JP6674996B1 - Water-soluble lubricating rust inhibitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble lubricating rust preventive agent which is excellent in lubricity and prevents oxidation without corroding even a water-soluble type having no risk of catching fire. SOLUTION: The water-soluble lubricating rust preventive comprises a metal salt of polyoxyethylene alkyl ether acetic acid represented by the following general formula (1), a water-soluble rust preventive component, and water. . Wherein R represents an alkyl group having a carbon number of C12: 0 to C18: 1, m = 4 to 10, X is a metal, and n is a valence of the metal [Selection diagram] None

Description

  The present invention relates to a lubricating rust inhibitor. In particular, it relates to a water-soluble lubricating rust inhibitor suitable for lubrication and rust prevention of metal members.

  Conventionally, LPG (Liquidified Petroleum Gas) used as a pressurized gas such as an oil-based spray-type lubricant, a rust preventive and the like, and a mixture of propane and butane, which are commercially available for general household use, have been used. The mainstream is -50 ° C or lower, and there is a risk of ignition due to frictional heat in actual use, and there is a problem in that storage and display of products are handled as dangerous goods.

Patent Literatures 1 to 4 disclose oil-based lubricants and rust preventives.
Patent Document 1 discloses, as a lubricating oil containing a corrosion inhibitor for a copper-based material, a processing oil lubricant for a copper-based material containing a corrosion inhibitor composed of a benzothiazole-based organic compound.
Patent Literature 2 discloses a light lubricant having improved permeability and applicability, which contains volatile silicone and hydrocarbon oil.
Patent Literature 3 discloses a lubricant containing benzotriazole, benzimidazole, benzothiazole, or the like in a base oil as a lubricant for metal working of copper and copper alloys.
Patent Document 4 discloses a refrigerating machine oil composition for a carbon dioxide refrigerant in which the SP value of a base oil and the SP value of an oil-soluble polymer are specified with respect to a refrigerating machine oil composition.

In recent years, when these oil-based types have been stored in a warehouse, there is an incalculable danger of a fire, which has become a serious problem.
In order to avoid the danger of such an oily type, it is considered that water solubility is most suitable. However, water solubility is difficult to ignite, but there is a problem of corrosion. Generally, the lubricant reacts with the metal surface to lower the melting point of the metal to obtain slip, whereas the rust inhibitor reacts with the metal surface and adsorbs to prevent the intrusion of oxygen. It is desirable that the substance does not slip, and it is difficult to exert both effects at the same time because these actions are opposite to each other. Furthermore, when the form of the component is water-soluble (emulsion (O / W)), it has been considered that it is difficult to exhibit a stable effect under temperature conditions and the like.

JP-A-6-10166 JP-A-8-302375 JP-A-11-349975 JP 2007-204568 A

As described above, a liquid lubricating preventive containing pressurized gas, mineral oil, organic solvent, etc., is used for spraying the friction surface with a can sprayer to lubricate the members, prevent rust and loosen the fixed members such as screws. Most rust agents are extremely dangerous because they contain flammable liquids and gases, and there are problems such as extremely limited or restricted storage amounts and locations, and there is no example examined from the viewpoint of dangerous substances.
Accordingly, an object of the present invention is to provide a water-soluble lubricating rust preventive agent that prevents oxidation without corrosion even in a water-soluble type having no danger of ignition and has excellent lubricity.

ここで、Ｒは炭素数がＣ１２：０〜Ｃ１８：１のアルキル基を示し、ｍ＝４〜１０、Ｘは金属であり、ｎは金属の価数を示す。
＜２＞
ポリオキシエチレンアルキルエーテル酢酸の金属塩が、以下の一般式（２）で示される前記＜１＞に記載の潤滑防錆剤。

＜３＞ポリオキシエチレンアルキルエーテル酢酸の金属塩を、水を除いた有効成分中、２０〜６０％含む前記＜１＞又は＜２＞に記載の潤滑防錆剤。
＜４＞潤滑剤全組成中、水を５０重量％以上含む前記＜１＞〜＜３＞のいずれかに記載の潤滑防錆剤。
＜５＞水溶性防錆成分として、アルミニウムに対する防錆成分、銅に対する防錆成分、鉄に対する防錆成分のいずれか１以上を含む前記＜１＞〜＜４＞のいずれかに記載の潤滑防錆剤。 The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by selecting a lubricating component, optimizing the blending amount, and selecting a rust-preventive component, the superiority is superior to that of an oil-based lubricating rust inhibitor. We succeeded in obtaining a safe water-soluble lubricating rust inhibitor with excellent lubricity and rust prevention.
That is, the present invention has the following configuration.
<1>
A water-soluble lubricating rust inhibitor,
The lubricating rust inhibitor comprising a metal salt of polyoxyethylene alkyl ether acetic acid represented by the following general formula (1), a water-soluble rust-preventive component, and water.

