alone.

On the other hand, sodium silicate is also effective as a corrosion inhibitor, but there is a problem in that sodium silicate tends to gel and separate during long-term storage.

That is, an object of the present invention is to provide an antifreeze solution that is a composition that does not contain amines and has particularly excellent aluminum corrosion resistance. As a result of intensive investigation, Mizuben Akashi et al. found that (A) phosphoric acids, (B) aromatic polybasic acids, (C) molybdates or tungstates, (
D) Corrosion inhibitor and (E) General formula (1), CH2= CII ■ ...(1)C
II O(C,, 1140), (C3I+601゜■ (wherein m and n are O or positive integers from mtn-1 to 100, and (C2++4o) Di position (
It may be combined with position C21140JIt in any order. ) Polyalether glycol monoallylic ester (1) represented by the general formula (1), R1R2 CC...■ CO2X C02Y [wherein R and R2 each represent hydrogen or a methyl group, and X and Y are Each (C,,
I+40), (C31160), R3 (However, R
3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, p and q are O or a positive integer, and p+q=o to 100
(02■40) intermediate (C3I+601 units may be bonded in any order), and represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. Maleic acid system shown by 1! 11-mer (If) and/or FJi lfi-form (I [[)
The object of the present invention can be achieved by containing a copolymer derived from the following and having a pH in the range of 6.5 to 9.0.

(Means for Solving the Problems) The present invention provides an antifreeze solution consisting of glycols and water.
(A) Phosphoric acid, (13) Fragrance? Fj family polysalt! , X acids, (C) molybdenum M salt or tungstate, (D) anticorrosion agent, and (E) general formula (1), C11,, = C11 I
...(1)C11,,O(C21140)IIl(C
31160). 11 (However, in the formula, mJ3 and n are O or a positive integer, m) n = 1 - 100, and is expressed as (C2I + 401 units (can be bonded to the C211401In position in any order) Boreal-1-rangelicol monoallyl ether (I>, general formula 〇, R1R2 CC...■ CO2X CO2Y [However, in the formula 1, J and R2 each represent a water thread or a methyl group, and Y is (C2I+
401. (C311601, R3 (However, R3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, p and q are O or an integer of 11, p+q=o to 100, and (C110) unit and ( Maleic acid monomer (■ ) and/or a copolymer derived from a hollow body (I[I) which can be co-formed with these, and has a pH in the range of 6.5 to 9.0 ( This is Kerurano Seki.

The phosphoric acids of the present invention include phosphoric acids and salts thereof. In addition to orthophosphoric acid, first to tertiary salts of alkali metals such as lithium, sodium, and potassium can be used. The amount added is 0.1 to 5.0 to the undiluted antifreeze solution.
Weight%, preferably 0.5 to 3.0 pieces%.

As the aromatic polybasic acids of the present invention, benzene polycarboxyl L4-substituted products such as phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, and pyromellitic acid can be used. Moreover, salts of these aromatic polybasic acids can also be used. The amount of aromatic polybasic acids added is 0.05 to 1.0% by weight, preferably 0.1 to 0.5% by weight.

As the molybdate J3 and tungstate of the present invention, alkali metal salts such as sodium salts and potassium salts are used. The amount of heptalybdenum M salt and tungstate to be added is 0.05 to 1.0% by weight, preferably 0.1 to 0.5% by weight, based on the antifreeze liquid.

The anticorrosive agent of the present invention is at least selected from sulfites, nitrates, silica M salts, vanadate vanadate, sodium benzoate, p-tajarybdel sodium benzoate, mercaptobenzothiazole sodium triazole, benzotriazole, etc. It is used with the addition of one type of mucilage. Among these, the most representative one is Nitsu 1! i! i salt, sodium mercaptobenzothiazole, methylbenzotriazole, and sodium benzoate. The amount of anticorrosive added is 0.05 to 5.0 to the undiluted antifreeze solution.

0 weight resistance %, preferably 0.1 to 3.0 Fn hanging %C.

