JPS63117099A - Additive for emulsion-type lubricant - Google Patents

Abstract

PURPOSE:To provide the title additive which is useful for preparing an emulsion- type lubricant having excellent emulsifying, bactericidal, wear-resistant and defoaming properties and undergoing little performance lowering during the usage thereof and which comprises a particular compd. such as octylphenoxyacetic acid. CONSTITUTION:The title additive is obtd. from a compd. (e.g., octylphenoxyacetic acid) of the formula (wherein R<1>-R<3> are each H or a 6-30C, n is 1 or 2, and X is H, Li, Na, K, Mg, Ca, Ba, NH4, or an amine- neutralized N-ammonium group, provided that R<1>-R<3> are not simultaneously H), optionally together with another type of additive added thereto according to necessity. This additive is added to a mixture of a base oil, such as a mineral oil, a synthetic oil, an animal oil, or a vegetable oil having a dynamic viscosity (100 deg.C) of 1.5-50cst, water, etc., thereby preparing an emulsion-type lubricant.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to additives used in emulsified lubricants, and more specifically, the present invention relates to additives used in emulsified lubricants, and more specifically, the present invention relates to additives used in emulsified lubricants, and more particularly, The present invention relates to an additive for emulsified lubricants that has the following properties and exhibits little performance deterioration during use.

The additive for emulsified lubricants of the present invention can be used in lubricants such as rolling oils, cutting oils, grinding oils, and rolling fluids.

[Prior art and its problems] Generally, emulsified lubricants are required to have various performances such as emulsifying ability, sterilization resistance, anti-wear performance, and antifoaming performance.

In conventional emulsion type lubricants, additives have been used to obtain these various performances.

However, conventionally used emulsifiers, disinfectants,
Additives such as anti-wear agents and anti-foaming agents are all single-sided, and if they are used in combination, for example, emulsifiers may reduce the bactericidal ability and anti-abrasion properties of the residue. In addition, they often degrade the performance of each other, and satisfactory performance has not been achieved.

On the other hand, a lubricant (abrasive) using an alkylphenoxyalkylene carboxylate as a multifunctional additive has been proposed (see Japanese Patent Publication No. 81-21513).

However, since the alkylphenoxyalkylene carboxylate having an alkyl group having 3 to 4 carbon atoms does not have an emulsifying moat, there is a problem that it is not suitable as an additive for an emulsifying type lubricant.

[Purpose of the invention] This invention has been made based on the above circumstances.

That is, an object of the present invention is to provide an additive for emulsified lubricants that has emulsifying ability, sterilization properties, wear resistance properties, and antifoam properties, and which exhibits little performance deterioration during use.

In order to achieve the above object, the inventor conducted various studies and found that an additive containing a specific compound satisfies the above object, and thus arrived at the present invention No. 11JI.

[Means for Solving the Problems] The outline of the present invention for solving the problems and achieving the objects is as follows: [1F] (wherein R1, R2, R3 is a hydrogen atom or has 6 to 3 carbon atoms
0 hydrocarbon group, n is an integer of 1 or 2, and X is H, Li, Na, Mg, Ca, Ba.
, NH43, which represents an amine-neutralized N-ammonium group; however, R1, R2, and R3 are not all hydrogen atoms at the same time). It is an additive for

The compound represented by the formula [1] is 1lil, R2, R
At least one of 3 is a hydrocarbon group having 6 to 30 carbon atoms, and this hydrocarbon group may be either linear or branched, and may be saturated or unsaturated. Among hydrogen groups, particularly preferred are alkyl groups having 7 to 12 carbon atoms.

Examples of compounds in which X in the formula [1] is a hydrogen atom (hereinafter, the [A] acid component may be abbreviated) include hexylphenoxyacetic acid, heptylphenoxyacetic acid,
Octylphenoxyacetic acid, nonylphenoxyacetic acid, decylphenoxyacetic acid, undecylphenoxyacetic acid, dodecylphenoxyacetic acid, tridecylphenoxyacetic acid, tetradecylphenoxyacetic acid, pentadecylphenoxyacetic acid,
hexadecylphenoxyacetic acid, heptadecylphenoxyacetic acid, octadecylphenoxyacetic acid, nonadecylphenoxyacetic acid, eicosylphenoxyacetic acid, tocosylphenoxyacetic acid m, hlycosylphenoxyacetic acid, tetradecylphenoxyacetic acid, bentacosylphenoxyacetic acid, Examples include hexacosylphenoxyacetic acid, hexacosylphenoxyacetic acid, heptadecylphenoxyacetic acid, ophtacosylphenoxyacetic acid, nonadecylphenoxyacetic acid, triacosylphenoxyacetic acid, and the like. Among these, preferred is phenoxyacetic acid substituted with an alkyl group having 6 to 10 carbon atoms, and particularly preferred are octylphenoxyacetic acid, hexylphenoxyacetic acid, and nonylphenoxyacetic acid.