Here, R represents an alkyl group having a carbon number of C12: 0 to C18: 1, m = 4 to 10, X represents a metal, and n represents a valence of the metal.
<2>
The lubricating rust inhibitor according to <1>, wherein the metal salt of polyoxyethylene alkyl ether acetic acid is represented by the following general formula (2).

<3> The lubricating rust inhibitor according to the above <1> or <2>, wherein the metal salt of polyoxyethylene alkyl ether acetic acid is contained in an active ingredient other than water in an amount of 20 to 60%.
<4> The lubricating rust inhibitor according to any one of the above <1> to <3>, which contains water in an amount of 50% by weight or more in the total composition of the lubricant.
<5> The anti-lubricating composition according to any one of <1> to <4>, wherein the water-soluble anti-rust component contains at least one of an anti-rust component against aluminum, an anti-rust component against copper, and an anti-rust component against iron. Rust agent.

  According to the present invention, a so-called all-in-one water-soluble lubricating prevention having both effects of imparting lubricity for reducing frictional force generated on a friction surface and preventing corrosion of the surface due to frictional heat generated on the friction surface. A rust agent can be provided. Commercially available lubricants and rust preventives are oily and contain LPG of pressurized gas and mineral oil as an effective component. Their flash points are extremely low and are dangerous. There is a need. On the other hand, since the rust preventive lubricant of the present invention is a water-soluble type, it is extremely safe regardless of where it is used or stored.

It is a figure which shows the rust prevention test method with respect to iron. It is a figure which shows the evaluation criteria of the rust prevention test with respect to iron. It is a figure which shows the wet rust prevention test method with respect to aluminum and copper.

The present invention is characterized in that both the lubricating component and the rust preventive component are water-soluble, all-in-one water-soluble lubricating rust preventive agents. Therefore, the essential components of the lubricating rust inhibitor of the present invention include a water-dispersible lubricating component, a water-soluble rust preventing component, and water.
As the water-dispersible lubricating component, a metal salt of polyoxyethylene alkyl ether acetic acid is desirable.
The general formula (1) of the polyoxyethylene alkyl ether acetate of the present invention is shown below.

ここで、Ｒは炭素数がＣ１２：０〜Ｃ１８：１のアルキル基を示し、ｍ＝４〜１０、Ｘは金属でありｎは金属の価数を示す。
アルキル基は、直鎖状、分岐状でもよく、また、芳香族であってもよい。
ポリオキシエチレンアルキルエーテル酢酸の末端のカルボキシル基と結合する金属Ｘとしては、重金属類（酸化物や水酸化物も含む）、アルカリ土類金属等が挙げられ、所謂 金属石鹸となり、潤滑性能を発揮するものであればいずれでもよい。そのような金属の具体例としては、カルシウム、銅、アルミニウム、マグネシウム等が挙げられ、このうちでもカルシウムが望ましい。
後述する実施例の処方に用いたポリオキシエチレンアルキルエーテル酢酸カルシウム塩（アルキル基 Ｃ１６：０〜Ｃ１８：１、ＥＯ９ｍｏｌ）の分子構造を以下（２）に示す。
なお、Ｃ１６：０〜Ｃ１８：１と表示した場合には、Ｃ１６：０、Ｃ１８：０、Ｃ１８：１が含まれる。

Here, R represents an alkyl group having a carbon number of C12: 0 to C18: 1, m = 4 to 10, X is a metal, and n is a valence of the metal.
The alkyl group may be linear, branched, or aromatic.
Examples of the metal X bonded to the terminal carboxyl group of the polyoxyethylene alkyl ether acetic acid include heavy metals (including oxides and hydroxides), alkaline earth metals, and the like. Any of them may be used. Specific examples of such a metal include calcium, copper, aluminum, magnesium and the like, and among them, calcium is desirable.
The molecular structure of the polyoxyethylene alkyl ether acetate calcium salt (alkyl group C16: 0 to C18: 1, EO 9 mol) used in the formulations of Examples described below is shown in (2) below.
When C16: 0 to C18: 1 are displayed, C16: 0, C18: 0, and C18: 1 are included.