The copolymer of the present invention is polyalkyl: 1-lengellicol monoallyl L--7ol (■〉゛, maleic acid-based M(
Copolymers derived from A(If) J3 and monomers copolymerizable with these (I[I) can be used, preferably, general formula (1), C112・C11... (1)C
I+20 (C2H40), (C3I+601.11
(1.: In the formula, m and n are O or positive integers, f■1tn-1 to 100, and LC2 114 0
The 1 center and the (C3 11e O) unit can be combined in any order. ) Polyalkylene glycol monoallylic ethyl(I) represented by the general formula 〇, R1 R2 C C ...■C02X
C○2Y [However, in the formula, RJ3J:. and R2 each represent hydrogen or a methyl group, and X and Y each represent (C21
1401, (C31160)qR, (where R3 represents hydrogen or an alkyl sphere having 1 to 20 m carbon atoms, p and q are 0 or a positive integer, and D+q=0 to 1
00, (C2+1401 units and (C3II60)
Units may be combined in any order. ), -(I
Ii represents a divalent metal, an ammonium group or an organic amine group. ] Maleic acid system 'i! It is a copolymer obtained from the ffi body (I[) and/or the upper suspension body (III) which can be copolymerized with these.

Polyalkylene glycol monoallyl ether (1) can be synthesized by a known method of directly adding ethylene oxide and/or propylene oxide to allyl alcohol using an alkali such as KOH or NaOH as a catalyst. As long as it is represented by the above general formula, either a single structure of 6 or a mixture thereof can be used.

ff1 for maleic acid (AQD is represented by the above general formula, but specifically 4, maleic acid, phthalic acid,
Citraconic acid, mesacone M, monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts of these acids, and these acids with HO (C21140).

(C31160)q R3 (wherein, R3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, and p and q are O
or a positive integer, p+q=o~100, and (CI
Alcohols represented by t 01111 (1/ and (C21140) intermediate may be bonded in any order), such as secondary flu]letho A sylate motumarate, can be preferably used. Also, one or more of these can be used.

In addition, the six substances that can be co-combined with these include acrylic acid, methacrylic acid, itaconic acid, croton la, and monovalent metal salts, divalent metal salts, and anhydrous metal salts of these acids.
salts, organic amine salts, and these acids and alcohols [[
], (meth)acrylamide,
Examples include vinyl acetate, propenyl acetate, aromatic vinyl compounds such as styrene and p-methylstyrene, and vinyl chloride, and one or more of these can be used.

The copolymer contains 24% each of polyalkylene glycol monoallyl ether (■), a maleic acid monomer (n), and/or a monomer copolymerizable with these (III).
~75 mol%, 24-75 mol% and 0-50 mol%
(However, the sum of components (I), (It) and (III) δ
1 is 100 mol%. 〉 ratio was used and was derived.

In order to produce a copolymer, the monomer components may be copolymerized using a polymerization initiator. The Jt=fi combination can be carried out by polymerization in a solvent, bulk polymerization, or the like.

Polymerization in a solvent can be carried out either batchwise or continuously, and the solvents used include water; lower alcohols such as methyl alcohol, ethyl alcohol, isobyl alcohol; benzene, toluene, xylene, Examples include aromatic or aliphatic hydrocarbons such as cyclohexane and n-he-V phosphorus; ethyl acetate; acetone and ketone compounds such as methyl 1-derketone. Raw material rim body and 1! In view of the solubility of the copolymer and the convenience before use of the copolymer, at least 1. It is preferable to use type +1. Among the lower alcohols having 1 to 4 carbon atoms, 44) methyl alcohol, ① pull alcohol, and isopropyl alcohol are particularly effective.

When polymerization is carried out in an aqueous medium, a water-soluble polymerization initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used as the polymerization initiator. At this time, an accelerator such as sodium hydrogen sulfate is used. In addition, for polymerization using lower alcohols, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ethyl acetate, or ketone compounds as solvents, benzoyl peroxy 1ζ, lauroyl peroxide, peroxide in a cellulose; cumenehyde [1 per A Hydroperoxides such as oxide; aliphatic azo compounds such as azobisisobutyronitrile, etc. are used as the 11th initiator. At this time, an accelerator such as an amine compound is added to
It's a monkey because of the things you use. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from among the above-mentioned combinations of the various Φ-coupling 1n1 initiators or Φ-coupling 1'iil initiators and accelerators. The polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but is usually O~
It is carried out within a range of 120°C.

Bulk polymerization can be carried out using peroxides such as penzoyl peroxide and lau 1''yl peroxide; hydrocarbons such as cumene hydroperoxide;
The process is carried out using an aliphatic azo compound such as azobisisobut[]21-lyl within a temperature range of 50 to 150''C.

