KR100305029B1 - Water-based heat treatment solution - Google Patents

Abstract

It is to develop a water-based heat treatment solution containing a water-soluble polymer which is hard to cause deterioration by use and can maintain a good quench cracking effect for a long time.

(a) 10 to 70% by weight of water (b) 10 to 70% by weight of water-soluble polyoxyalkylene derivative mainly composed of ethylene oxide components and (c) 0.1 to 20% by weight of alkali metal salt of carboxylic acid and / or alkali metal salt of sulfonic acid A water-based heat treatment liquid containing. As needed, you may contain 0.01-20 weight% of (d) organic amination loads.

Description

[Name of invention]

Water-based heat treatment solution

Detailed description of the invention

The present invention relates to a water-based heat treatment liquid, and in detail, it is used for metal heat treatment such as hardening treatment after diluting to a desired concentration in use, and it is difficult to cause deterioration by use. A diluent for heat treatment prepared by dilution of a treatment liquid.

Heat treatment liquids used for heat treatment of metals such as hardening treatments are roughly classified into aqueous (aqueous solution) emulsions and oils.

Water-based heat treatment liquids have the advantage of high cooling capacity and low oil and low risk of pollution and fire. On the other hand, the water-based heat treatment liquid has a drawback that it is easy to cause crack damage of a processing body called a hardening crack.

Water has a large heat capacity and a low viscosity, and is likely to cause convection. For this reason, the processing body loses heat in a very short time by the water-based heat treatment liquid and cools rapidly. In order to solve such a fault, the method of mix | blending various water-soluble polymers with a water-based heat processing liquid is known.

Incorporating a water-soluble polymer into the water-based heat treatment solution increases the viscosity, thereby suppressing convection and consequently preventing quenching cracks. As the water-soluble polymer, for example, polyoxyalkylene such as polyethylene glycol, polypropylene glycol, polyethylene glycol and polypropylene glycol having a weight ratio of 75:25, salts of interpolymers of olefins and maleic anhydride, and the like are used.

Japanese Unexamined Patent Application Publication No. 4-180515 discloses a copolymer of polyoxyalkylene derivative and maleic acid as such a water-soluble polymer.

However, these water-soluble polymers are liable to cause decomposition or deterioration when contacted with a high temperature treatment body. For this reason, it was difficult for the water-based heat treatment liquid containing a water-soluble polymer to easily deteriorate and to maintain a good anti-quenching effect for a long time.

Japanese Unexamined Patent Application Publication No. 57-39294 discloses a method of preventing quenching cracks by blending lauryl fat upstream with an aqueous heat treatment liquid. Japanese Unexamined Patent Application Publication No. 57-85923 discloses a method of improving the cleanliness of the surface of a treatment body by blending a water-soluble organic acid-soluble organic amine and a water-soluble polyalkylene glycol in an aqueous heat treatment liquid. Japanese Unexamined Patent Application Publication No. 3-12129 discloses a method of preventing corrosion of the apparatus for heat treatment by blending a water-soluble polyalkylene glycol, a carboxylic acid, an amine and a copper chelating agent in an aqueous heat treatment solution. However, even with these methods, it was difficult to maintain a good quenching prevention effect for a long time.

Under such circumstances, the present inventors have made intensive studies to develop a water-soluble polymer-containing water-based treatment solution which is hard to cause deterioration and can maintain a good quench crack preventing effect for a long time. As a result, when the water-soluble polymer is blended with a water-soluble polyoxyalkylene derivative mainly composed of ethylene oxide components, and when an alkali metal salt of carboxylic acid and / or an alkali metal salt of sulfonic acid is blended, the above-mentioned object can be achieved and its life is long. It was found that an aqueous heat treatment liquid was obtained. The present invention has been completed based on such findings. That is, the present invention comprises (a) 10-89.9% by weight of water (b) 10-70% by weight of a water-soluble polyoxyalkylene derivative mainly composed of ethylene oxide components and (c) an alkali metal salt of carboxylic acid and alkali metal salt of sulfonic acid. It is to provide a water-based heat treatment liquid containing 0.1 to 20% by weight of at least one alkali metal salt selected from the group.

Moreover, this invention provides 0.01-20 weight% of (d) organic amine compounds in addition to said (a) component (b) component and (c) component, The water-based heat processing liquid characterized by the above-mentioned.

In another aspect, the present invention also provides a diluent for heat treatment of 5 to 40% by weight and 95 to 60% by weight.

