JP4718200B2 - Dicarboxylic acid and its salt - Google Patents

Description

The present invention relates to a dicarboxylic acid or a salt thereof that is not easily assimilated by microorganisms and has excellent hard water resistance, and a water-soluble processing oil agent and a water-soluble cleaning agent containing these dicarboxylic acid salts or salts thereof. More particularly, ethylene oxide, propylene oxide, each of the dicarboxylic acids or their alkali metal salts are composed of a polymer or a combination diacylated reaction of the polymer and f Kisahidoro phthalic anhydride-butylene oxide, ammonium salts or amine salts, And a water-soluble processing oil and a water-soluble cleaning agent characterized by containing these dicarboxylic acids and salts thereof.

  Alkali metal salts, ammonium salts, or amine salts of fatty acids are used as rust inhibitors and surfactants. Water-soluble processing oils and water-soluble detergents often contain fatty acid alkali metal salts, ammonium salts, or amine salts as main components. Fatty acids can also be used for neutralization of alkali metals, ammonium, or amines added to exert antiseptic and rust preventive effects, and play an important role in pH adjustment.

  The fatty acid has a lipophilic group (hydrocarbon moiety) and a hydrophilic group (carboxyl group), and exhibits surface activity. Fatty acid has different lipophilic group carbon length depending on the type, but the surface active property can be changed by selecting the carbon length.

  However, an alkali metal salt, ammonium salt or amine salt of a fatty acid having 9 or more carbon atoms in the main chain produces an insoluble calcium salt in the presence of calcium ions in an aqueous solution and loses its effectiveness as a surfactant. . In addition, when fatty acids with 9 or more carbon atoms in the main chain are contained in water-soluble processing oils or water-soluble cleaning agents, the insoluble calcium salt causes adhesion to the work material or machine, filter clogging, etc. Can cause problems.

  Typical industrial fatty acids include tall oil fatty acids and ricinoleic acid, but these fatty acids are derivatives of vegetable fats and oils, are easily assimilated by microorganisms, and contained in water-soluble processing oils, It becomes a factor causing corruption.

  On the other hand, as a metal corrosion inhibitor having excellent anti-corrosion, anti-corrosion, and anti-microbial degradation, a monoethylenic acid containing an unsaturated carboxylic acid monomer as an essential component in a polyether compound. A water-soluble graft polymer obtained by graft polymerization of a saturated monomer is known. (Patent Document 1)

Japanese Patent Laid-Open No. 11-264085

  The present invention relates to a dicarboxylic acid and a salt thereof that are not easily assimilated by microorganisms and have excellent hard water resistance, and a water-soluble processing oil agent and a water-soluble cleaning agent characterized by containing these dicarboxylic acid and a salt thereof. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventor has dicarboxylic acids useful as surfactants (especially rust preventives and cleaning agents) that are not easily assimilated by microorganisms and have excellent hard water resistance. The salt was found and the present invention was completed.

That is, the present invention provides the following.
1. Ethylene oxide, propylene oxide, each of the dicarboxylic acids or their alkali metal salts are composed of a polymer or a combination diacylated reaction of the polymer and f Kisahidoro phthalic anhydride-butylene oxide, ammonium salt or the dicarboxylic acid salt consisting of an amine salt A water-soluble processing oil characterized by comprising
2. A water-soluble cleaning agent comprising the dicarboxylic acid or a salt thereof according to claim 1.

  The dicarboxylic acid and its salt according to the present invention are not easily assimilated by microorganisms, and even when calcium ions are present in the diluted water, an insoluble salt is not generated, and the efficacy as a surfactant can be maintained for a long period of time. Moreover, also in the preparation to a water-soluble processing oil agent or a water-soluble detergent, it exhibits good solubility and can be blended stably.