The compounding amount of the water-dispersible lubricating component of the present invention is desirably 20 to 60% of the active component in the lubricant composition. The active ingredient refers to a component obtained by removing water from all components of the lubricant composition. In this specification,% means% by weight unless otherwise specified.
The water-dispersible lubricant component of the present invention is dispersed in water to form an emulsion. The ratio of water to the water-dispersible lubricant component is preferably greater than 50% for water and less than 50% for the water-dispersible lubricant component. If the amount of the water-dispersible lubricant component exceeds 50% of water, the viscosity becomes high and the fluidity is poor, which is not preferable for use.
The viscosity of this emulsion can be adjusted by (i) the ratio of the water-dispersible lubricant component (formula 1) to water, (ii) adding a solid lubricant as appropriate, or (iii) adding a nonionic surfactant (alkyl- ( It is also possible to adjust by increasing or decreasing EO) _n- OH).

As the water-soluble rust preventive component of the present invention, any water-soluble rust preventive component corresponding to the metal species may be used. For example, N, N-bis (2-hydroxyethyl) -N-cyclohexylamine salt is a representative example of a water-soluble iron rust preventive component.
As a water-soluble aluminum rust preventive component, a sodium salt of polyoxyalkylene dialkyl phenyl ether phosphate ester can be exemplified.
Any water-soluble copper rust preventive component may be used as long as it is a 1,2,3-benzotriazole compound, such as 1,2,3-benzotriazole, 1,2,3-benzotriazole salt, 1,2,3-benzotriazole. Examples include 3-benzotriazole derivatives (tolyltriazole and its salts, carboxybenzotriazole and its salts, and the like), and among them, 1,2,3-benzotriazole sodium salt is preferable.
The compounding amount in the present lubricant composition may be an amount capable of exhibiting the respective rust-preventing effects, and the ratio to the water-dispersible lubricating component is as follows. The rust-preventive component of iron is preferably from 0.5 to 1.2, more preferably from 0.6 to 0.9, most preferably from 0.75 to 0.85, based on the water-dispersible lubricating component.
The rust preventive component of aluminum is preferably 0.1 to 0.5, more preferably 0.2 to 0.4, and most preferably 0.25 to 0.35. The rust-preventive component of copper is preferably 0.001 to 0.1, more preferably 0.005 to 0.05, and most preferably 0.008 to 0.02, based on the water-dispersible lubricating component.

  Since the water-soluble lubricating rust preventive of the present invention is water-soluble, it is desirable that the water-soluble lubricating rust preventive contains an aqueous solution-stable component in order to stably maintain an emulsion state of water and the above-mentioned lubricating component and rust-preventive component. Specifically, a β-alanine type amphoteric surfactant was used as the aqueous solution stable component.

  The water-soluble lubricating rust preventive of the present invention may further contain components contained in other lubricating rust preventives, such as a preservative, within a range not to impair the effects of the present invention.

  Since the water-soluble lubricating rust preventive of the present invention is in a liquid state, the container for filling the product may be the one used for the conventional oil-based type, but may be the plastic used for so-called cosmetics. Absent. Similarly, a spray type or a spray type can be adopted.

[Example] Method for producing water-soluble lubricant Production of water-dispersible lubricating component (1) Production of polyoxyethylene alkyl ether calcium acetate (alkyl group C16: 0 to C18: 1, EO 9 mol) Polyoxyethylene alkyl ether acetic acid (Kao Corporation, AKYPO LS-090) It was produced by reacting with calcium hydroxide (Kanto Chemical Co., Ltd.).
(2) Preparation of calcium polyoxyethylene alkyl ether acetate (alkyl group C = 8, EO 8 mol) Polyoxyethylene alkyl ether acetic acid (Kao Corporation, AKYPO LS-F2) is reacted with calcium hydroxide (Kanto Chemical Co., Ltd.) Manufactured.
(3) Production of polyoxyethylene alkyl ether calcium acetate (alkyl group C16: 0 to C18: 1, EO 2 mol) Polyoxyethylene alkyl ether acetic acid (Kao Corporation, AKYPO RO-20) was converted to calcium hydroxide (Kanto Chemical Co., Ltd.) Company).
(4) Sodium polyoxyethylene alkyl ether acetate (alkyl group C16: 0 to C18: 1, EO 9 mol)
It was produced by reacting polyoxyethylene alkyl ether acetic acid (Kao Corporation, AKYPO LS-090) with sodium hydroxide (Kanto Chemical Co., Ltd.).
(5) Production of polyoxyethylene alkyl ether acetate triethanolamine (alkyl group C16: 0 to C18: 1, EO 9 mol) Polyoxyethylene alkyl ether acetate (Kao Corporation, AKYPO LS-090) was converted to triethanolamine (Kanto) (Chemical Co., Ltd.).

2. The following commercially available products were used as such as rust-preventive components, preservatives, and aqueous-solution-stable components as they were, or prepared by known methods.
・ N, N-bis (2-hydroxyethyl) -N-cyclohexylamine (ADEKA Corporation)
-Β-alanine-type amphoteric surfactant (β-alanine (sodium N-hydroxyalkyl-N- (EO) 3 aminoethylalkylcarboxylate (alkyl group C10-12))) (Miyoshi Oil & Fat Co., Ltd.)
-Polyoxyalkylene dialkyl phenyl ether phosphate sodium salt Polyoxyalkylene dialkyl phenyl ether phosphate sodium salt (Daiichi Kogyo Seiyaku Co., Ltd.) was produced by reacting with sodium hydroxide (Kanto Chemical Co., Ltd.).
・ Hexahydro-1,3,5-tris (2-hydroxyethyl) -1,3,5-triazine (San-ai Sekiyu KK)
・ 1,2,3-benzotriazole sodium salt (Daiwa Chemical Co., Ltd.)

3. Production of Water-Soluble Lubricant A water-soluble lubricant was produced according to the following procedure so as to obtain the composition shown in Table 1 for Formulation Example 1.
10% of polyoxyethylene alkyl ether calcium acetate, 3% of sodium salt of polyoxyalkylene dialkyl phenyl ether phosphate and 20% of water are mixed at 40 to 60 ° C. When a uniform solution is obtained, heating is stopped. 8% of the remaining N, N-bis (2-hydroxyethyl) -N-cyclohexylamine, β-alanine type amphoteric surfactant (sodium N-hydroxyalkyl-N- (EO) 3 aminoethylalkylcarboxylate (alkyl group C10-12)) 4%, hexahydro-1,3,5-tris (2-hydroxyethyl) -1,3,5-triazine 0.2%, 1,2,3-benzotriazole sodium salt 0.1% And 54.7% of water and mix.
Formulation Examples 2 to 13-2 were similarly produced.

[Test Example 1] Evaluation of aqueous solution stability Test Method For the water-soluble rust-preventive lubricant of each formulation example, the presence or absence of separation after 5 minutes by centrifugation (rotation speed: 2000 rpm) under the conditions of room temperature and 5 ° C. was visually observed. X), when not separated, the stability was evaluated as good (〇). For reference, KURE5-56 (registered trademark, Kure Kogyo Co., Ltd.) as an oily lubricating rust inhibitor was also evaluated by performing the same test and the test described later.

2. Test Results Table 4 shows the results of the above test evaluation of the lubricant composition of the present invention. Formulation Examples 1-7, 9-11, 13-1, and 13-2 had good stability. In Formulation Example 8, polyoxyethylene alkyl ether calcium acetate (2 mol of EO) did not disperse in water, and a stable aqueous solution was not obtained, and thus could not be evaluated in the following lubrication performance tests and rust prevention tests. Formulation Example 12 had a composition obtained by removing the aqueous solution stable component from Formulation Example 1. However, a stable aqueous solution was not obtained, and similarly, it could not be evaluated by the following lubrication performance test and rust prevention test. The aqueous stability of the oil-based lubricating rust inhibitor of the reference example was also poor.

[Test Example 2] Lubrication performance test
1. Test method
The lubricating performance, which is a basic characteristic of the present invention, was evaluated from the coefficient of friction (μ).
Using a tribogear surface measuring machine TYPE: 38 (manufactured by Shinto Kagaku Co., Ltd.), each sample was uniformly applied to a test plate and measured. The measurement was performed at room temperature (22 to 24 ° C.) and a load of 9.8 N.

2. Test Results Table 2 shows the measured values of the coefficient of friction of the lubricant composition of the present invention. The measured values are shown in Table 4 as "x" for 0.1 or more and "〇" for less than 0.1.
According to the results, Formulation Examples 1, 5, 9-11, 13-1, and 13-2 had a coefficient of friction of less than 0.1 between any dissimilar metals and were excellent in lubrication performance. 3,4,6,7, and commercial products were 0.1 or more between any of the dissimilar metals, and sufficient lubrication performance was not obtained.