These may be used alone or in combination of two or more.

In the formula [1] above, X is Li, Na, Mg, Ca
, Ba, NH4 group, and amine-neutralized N-an-+==um group can be obtained by reacting the [A] acid component with the alkali compound. This alkali compound (hereinafter referred to as [B
] ff1 min) is an inorganic alkali compound such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide; jetanolamine, triethanolamine, etc. Alkanolamine, hexylamine, isohexylamine, heptylamine, 2-hebutylamine, octylamine, dioctylamine, diheptylamine, di-2-heptylamine, dioctylamine, di-2-octylamine, N-methyl-hexylamine,
Alkylamines such as N-methyl-hebutylamine, N-methyl-octylamine, N-(hydroxymethyl)piperazine, N-(hydroxymethyl)-1-methylbiperazine, N-(2-hydroxyethyl)piperazine, N
-(2-hydroxypropyl)piperazine, N-(2-
Examples include organic alkali compounds such as cyclic amines such as hydroxymethyl-1-methylpiperazine. Among these, alkanolamines and piperazine compounds are preferred, particularly jetanolamine, N-(2-hydroxyethyl)piperazine and N~(2-hydroxypropyl)
Piperazine is preferred.

These alkali compounds may be used alone or in combination of two or more.

The emulsified lubricating oil additive of the present invention may be composed of only the [A] acid component, or may be composed of a reaction product of the [A] acid component and the [B] acid component. However, the reaction product described in @ is more suitable.

In order to obtain a reaction product between the [A] acid component and the [CB] component, the [A] acid component and the [B] acid component are usually mixed together at a temperature of room temperature to 80'C. B] is 1:0
They may be blended at a ratio of 10 to 10 (molar ratio), preferably 0.5 to 5 (molar ratio).

The emulsified lubricant in the present invention can be produced by blending the [A] acid component represented by the formula [11] with base oil, other additives, and water as necessary.

The emulsified lubricant of the present invention can be produced by blending the [A] acid component, the [B] acid component, a base oil and other additives added as necessary, and water.

The base oil (hereinafter sometimes abbreviated as [C] acid component) is not particularly limited, and any of mineral oils, synthetic oils, animal and vegetable oils, etc. can be used, but among these, 100 ° C. It is preferable that the kinematic viscosity is 1.5 to 50 cst.

The other additives (hereinafter sometimes abbreviated as [D] acid component) include emulsifiers, bactericidal agents, oily agents, de-foaming agents, antioxidants, extreme pressure agents, detergents, viscosity modifiers, and rust-preventing agents. Additives commonly added to lubricants can be used, such as stopping additives. In addition, other additives may be added as necessary.
For example, amines such as jetanolamine, water repellents such as organic silicon compounds, adhesives such as polymethacrylate, anti-separation agents such as glyceride, colorants such as azo or anthraquinone dyes, etc. are added. You can also.

As the emulsifier, any of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be used. It is also possible to use a mixed emulsifier such as a mixture of a nonionic surfactant and an ionic surfactant. That is, various emulsifiers (surfactants) that are incorporated into known additives for emulsified lubricating oils can be used.

More specifically, for example, soaps such as natural fatty acid sodium salts; synthetic soaps such as synthetic higher fatty acid sodium salts; alkyl sulfate ester salts such as alkyl sulfate sodium salt and oleyl M acid ester sodium salt; alkylbenzene sulfonic acids. Alkylaromatic sulfonic acid salts such as sodium salts and sodium alkylna-2-talenesulfonates; anionic surfactants such as sodium dialkylsulfosuccinate; cationic surfactants such as quaternary amine salts such as alkyltrimethylammonium halides; Agent: polyoxyethylene alkyl ether,
Nonionic surfactants such as polyoxyethylene fatty acid ester, polyoxyethylene alkyl phenyl ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol ester, sucrose fatty acid ester, alkyltrimethylaminoacetic acid, alkyldiethylenetriacetate, etc. Examples include amphoteric surfactants such as minoacetic acid.