The water-soluble polyoxyalkylene derivative mainly composed of the ethylene oxide component (b) component of the present invention is a compound obtained by polymerizing alkylene oxide to an aliphatic hydroxy compound or aromatic hydroxy compound having one or two or more hydroxyl groups. The polyoxyalkylene group mainly having a component derived from ethylene oxide is said to have water solubility.

The chemical structure is represented by the following general formula (1).

[Wherein X represents a residue derived from an aliphatic hydroxy compound or an aromatic hydroxy compound having one or two or more hydroxyl groups, Y represents a polyoxyalkylene group mainly composed of components derived from ethylene oxide, and Z represents a polyoxyalkyl The hydroxyl group or functional group converted from the hydroxyl group which exists in the terminal of a len group is shown. Plural Y and Z may be the same or different. a represents the number of hydroxyl groups of an aliphatic hydroxy compound or aromatic hydroxy compound having one or two or more hydroxyl groups, and b represents the number of polyoxyalkylene groups bonded to the residue X.] .

The type of aliphatic hydroxy compound aromatic hydroxy compound and alkylene oxide is not particularly limited.

As an aliphatic hydroxy compound which has one, two, or more hydroxyl groups, For example, methanol; ethanol; Propanol; Butanol; Hexanol; 2-butanol; Straight chain or branched monoalkanols such as 2-methylpropanol, ethylene glycol; Propylene glycol; Hexane-1,2-diol; Butane-2,3-diol; Straight chain or branched dialkanols such as 2-methylpropane-1,2-diol, glycerin; Pentane-1,3,5-triol; Straight chain or branched trialkanols such as trimethylolpropane and erythritol; Sucrose; Sorbitol; Straight chains such as pentaerythritol or branched polyalkanols.

As an aromatic hydroxy compound which has one or two or more hydroxyl groups, For example, Phenol; (Substituted) monophenols such as 4-methylphenol, pyrocatechol; Resorcinol; Phloroglucinol; (Substituted) polyphenols such as 2,4-dihydroxy toluene. The aliphatic hydroxy compound and the aromatic hydroxy compound described above also include intramolecular ethers, partial ethers, partial esters, condensates of the same compounds, or condensates of different compounds of these compounds.

The condensate between different compounds may be a condensate of an aliphatic hydroxy compound and an aromatic hydroxy compound.

Among these, glycerin; Hexane-1,2-diol; Ethylene glycol; Propylene glycol is preferred, and glycerin is particularly preferred. Moreover, when the alkylene oxide is polymerized, the compound which produces | generates the residue similar to the case where glycerin is used is also used preferably.

As said alkylene oxide, ethylene oxide, a propylene oxide, butylene oxide etc. are mentioned, for example. The polyoxyalkylene group in the component (b) does not need to be a homogeneous polymer containing only ethylene oxide components, but needs to be mainly composed of ethylene oxide components. In the case where the polyoxyalkylene group is an interpolymer group containing alkylene oxides other than ethylene oxide, it is preferable that ethylene oxide occupies at least 50% by weight of the total alkylene oxide and ethylene oxide occupies at least 65% by weight. Again more preferred. The interpolymer group may be either a random interpolymer group or a block interpolymer group.

The polyoxyalkylene derivative as the component (b) may have a hydroxyl group liberated at a residue derived from an aliphatic hydroxy compound or an aromatic hydroxy compound having one or two or more hydroxyl groups. Moreover, the hydroxyl group which exists in the terminal of a polyoxyalkylene group may be converted into other functional groups, such as an ether group and an ester group. Again, the polyoxyalkyrene group bound to the same residue may be the same or different.

The molecular weight of the polyoxyalkylene derivative is not particularly limited, but a weight average molecular weight (Mw) of 2,000 to 500,000, preferably 10,000 to 200,000, is used.

Moreover, a polyoxyalkylene derivative may be used individually by 1 type, and even if it uses 2 or more types together, it does not interfere.

The kind of alkali metal salt of carboxylic acid and sulfonic acid as the component (c) of the present invention is not particularly limited, and salts prepared with an acid and an alkali metal such as aliphatic carboxylic acid aromatic carboxylic acid aliphatic sulfonic acid or aromatic sulfonic acid can be widely used.

As aliphatic carboxylic acid, C3-C36 aliphatic dicarboxylic acid of preferably 6-20 is used normally. Specifically, for example, malonic acid; Adipic acid; Sebacic acid; Azelaic acid; Eicosan diacid; 4-methylnonan-1,9-dicarboxylic acid; Dimer acid; 1,2-hexanedicarboxylic acid; 1,3-octanedicarboxylic acid; 4,5-decanedicarboxylic acid etc. are mentioned. In these, the aliphatic dicarboxylic acid which the carboxylic acid couple | bonds with the two terminal of a hydrocarbon chain, respectively is preferable.

As the aromatic carboxylic acid, aromatic carboxylic acid having 7 to 20 carbon atoms is usually used. Specifically, for example, benzoic acid; 4-ethylbenzoic acid; Phthalic acid; Isophthalic acid; Salicylic acid. Moreover, the aromatic carboxylic acid also includes the compound in which the carboxyl group couple | bonded only to the side chain of an aromatic ring. Specifically, for example, phenoxy acetic acid; Nonylphenoxy acetic acid, and the like. Among these, the compound in which the carboxyl group couple | bonds only to the side chain of an aromatic ring is preferable.

As the aliphatic sulfonic acid, aliphatic sulfonic acid having 3 to 36 carbon atoms, preferably 6 to 22 carbon atoms is usually used. Specifically, for example, hexanesulfonic acid; Udecansulfonic acid; Eicosulfonic acid; 3-methylnonanesulfonic acid; Decane-2-sulfonic acid, and the like. The aliphatic sulfonic acid also contains α-olefinsulfonic acid. Specifically, for example, 1-butenesulfonic acid; 1-decenesulfonic acid, etc. are mentioned.

As the aromatic sulfonic acid, an aromatic sulfonic acid having 6 to 36 carbon atoms and preferably 6 to 20 carbon atoms is usually used. Specifically, for example, benzene sulfonic acid; Toluenesulfonic acid; Dodecylbenzenesulfonic acid, and the like. In these, benzene sulfonic acid is preferable.

On the other hand, potassium and sodium are preferably used as the alkali metal.

In addition, the alkali metal salt of carboxylic acid and the sulfonic acid alkali metal salt which are (c) component may be used individually by 1 type, or may use 2 or more types together.

The organic amine compound can be mix | blended with the heat processing liquid of this invention as (d) component as needed. When the organic amine compound is blended in the heat treatment liquid of the present invention, it is possible to maintain the quenching crack prevention effect for a longer period of time. The kind of the organic amine compound as the component (d) is not particularly limited, and various primary secondary tertiary tertiary amine compounds can be used.

As an organic amine compound, it is C4-C14 preferably 6-12 cycloalkylamine, C1-C12 preferably 2-9 alkanolamine, C4-C24 piperazine derivative, and A morpholine derivative having 4 to 34 carbon atoms and preferably 4 to 16 carbon atoms is used. Specific examples of the cycloalkylamine having 6 to 12 carbon atoms may include, for example, monocyclohexylamine dicyclohexylamine mono (2-methylcyclopentyl) ami.

Specific examples of the alkanolamine having 2 to 9 carbon atoms include monoethanolamine diethanolamine triethanolamine monomethanol diethanolamine triisophoropanolamine and the like. As a specific example of a C4-8 piperazine derivative, piperazine methyl piperazine t-butyl piperazine N-methyl piperazine etc. are mentioned, for example. Piperazine derivatives also include compounds containing hydroxyl groups. Specific examples of such compounds include, for example, hydroxypiperazine N-hydroxypiperazine monohydroxydiethylpiperazine dihydroxy-monoethylpiperazine hydroxy-N-methylpiperazine N-hydroxy-propylpipe Rajin etc. can be given. As a specific example of a C4-C16 morpholine derivative, morpholine ethyl morpholine t-butyl morpholine dimethyl morpholine N-methyl morpholine etc. are mentioned, for example.

Among these, piperazine derivatives containing an alkanolamine having 2 to 9 carbon atoms and a hydroxyl group having 4 to 8 carbon atoms are preferred, and diethanoxamine and monohydroxy monoethyl piperazine are particularly preferred.

In addition, these organic amine compounds may be used individually by 1 type, or may use 2 or more types together.

Other additives can be mix | blended with the heat processing liquid of this invention as needed, unless the objective of this invention is impaired. Such additives include, for example, sodium nitrite, potassium nitrate, sodium carbonate, potassium carbonate, sodium metaborate, potassium metaborate, sodium phosphate, potassium hexametaphosphate, hexametaphosphate, potassium orthosilicate, sodium orthosilicate, potassium metasilicate, potassium metasilicate, benzotriazole and tolyltria Corrosion inhibitors such as sol, anticorrosive, silicone-based antifoaming agents, and coloring agents.