[Test Example 3] Rust prevention test on iron Test method A rust prevention test on iron was performed according to the following method based on the German Industrial Standard (DIN 51360).
(1) Test procedure (i) Spread 2 g of gray cast iron chips as shown in FIG.
(Ii) Spray 2 ml of the sample (water-soluble lubricant composition of the present invention) adjusted to the measured concentration from above the cuttings, close the container and allow it to stand at room temperature for 2 hours, then take out the filter paper and add water and acetone. Wash and dry the filter paper.
(Iii) The degree of coloring of the filter paper is visually observed and evaluated.
(2) Evaluation criteria are shown in FIG.

2. Test Results Table 3 shows the test evaluation results of the lubricant composition of the present invention. In addition, Table 4 shows the results of the evaluation, where 1, 2 and 3 to 5 of the evaluation results were evaluated as x.
According to this result, Formulation Examples 1-7, 10, 11, 13-1, and 13-2 were excellent in rustproofness against iron, and Formulation Example 9 and a commercial product were poor in rustproofness against iron. .

[Test Example 4] Rust prevention test for aluminum and copper Test method Rust prevention tests on aluminum and copper were performed by the wet method described below.
(1) Preparation of test piece The test piece was polished uniformly with a cleanser and thoroughly washed with tap water.
This test piece was subjected to ultrasonic cleaning for 5 minutes each for a liquid in which ethanol and water were mixed one-to-one, then a liquid in which ethanol and ether were mixed in a one-to-one ratio, and finally, a liquid containing only ether. It was used for.
(2) Application of Sample A test piece was immersed in a sample solution adjusted to a concentration for performing a test for 10 seconds, and then water was dried with warm air.
(3) Test method The test piece on which the sample was applied was attached to an apparatus as shown in FIG. 3, and was heated at 60 ° C. for 24 hours and evaluated.
(4) Evaluation criteria No discoloration: A (including coloring by oil film)
Slight discoloration: B
Slight discoloration: C
Discoloration considerably: D
Significant discoloration: E

2. Test Results Table 3 shows the test evaluation results of the lubricant composition of the present invention. In addition, Table 4 shows the results of the evaluation, in which A and B were evaluated as Δ and CE was evaluated as (x).
According to the results, Formulation Examples 1-7, 13-1, and 13-2 were excellent in rust prevention properties against iron. On the other hand, Formulation Example 9 was excellent in rustproofness against aluminum but was inferior to copper, and Formulation Examples 10 and 11 and the commercial product were poor in rustproofness against both aluminum and copper.

(Discussion)
Table 4 shows the overall evaluation of the above test results. When any one of the aqueous solution stability, lubricity, and rust prevention was inferior (x), when all were excellent, it was expressed as (〇).
According to this comprehensive evaluation, Formulation Examples 1, 5, and 13 containing 20 to 60% of the polyoxyethylene alkyl ether calcium acetate of the present invention (alkyl group C16: 0 to C18: 1, EO 4 to 10 mol) in the active ingredient. -1, 13-2 were excellent in all of the aqueous solution stability, lubricity, and rust prevention, and the other formulations were inferior to any of them. Also, the commercial products were inferior to all.

  According to the present invention, as an extremely safe form of water solubility, both the lubricating property for reducing the frictional force generated on the frictional surface and the rust preventing effect for preventing the surface oxidation due to the frictional heat generated on the frictional surface are sufficiently provided. The present invention can provide a water-soluble lubricating rust inhibitor provided.

Claims (4)

A water-soluble lubricating rust inhibitor,
The above water-soluble lubricating rust inhibitor comprising a metal salt of polyoxyethylene alkyl ether acetic acid represented by the following general formula (2) , a water-soluble rust preventive component, and water.

2. The water-soluble lubricant according to claim 1 , wherein the water-soluble lubricant contains 20 to 60% of a metal salt of polyoxyethylene alkyl ether acetic acid in the active ingredient excluding water. The lubricant total composition, a water-soluble lubricant of claim 1 or 2 containing water of 50% or more.   The water-soluble lubricating rust inhibitor according to any one of claims 1 to 3, wherein the water-soluble lubricating rust inhibitor comprises at least one of a rust preventing component for aluminum, a rust preventing component for copper, and a rust preventing component for iron.

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