Examples of the disinfectant include hydroxybenzene,
Phenols such as cresol, thymol, resorcinol, hydroquinone, pyrogallol, and hydroxyhydroquinone, triazoles, imidazoles, and pyridine derivatives can be used.

Examples of the oily agents include higher alcohols, higher ketones, higher amines, and metal soaps.

Examples include long chain compounds having polar groups such as fats and oils.

As the anti-foaming agent, for example, silicone oil (organic silicone polymer such as polymethylsiloxane) or the like can be used.

The antioxidants include, for example, 2.6-ditertiarybutoxy para-cresol, tetramethyldiaminodiphenylmethane, phenothiazine, zinc dialkyldithiophosphate, α-pinene-P2S5, ft-terpene, 2.2°-methylenebis(4- Methyl-6-tert-butylphenol), 4,4'-methylenebis(
2,6-ditertiarybutylphenol), N, N
”-di-sec-butyl-p-phenylenediamine,
2. Aromatic amine-based antioxidants such as 2°-thiobis(4-methyl-6-tert-butylphenol), dialkyldithiophosphate-based antioxidants, phosphorous compound-based antioxidants, phosphorus compound-based antioxidants A variety of things can be used, such as:

Examples of the extreme pressure agent include chlorine compound-based extreme pressure agents,
Any of sulfur compound-based extreme pressure agents, phosphorus-containing compound-based extreme pressure agents, etc. can be used.

Examples of the detergent include multipolar polymer detergents, alkenyl succinimides, petroleum-based calcium sulfonates, basic barium sulfonates, sulfurized phenols, carponate salts, dichlorinated polyolefin detergents, thiophosnates, and the like. be able to.

Examples of the viscosity modifier include viscosity index improvers such as polybutene and polymethacrylate, pour point depressants such as chlorinated paraffin naphthalene condensate: polymethacrylate, and the like.

Examples of the anti-rust additive include sulfonate salts, amines, organic acids or salts thereof.

Examples include compounds having various polar groups such as esters.

These various additives may be used alone.

Two or more types may be used in appropriate combination.

The emulsified lubricant is a stock solution (the above-mentioned [AI component or [A
] Acid component A reaction product of the above [B] acid component, with the above [C] acid component and/or the above [D] acid component added as necessary, and with or without the addition of a small amount of water) It is common to first manufacture and then use the stock solution as it is or diluted with water, so the amount of the [A] acid component [B] acid component [C] acid component [01 component] It cannot be determined in general.

A preferable blending ratio can be defined as follows.

That is, [A] acid component [B] acid component [C] acid component [D
] and water, for jX liquid, [A] acid component 1-10% by weight, [B] acid component 0-15% by weight, [
C] Acid component 50-85% by weight, [D] Acid component 5-50@
%, and water is 0-10% by weight.

It is preferable to use the emulsified lubricant of the present invention by diluting a stock solution having such a blending ratio with water 2 to 100 times.

To obtain an emulsified lubricant in this invention.

There are no particular restrictions on the order and method of blending the [A] acid component [B] acid component [C] acid component [DJ component] with water, but for example, the following method is preferably used.

That is, an alkali compound (if the above [B] acid component is not used, the [A] acid component and if necessary, the [CI component and [D] IJt component are blended, and this blend is blended with water. .

In addition, when using an alkali compound, [A] seismic fraction,
[B] Acid component and optionally [C] component and [0] may be blended together, and this blend and water may be blended.
In addition, the above-mentioned [AI acid component [B] acid component is blended, and the
At a temperature of 80°C, [Al IO & min and [B] r! [C] IR, min and [C]
D] The acid component may be blended, and then water may be blended.

When the additive for emulsified lubricants of the present invention is added to an emulsified lubricant containing water, the lubricant can simultaneously obtain emulsifying ability, sterilizing ability, wear resistance performance, and antifoaming performance.

[Effects of the Invention] Unlike conventional additives, the additive for emulsified lubricants of the present invention is a compound that has multiple functions such as emulsification ability, sterilization ability, wear resistance performance, and antifoaming performance. Because there is
The number or type of conventional additives added simultaneously to an emulsified lubricant can be reduced or reduced.

Therefore, according to the present invention, a new emulsifying lubricant is provided which is excellent in emulsifying properties, sterilizing ability, wear resistance performance, antifoaming performance, etc., and which can prevent a decrease in performance due to interaction between additives. Additives can be provided.