  The polymer consisting of each polymer and combination of ethylene oxide, propylene oxide, and butylene oxide (hereinafter referred to as alkylene oxide) used in the present invention is a copolymer of a homopolymer of each alkylene oxide and a combination of two or more of various alkylene oxides ( Random or block polymers). The molecular weight of the polymer is generally preferably from 300 to 10,000. More preferably, the molecular weight is 500 to 5000. Particularly preferably, the molecular weight is 500 to 3000. When the molecular weight of the polymer is smaller than 300, sufficient surface activity is not exhibited, and when it is larger than 10,000, sufficient effects cannot be obtained in terms of neutralization of amine and pH adjustment.

  The acylation reaction between an acid anhydride and a hydroxyl group usually proceeds without catalyst, at normal pressure, and at a reaction temperature of about 100 to 150 ° C. However, the use of a catalyst (p-toluenesulfonic acid or the like) or extreme temperature conditions is not preferable because an esterification reaction between a carboxyl group and a hydroxyl group formed by ring opening after the acylation reaction proceeds.

  The reaction ratio between the alkylene oxide and the acid anhydride used in the present invention is usually an excess of 2.2 to 3 equivalents of acid anhydride relative to 1 equivalent of the polymer of alkylene oxide.

  The above diacylated reaction product may be neutralized with an alkali metal, ammonia or an amine by a conventional method.

  Sodium and potassium are particularly preferred as the alkali metal, and these may be used in combination as desired.

  Examples of the amine include alkylamines having 1 to 5 carbon atoms (for example, ethylamine, propylamine, etc.), alkanolamines having 2 to 10 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, dioxygen). Amines of the above-mentioned dibasic acids prepared from isopropanolamine, triisopropanolamine, cyclohexyldiethanolamine, etc.), morpholine, cycloalkylamines having 5 to 20 carbon atoms (for example, dicyclohexylamine etc.), 3,3-dimethylpropanediamine, etc. Examples of the salt include alkanolamines having 2 to 10 carbon atoms. Two or more of these amine salts may be used in combination as desired.

  Alkali metal salts, ammonium salts or amine salts may be used in combination.

The synthesis method of the general diacylation reaction product of this invention is shown.
Synthesis Method The diacylation reaction between an alkylene oxide polymer and an acid anhydride is carried out by heating at 120 to 150 ° C. for 5 to 12 hours under no catalyst, no solvent, and normal pressure. After completion of the reaction, the excess may be removed by sublimation or distillation, or may be purified by chromatography or the like. Or you may neutralize as it is in the subsequent neutralization process.

The end point of the reaction is the disappearance of the two absorption peaks (1779 cm ⁻¹ , 1848 cm ⁻¹ ) derived from the acid anhydride by the acylation reaction using FT-IR (absorption due to the strong ester group as the reaction proceeds ( The time when 1728 cm ⁻¹ ) appears) was taken as the end point of the reaction.

  When the dicarboxylic acid of the present invention is used in a water-soluble processing oil or water-soluble detergent, the ratio (weight molar ratio) of the dicarboxylic acid to the alkali metal, ammonia or amine is preferably 1: 2 to 1:20, particularly Preferably it is 1: 5 to 1:10. When the molar ratio is larger than 1: 2, solubilization is difficult and sufficient surface activity is not exhibited. When the molar ratio is smaller than 1:20, not only the surface activity is lowered, but also Occupational hygiene problems (for example, irritation of the respiratory system, rough skin, etc.) appear.

  When blended with a water-soluble processing oil or water-soluble cleaning agent, it is generally 1 to 80% by weight, preferably 2 to 50% by weight as a dicarboxylic salt. Water-soluble processing oils include mineral oils (for example, machine oil, spindle oil), animal and vegetable oils (for example, rapeseed oil, palm oil, beef tallow, castor oil), and oiliness improvers (for example, fatty acids, fatty acid esters). ), Extreme pressure additives (for example, chlorinated paraffins, sulfurized fats and oils), rust inhibitors (for example, alkanolamines), surfactants (for example, anions, nonions, cationic surfactants), preservatives (for example, 1 , 2-benzoisothiazolin-3-one), an antifoaming agent (for example, silicone-based), an anticorrosive agent (for example, benzotriazole), and the like can be appropriately blended. In addition, water-soluble detergents include fatty acids (for example, isononanoic acid and caprylic acid), rust inhibitors (for example, alkanolamines), surfactants (for example, anions, nonions, and cationic surfactants), antiseptics, as desired. Additives such as an agent (for example, 1,2-benzisothiazolin-3-one), an antifoaming agent (for example, silicone), and an anticorrosive agent (for example, benzotriazole) can be appropriately blended.