The copolymer thus subjected to VI may be used after being further neutralized with an alkaline substance C, if necessary. Preferred examples of such alkaline substances include hydroxides, chlorides and carbonates of -valent metals and divalent metals, ammonia and organic amines.

Further, the molecule j1 of the copolymer can be used in a wide range, but it is preferably in the range of 500 to 50,000.

Polyalkylene glycol monoallyl ether (■) and maleic acid-based suspension (If) contained in the antifreeze of the present invention
and a η-form (1) /p r copolymerizable with these,
In addition to inhibiting corrosion of iron-based materials, the copolymer has an excellent anti-scaling effect. Thus, the antifreeze of the present invention overcomes the problems faced by automotive antifreeze containing phosphates.

Polyalkylene glycol monoallyl ether (■) of the present invention, maleic acid-based suspended body (H) together with these i
(The amount of polymer added is 0.01% or more with respect to the stock solution of antifreeze.)

Normal basic substances can be used to adjust the pH of antifreeze, but
Preferably, hydroxides of alkali metals such as lithium, sodium, potassium cum, etc. are used.

Acidic substances such as phosphoric acid can be used if necessary.

The adjustment range for PH is 6.5 to 9.0, preferably 7.0 to 8.0. If the pH is lower than this range, the corrosion resistance against aluminum will be inferior, and if the pH is lower than this range, the corrosion resistance against aluminum will be poor.
Since gluttony occurs, it should be adjusted within the above range.

The antifreeze of the present invention includes silicone oil, mineral oil, alcohol,
Antifoaming agents such as higher fatty acid esters can be added.

(Function) It is clear from the results of Example J3 and σ Comparative Example that the antifreeze of the present invention will be described later. In the antifreeze containing glycols and water, (△) phosphoric acids, (B) aromatic polysalts. 1. L acids, (C) Molybdenum MW or C5i tungsten MB
A, (D> anticorrosive agent and ([) General formula, CI+2= C11 1...(1) CIl O(C2I+401. (C311601n
I+ (where n in the formula is O or a positive ?l! number and is m+n-1 to 100, and the (C21140) unit and the (C31160) unit may be combined in the following order. ) Polyalkylene glycol monoallyl ether (I>, general formula 〇, 1R2 I C-C...■ CO2× C02Y [wherein R and R2 each represent hydrogen or a medyl group, and X J3 and Y are respectively (C
,,I+40) p(C31160)qR3 (1te3 is hydrogen or alkyl having 1 to 2 carbon atoms) 5, p and q are 0 or a positive integer, p+q=o to 10
0, and the (C2H40) unit and the (C311RO) intermediate may be bonded in any order. ), represents a monovalent metal, a divalent metal, an ammonium group, or a monovalent amine group. Maleic acid system shown by 1! 11 specimens (H) J3 and/
Or, since it contains a copolymer derived from copolymerizable Chihani (I) and has a pH in the range of 6.5 to 9.0, the anti-corrosion effect against aluminum is several times greater. There is C of b that is done.

As is clear from the results of Examples and Comparative Examples described below, the antifreeze solution of the present invention is composed of glycols and water, and each component is essential. If each ingredient is missing, the following problem will occur.

Medium (A> If phosphoric acids are not included, there is a problem that the corrosion resistance of aluminum and iron is poor (1 = Yes).

■ (B) If it does not contain aromatic polychlorinated acids, DH
The problem arises that the increase in aluminum cannot be suppressed, causing pitting corrosion of aluminum.

(3) (C) '[If the rib f is 1 m or does not contain tungstate, a problem arises in that the corrosion resistance of aluminum and iron is poor.

(4) (D) If no anticorrosive agent is included, there is a problem that the anticorrosive performance of the metal as a whole is poor and durability is lost.

(5) ([E) Polyalkylene glycol noallyl ether (I), maleic acid derivative (II), and a combination of these and the like! fs IA (I[I
31), there is a problem that the production of 1- from the aluminum ions and magnesium ions in the antifreeze dilution water cannot be suppressed, resulting in the adhesion of school.

(6) When the pH of the antifreeze of the present invention is outside the range of 6.5 to 9.0, if the p value exceeds 9.0, the corrosion resistance of aluminum will be poor, and if the DH value is less than 6.5, the corrosion resistance of aluminum will be poor. A problem arises in which pitching occurs.

<Examples> Next, the antifreeze solution of the present invention will be further explained in detail with reference to Comparative Example J3 and Examples, but the present invention is not limited thereto.

[A1' Metal corrosion test method [JIS-2234 (
Antifreeze)] Using metal test pieces of aluminum casting, cast iron, steel, brass, solder, and copper, mixed water (148 mg of sodium sulfate,
Sodium chloride 165mQ and hydrogen carbonate)-TriuIs
Dissolve 138 mg g in distilled water 11) to make 30
Soak in antifreeze solution diluted to 100% by volume h) and dry air to 100±
10ffii! Antifreeze I11!2 Lagoon Tsume was maintained at 88±2°C between 3361+ islands while being fed with the outflow of /win. The quality 16 of each metal piece before and after the test was measured, and the change in 71 suspension was determined.

The change in mass of each metal was determined from the following equation.

C-(m 2-m 1)/S where, c: 11g change (m g/c
ti)m1: Mass of test piece before test (mg)
m2: Mass of test piece after test (mix)S:
Total surface area of test piece before test (IJi > [B] Heat transfer surface corrosion test method (1) Apparatus The upper surface of the disk-shaped test piece is in contact with the antifreeze, the lower surface is heated with a reheater, and the test piece is heated. The test was carried out using an apparatus in which heat was transferred to the antifreeze through the antifreeze solution.

■ Test conditions Test piece: Aluminum casting (AC-4B
) Test piece temperature: 130℃ Antifreeze concentration = 30% by volume aqueous solution Antifreeze liquid suspension
" 300te Test time ° 10 hours (3) Test item Test piece Appearance test After liquid phase test Aluminum Fuchimaro in liquid 400 mj! each, and added 4 Q Q rn of tap water containing 9 ppm of calcium and 5 pDm of magnesium to this.
j! I got it. This was maintained at a temperature of 88°C in an oil bath, left undisturbed for 24 hours, and the generated scale was transferred to a sedimentation section (m
! /800m! ) was measured. The results were as shown in Table-1.

Reference example 1 [Copolymer (1) scale FJ] thermometer, 1
Party 1 Ma, dropping funnel, gas introduction pipe and reflux cooling 141
334 parts of polynibrene gelicol monoallyl ether (containing an average of 5 ethylene oxide units per molecule) and 100 parts of water were added to a glass reaction vessel equipped with a water heater, and the inside of the reaction vessel was heated with nitrogen ii under IjX ff. ! The mixture was heated to 95° C. in a nitrogen atmosphere. Then Maraine M
An aqueous solution of 139.3 parts and 14.2 parts of am7nium persulfate dissolved in 225 parts of water was added over 120 minutes. After the addition is complete, add 14.2 parts of 20% excess to 1 liter! l1fff ammonium aqueous solution was added for 20 minutes. After completion of addition, 1
The temperature inside the reaction vessel was maintained at 95° C. for 00 minutes to complete the polymerization reaction, and an aqueous copolymer solution was obtained. Next, a 40% aqueous solution of caustic soda was added to neutralize the mixture to obtain the sodium salt of copolymer (1) (hereinafter abbreviated as copolymer (1) Na salt).

) aqueous solution 1! It's I.

The sodium salt aqueous solution of this copolymer (1) is CI H=
9.5, and the viscosity was 203 tons.

Reference Example 2 [Preparation of copolymer (2)] Polyethylene glycol monoallyl ether (average of 1 molecule 317.3 #Jj J: 88.5 parts of water was charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95° C. in an atmosphere of nitrogen. Then Mullein 1M139.
3 parts and 11.1 parts of amseptinium peroxide to 209 parts of water.
1 part of the aqueous solution and 126.2 parts of Ste were added in parallel over 120 minutes. After the addition is complete, an additional 27.8 parts of 20
% aqueous ammonium per 1 iQFa solution was added over 60 minutes.

After the addition was completed, the temperature in the reaction vessel was maintained at 95° C. for 90 minutes to complete the polymerization reaction, and copolymer (2) was obtained.

Then, a 40% by weight aqueous solution of IIY bamboo soda was added to perform neutralization, thereby obtaining an aqueous solution of copolymer (2). The aqueous solution of this copolymer (2) is 1) H=9.5, viscosity 198
It was a sentient voice.