The heat treatment solution of the present invention dissolves an alkali metal salt of carboxylic acid and / or an alkali metal salt of sulfonic acid in component (b) and polyoxyalkylene derivative of component (c) in water of component (a) and again (d) It is prepared by dissolving the component organic amine compound and / or other additives. The compounding order or dissolution method is not particularly limited.

The blending ratio is based on the total amount of the heat treatment solution, based on the total amount of the heat treatment solution, (a) component water at least 10% by weight, (b) component 10-70% by weight, preferably 30-60% by weight, and (c) component 0.1-20 Weight% Preferably it is 2-10 weight%, and (d) component is 0.01-20 weight% Preferably it is 1-10 weight%.

When the compounding quantity of any component is less than the lower limit of the said ratio, a favorable hardening crack prevention effect cannot be maintained over a long term. On the other hand, when the compounding quantity of any component exceeds the upper limit of the said ratio, a good hardening crack prevention effect may not be maintained for a long time, and also it becomes disadvantageous economically.

The heat treatment liquid of the present invention is a so-called stock solution prepared for the convenience of storage and transportation. Therefore, in the case of performing the metal heat treatment, a heat treatment diluent prepared by diluting the heat treatment solution of the present invention with water is used. The preferred dilution ratio depends on the concentration of the heat treatment solution as a stock solution, but is usually 5 to 40% by weight of the heat treatment solution of the present invention and 95 to 60% by weight of water based on the total amount of the prepared heat treatment diluent.

In addition, as a method of preparing the diluent for heat treatment, in addition to the method of diluting the heat treatment solution, a method of preparing a dilution solution for heat treatment is prepared by dissolving the compounding component in water. And the heat treatment diluent of the present invention includes a heat treatment diluent prepared directly as described above.

EXAMPLE

Next, this invention is demonstrated in detail again based on an Example and a comparative example. However, the present invention is not limited thereto.

Example 1

(a) 57% by weight of water, (b) polyoxyalkylene derivatives (Mw = 20,000, residues derived from aliphatic hydroxy compounds are glycerin skeletal polyoxyalkylene groups consisting of 75% by weight of ethylene oxide and 25% by weight of propylene oxide). 40 wt% of the interpolymer group) and 3.0 wt% of (c) potassium sebacate were dissolved to prepare a water-based heat treatment solution.

Next, 80% by weight of water was added to and diluted with 20% by weight of this water-based heat treatment solution to prepare a diluent for heat treatment. Each test mentioned later was performed about the obtained dilution liquid for heat processing, and the change of the cooling capacity at the time of new liquid and the cooling capacity by deterioration was evaluated.

EXAMPLES 2-8

Dissolve each component of (a), (b), (c) and (d) in the ratio shown in the first table to prepare a water-based heat treatment solution, and the water-based heat treatment solution is 20% by weight as in Example 1. It diluted with and prepared the dilution liquid for heat processing. The obtained dilution liquid for heat treatment was tested in the same manner as in Example 1. The results are shown in the first table.

[Comparative Examples 1-3]

Dissolve each component of (a), (b), (c) and (d) in the ratio shown in the second table to prepare a water-based heat treatment solution, and the water-based heat treatment solution is 20% by weight as in Example 1. It diluted with and prepared the dilution liquid for heat processing. The obtained dilution liquid for heat treatment was tested in the same manner as in Example 1. The results are shown in Table 2. The test of the dilution liquid for heat processing was performed by the method shown next.

[Cooling capacity evaluation test at new liquid]

The average cooling rate (° C./sec) between cooling from 350 ° C. to 150 ° C. was measured when the processed body heated to 800 ° C. was cooled in the diluent for heat treatment. The test was carried out in accordance with Japanese Industrial Standard (JIS) K2242. In this test, the average cooling rate V is calculated by the following formula.

V = (350-150) ÷ (M ₂ -M ₁ )

[Wherein M ₁ represents the time when the processing body reaches 350 ° C and M ₂ represents the time when the processing body reaches 150 ° C.]

The lower the value of the average cooling rate V calculated by the above equation, the slower the cooling of the treated body in the martensite transformation region (350-150 ° C.) and the higher the hardening crack prevention effect.

[Degradation test]

In order to evaluate the change in cooling capacity due to deterioration, a deterioration test was conducted in accordance with Japanese Industrial Standard (JIS) K2514, 3.2. Deterioration condition _{95 ℃ Fe / Cu, O 2} : was a 3ℓ / h, liquid volume 350mℓ. The degradation was evaluated by comparing the average cooling rate (° C / sec) at the end of the degradation test (after 96 hours) and the time when the average cooling rate reached 150 ° C.

TABLE 1a

Polyoxyalkylene Derivatives: Any Examples Comparative Examples were used in the same manner as in Example 1.

* 2 sebacic acid: used in Comparative Example to compare with (c) component.

TABLE 1b

TABLE 2

As is apparent from Comparative Example 3, the average cooling rate in the case where only polyoxyalkylene derivative is added to water is good at 70 ° C / sec in fresh liquid, and the hardening crack can be sufficiently prevented. However, 1 hour after the start of the deterioration test, the temperature was 150 ° C / sec, and after completion of the deterioration test, that is, 96 hours, the temperature was 660 ° C / sec equivalent to that of water (Comparative Example 2). In addition, as apparent from Comparative Example 1, in addition to water and polyoxyalkylene derivatives, when the sebacic acid (free carboxylic acid) and diethanolamine (organic amine) were added together, the average cooling rate was 150 ° C / sec. It is 20 hours away and the quenching cracking effect is slightly maintained. However, at the end of the deterioration test, it became 580 ° C / sec equivalent to water (Comparative Example 2).

On the other hand, when potassium sebacinate was added in addition to water and polyalkylene derivatives (Example 1), it took 200 hours for the average cooling rate to be 150 ° C / sec. There is little change in the average cooling rate. This fact indicates that the heat treatment solution of the present invention maintains the hardening crack prevention effect for a long time and has a long life. When monohydroxy monoethyl piperazine was blended with potassium sebacinate (Example 2), the change of the average cooling rate was again small. This fact indicates that when the organic amine is added to the heat treatment solution of the present invention, a superior life extension effect is obtained. Also excellent in the case of blending alkali metal salts or alkali metal sulfonic acid salts other than potassium sebacinate (Examples 3, 4, 5, and 6) or in the case of blending organic amines other than monohydroxymonoethylpiperazine (Example 7) The life extension effect was confirmed. Good results were also obtained when two or more kinds of alkali metal carboxylic acid lead or sulfonic acid alkali metal salts were blended (Example 8).

As described above, the water-based heat treatment liquid and the dilution liquid for heat treatment are less likely to cause deterioration by use and have a long service life. Therefore, the aqueous heat treatment liquid and the heat treatment diluent of the present invention are suitably used in place of conventional water-based, oil-based, emulsion-based or inorganic-based heat treatment solutions for metal heat treatment such as quenching. It can also be used for hot casting or hot rolling.

Claims (5)

(a) 10-89.9% by weight of water, (b) 10-70% by weight of water-soluble polyoxyalkylene derivatives mainly composed of ethylene oxide components, and (c) alkali metal salts of carboxylic acids and alkali metal salts of sulfonic acids. A water-based heat treatment solution containing 0.1-20% by weight of at least one alkali metal salt selected. The alkali metal salt as the component (c) is a sodium salt of aliphatic dicarboxylic acid, a potassium salt of aliphatic dicarboxylic acid, a sodium salt of aromatic carboxylic acid, a potassium salt of aromatic carboxylic acid, a sodium salt of aliphatic sulfonic acid, and a potassium of aliphatic sulfonic acid. A water-based heat treatment liquid, characterized in that at least one compound selected from the group consisting of salts, sodium salts of aromatic sulfonic acids and potassium salts of aromatic sulfonic acids. (a) 10-89.9% by weight of water, (b) 10-70% by weight of water-soluble polyoxyalkylene derivatives mainly composed of ethylene oxide components, and (c) alkali metal salts of carboxylic acids and alkali metal salts of sulfonic acids. 0.1-20% by weight of at least one alkali metal salt selected and 0.01-20% by weight of (d) organic amine compound. The aqueous heat treatment liquid according to claim 3, wherein the organic amine compound as the component (d) is at least one organic amine compound selected from the group consisting of piperazine derivatives and alkanolamines. (a) 10-89.9% by weight of water, (b) 10-70% by weight of water-soluble polyoxyalkylene derivatives mainly composed of ethylene oxide components, and (c) alkali metal salts of carboxylic acids and alkali metal salts of sulfonic acids. It is prepared by diluting by adding water to the water-based heat-treatment stock solution composed of 0.1-20% by weight of at least one alkali metal salt, wherein the metal is composed of 5-40% by weight of the stock solution and 95-60% by weight of water. Diluent for heat treatment.