  Normally, these water-soluble processing oils or water-soluble cleaning agents are used after diluted in water. The dilution factor is generally used after diluting 5 to 100 times, but may be appropriately selected according to the intended use, but the concentration of the dicarboxylate of the present invention at the time of dilution is 0.01 to 16 % By weight (preferably 0.02 to 10% by weight). When the concentration is lower than 0.01% by weight, sufficient surface activity is not exhibited. On the other hand, if it exceeds 16% by weight, the surface activity does not increase, which is not economical.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Tables 1 and 2 show the diacylated reactants (Synthesis Nos. 1 to 23) of the present invention used in the examples.

  Table 3 shows the fatty acids used in the comparative examples as in Tables 1 and 2.

[Examples 1 to 24]
Test liquids having the blending compositions shown in Tables 4 to 5 were prepared, and the stability of the liquid against calcium ions (deposition state of insoluble calcium salt) was evaluated by the following evaluation method.

[Evaluation methods]
The calcium ion concentration of the test solutions shown in Tables 4 to 5 was adjusted to 100 ppm, and after standing in a thermostatic bath at 30 ° C. for 24 hours, the state of occurrence of precipitates was visually observed. The results are shown in Tables 4-5.
Judgment criteria A: No precipitate is generated.
○: A small amount of precipitate was generated.
Δ: A small amount of precipitate is generated.
X: A large amount of precipitates are generated.

[Comparative Examples 1 to 12]
Test liquids having the composition shown in Table 6 were prepared, and the stability of the liquid against calcium ions (deposition state of insoluble calcium salt) was evaluated by the evaluation method described above. The results are also shown in Table 6.

[Examples 25 to 34]
A solve type processing oil having the composition shown in Table 7 was prepared, and an evaluation test was conducted in the same manner as in the above examples. The results are shown in Table 7.

[Comparative Examples 13 to 22]
A solve type processing oil having the composition shown in Table 8 was prepared, and an evaluation test was conducted in the same manner as in the above-described Examples. The results are shown in Table 7.

[Example 35]
Degradability by microorganisms of the diacylated reaction products shown in Tables 1 and 2 and tall oil fatty acids in Table 3 were evaluated.

[Evaluation methods]
Synthesis No. 1 in Table 1 3, 12, Table 2, Synthesis No. 13 and No. 3 in Table 3. 500 ppm and 100 ppm septic solution were added to a Davis medium (phosphate buffer, ammonium sulfate, magnesium sulfate, carbon source) adjusted to pH 9.0 with 6 (tall oil fatty acid), stirred at a liquid temperature of 25 ° C., 1 After measuring BOD after a week, the degree of decomposition [BOD / ThOD × 100 (%)] was calculated. The results are shown in Table 9. BOD is the biochemical oxygen demand (measured value, unit is mg), and ThOD is the theoretical oxygen demand (calculated value, unit is mg).

  INDUSTRIAL APPLICABILITY The present invention is effective as a dicarboxylic acid and a salt thereof that are not easily assimilated by microorganisms and have excellent hard water resistance.

Claims (2)

Ethylene oxide, propylene oxide, each of the dicarboxylic acids or their alkali metal salts are composed of a polymer or a combination diacylated reaction of the polymer and f Kisahidoro phthalic anhydride-butylene oxide, ammonium salt or the dicarboxylic acid salt consisting of an amine salt A water-soluble processing oil characterized by comprising A water-soluble cleaning agent comprising the dicarboxylic acid or a salt thereof according to claim 1.