Reference example 3 [Preparation of copolymer (3)] Thermometer, stirrer, dropping funnel, gas introduction pipe J3 and reflux cooling 1n'L
6 parts of polyalkylene glycol monoallyl ether (with an average of 10 ethylene oxide units and 2 poly(containing 1 pyrene oxide unit) > 399° per molecule) and 203.5 parts of water were placed in a glass reaction vessel equipped with , the inside of the reaction vessel was replaced with nitrogen under stirring, and 9
Heated to 5°C. Thereafter, an aqueous solution prepared by dissolving 75.4 parts of Malein M and 17.1 parts of am7nium persulfate in 113.2 parts of water was added over 120 minutes. 17 during the end of addition
．． One part of 20% aqueous ammonium persulfate solution was added over 20 minutes. After the addition was completed, the temperature inside the reaction vessel was maintained at 95° C. for 100 minutes to complete the In polymerization reaction, and the copolymer aqueous solution was mixed at a ratio of 1:1. Next, neutralization was performed by adding a 40% aqueous solution of caustic soda to obtain an aqueous solution of copolymer (3). This aqueous solution of copolymer (3) had a DH of 9.5 and a viscosity of 135 centivoice.

Examples 1 to 7 The formulations shown in Table 1 were dissolved in 5 parts by weight of tap water or a small portion of Monoe Shohin Glycol 95 at the blending ratio shown in Table 1, and both solutions were mixed.

The following tests and measurements were performed on each sample.

[Δl metal corrosion test [B] Heat transfer surface corrosion test (Measurement of C1 precipitation The results were as shown in Table-1.

Comparative Examples 1-6 Samples prepared at the blending ratios shown in Table 1 in the same manner as Examples 1-7 were tested. The outcome was as shown in Table 1.

(Explanation 21 + Song Dynasty) Book 5 is translated into Ming's Guri] 1- In an antifreeze solution consisting of a3 and water, (△) phosphoric acids, ([3>I'J^M> chlorinated acids, (C) Libdate or Tungstate, (
1)) Anticorrosive agent J3 and (13) General formula (1), CI+2= CIl 1 ... (1)C
IllOfC2If40)Illfc3If60)n
If (in the formula, m and n are O or positive integers and m
+ n = 1 to 100, and the (C2I+40) unit and the (C3I+60) t1 position may be bonded in any order. ) Polyalkylene glycol monoallyl ether (I) represented by the general formula (1), R, R,.

CC...■ CO2X C02Y [However, in the formula, R1 and R2 each represent hydrogen or a methyl group, and X J3 and Y each represent (C2II
401. (C3II60), R3 (R3 represents hydrogen or an alumyl group having 1 to 20 carbon atoms, p and (1
is O or a positive integer e, p + q-0 to 100, and the (C2II40) unit and (C31160111i position may be bonded in any order), monovalent metal, divalent metal, ammonium group or i5113
Represents an amine group. A copolymer derived from a maleic acid monomer (II) and/or a monomer (III) copolymerizable with the maleic acid monomer (II) shown in 1. J to be within the range
However, the corrosion prevention effect of real aluminum is significantly improved.

Claims (1)

[Claims] (1) In an antifreeze solution consisting of glycols and water, (A) phosphoric acids, (B) aromatic polybasic acids, (C) molybdate or tungstate, (D)
Anticorrosive agent and (E) General formula (1), ▲Mathematical formula, chemical formula, table, etc.▼...(1) (However, in the formula, m and n are 0 or positive integers, and m+n
= 1 to 100, and (C_2H_4O) unit and (C_
3H_6O) units may be bonded in any order. ) Polyalkylene glycol monoallyl ether (I), general formula (2), ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) [However, R_1 and R_2 in the formula are hydrogen or methyl groups, respectively. , and X and Y are each (C_2H
_4O)_p(C_3H_6O)_qR_3(R_3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, p and q are 0 or a positive integer, p+q=0 to 100, and (C_2H_4O) unit and (C_3H_6O) Units may be bonded in any order), monovalent metals, divalent metals, ammonium groups, or organic amine groups. ] A copolymer derived from the maleic acid monomer (II) and/or the monomer (III) copolymerizable with these, and has a pH of 6.5 to 9.0. Antifreeze characterized by a range.