[Examples] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention.

(Examples 1 to 4. Comparative Examples 1 to 3) A stock solution was prepared by blending each component shown in Table 1 in the indicated ratio (weight percentage), and then this stock solution was diluted 30 times with water. An emulsified lubricant was prepared.

Each of the emulsified lubricants thus obtained was examined for emulsion stability, bactericidal properties, antifoaming properties, and rust prevention properties.

The results are summarized in Table 1.

Moreover, the evaluation method used is as follows.

Emulsion stability: The sample liquid was left standing in a 100 mJL graduated cylinder, and the state of oil separation in the sample liquid was observed after one month.

Bactericidal properties: N lubricant was inoculated with aerobic bacteria, enotrophic JIIJ bacteria, sulfuric acid reducing bacteria, mold, and yeast, and kept at 30°C for 14 days.

After culturing, the number of viable bacteria in each country is measured and the degree of reproduction (degree of difficulty in spoiling) is evaluated. That is, dilute the lubricant 50 times with tap water, collect 20ml of it in a test tube, and then add 200mg of casting chips and 1 liter of putrid oil to the test tube.
Add the drops and statically culture under the above conditions. In addition, the following culture medium culture method was adopted for each microorganism to measure the number of viable bacteria after culture.

(1) Aerobic bacteria (agar plate method, broth) medium composition:
Meat extract 0.5%, peptone! , 0%, sodium chloride 0.5%, agar 1.5% (pH 7,0) (2) Anaerobic bacteria (roll tube method using VL basal medium) Medium composition: peptone 1.0%, yeast extract 0 .5%, heart extract 0.14%, glucose 0.2%, potassium dihydrogen phosphate 0.045%, potassium hydrogen phosphate 0.0
8%, ammonium sulfate 0.08%, sodium chloride 0.09%, magnesium sulfate (anhydrous salt) o, oos%, calcium chloride (anhydrous salt) 0.09%, agar 1.5%, cysteine hydrochloride 0.4 % (pH 7,0) (3) Sulfuric acid reduction iJ (
Roll tube method) Starkey medium [American φ type φ culture collection 12th edition, p. 331 (1
978)] with 1.5% agar added.

(4) Mold, yeast (agar plate method) Potato dextrose agar medium: Potato infusion 200 gel, glucose 200g 1 sentence,
The number of viable bacteria when adding 15 g of agar/soil (pH 4,0) and putrid oil is as follows.

Aerobic bacteria 2. 3 OXIO/ml anaerobic bacteria 1. I X1G4 pieces/ml sulfate-reducing bacteria 5.
3 x 102 pieces/m mold 3. OX
1G2 pieces/ml yeast 1.5
X1G4 pieces/m! L Anti-foaming property: Pour the sample solution into a 100 m measuring cylinder, shake vigorously 50 times to create foam, then let it stand still and measure the time (seconds) until the foam disappears (cylinder method) ) Using an end mill tool on a rust-proof two-drilling machine, FCD-
This process involves cutting 40 materials using sample oil (cutting fluid).
After machining, the rust occurrence status of the cut material is observed for 7 days, and the rust prevention ability of the cutting fluid is evaluated.

(Hereinafter referred to as "margin") In Comparative Example 2, when 12% by weight of the emulsifier was blended, no emulsification occurred. In other words, in Comparative Example 2, a good emulsion cannot be obtained unless a large amount of emulsifier is blended.

As is clear from Table 1, the number of carbon atoms is at least 6.
A phenoxyacetic acid that substitutes ~10 alkyl groups
The emulsified lubricant blended as a component is a Ja-rich type lubricant that is excellent in emulsion stability, sterilizing properties, antifoaming properties, and rust prevention properties. In particular, the one according to Example 4 is excellent in multimotaxis. Comparative Examples 1 to 3 do not have multiple base runners like Examples 1 to 4.

Claims (1)

[Claims] (1) The following general formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (However, in the above formula [1], R^1, R^2, R^3 are hydrogen atoms or the number of carbon atoms. represents 6 to 30 hydrocarbon groups,
n represents an integer of 1 or 2, X represents H, Li
, Na, K, Mg, Ca, Ba, NH_4 group, and amine-neutralized N-ammonium group. In addition, R^1, R^2,
All of R^3 cannot be hydrogen atoms at the same time. )
An additive for emulsified lubricants characterized by containing a compound represented by: