JPH06271880A - Lubricant composition for metal - Google Patents

Abstract

PURPOSE:To obtain the subject new composition useful due to have a good balance between chemical/physical properties and lubricating oil properties, containing ester(s) composed of a specific butanetetracarboxylic acid or its anhydride, etc., as a base oil. CONSTITUTION:This lubricant composition contains, as base oil, at least one kind of ester of formula I and/or II [R<1>-R<4> are each H, alkyl, alkenyl or (un)saturated alicyclic hydrocarbon group; R<5>-R<8> are each the sane as R<1>-R<4> and formula III (R<9> is R<1>-R<4>, etc.; AO is 2-4C oxyalkylene group; (m) is 0-100), wherein R<1>-R<4> are not H at the same time, at least one of R<5>-R<8> has oxyalkylene group] selected from 1,2,3,4-butanetetracarboxylic acid or its anhydride and at least one kind of hydroxy compound selected from aliphatic alcohols (e.g. methyl alcohol, ethyl alcohol), alicyclic alcohols (e.g. cyclohexyl alcohol, cydecanol) and phenolic compounds (e.g. phenol, benzyl alcohol).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel oil agent composition for metals.

[0002]

2. Description of the Related Art Generally, ester-based synthetic lubricating oils are superior in thermal stability, oxidation stability, and low-temperature fluidity to mineral oil-based lubricating oils, have little change in viscosity with temperature, and other synthetic lubricating oils. Due to its well-balanced properties compared to oil (polyolefin, polyether, etc.), it has been widely used in various fields such as engine oil, instrument oil, pump oil and the like in recent years.

However, recently, the equipment using lubricating oil has been remarkably developed, and the lubricating oil is required to have a performance capable of being used under more special or severe conditions than ever. Therefore, under the present circumstances, in order to prepare these lubricating oils and metal oils, ester base oils having new properties according to their respective uses are required.

[0004] For example, in the field of refrigerating machines, as a countermeasure to the recent ozone layer depletion problem, there is an active movement to use CFCs containing no chlorine as a refrigerant. This refrigerant has a significantly higher polarity than conventional freon and does not dissolve in existing oil agents (for example, naphthenic mineral oil), so there is a need for an ester oil that dissolves without impairing lubricating performance.

Further, the proportion of water-based lubricating oil in metal oil agents is increasing year by year because of its nonflammability and environmental awareness, and there is a demand for a new base oil which can meet various demands accompanying it.

[0006] For example, butyl stearate contained in a certain type of water-based lubricating oil is rancid in water and its acid value increases, so that a biodegradable ester is required, and conversely. In some cases, a base oil component that biodegrades and disappears after being used as a lubricating oil is required.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel and useful metal oil agent composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, found that an ester having a specific structure has a chemical property and a physical property in good balance with lubricity. And is found to be an ester base oil that can constitute a metal oil agent composition having desired performance,
The present invention has been completed based on these findings.

That is, the oil agent composition for metals according to the present invention is
It is characterized by containing, as a base oil, one or more kinds of esters represented by the general formula (1) or the general formula (2) (hereinafter referred to as "present ester").

[0010]

[Chemical 4] [Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group or a saturated or unsaturated alicyclic hydrocarbon group. Represent However, R ¹ , R ² , R ³ and R ⁴ are not hydrogen atoms at the same time. ]

[0011]

[Chemical 5] [Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group, a saturated or unsaturated alicyclic hydrocarbon group, or

[Chemical 6] Represents a group represented by. R ⁹ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group, a saturated or unsaturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group. AO represents an oxyalkylene group having 2 to 4 carbon atoms. m represents an integer of 0 to 100. However, R ⁵ , R ⁶ , R
^At least one of ⁷ and R ⁸ has an oxyalkylene group. ]

The ester is 1,2,3,4-butanetetracarboxylic acid (hereinafter abbreviated as "BTC") or an acid anhydride thereof (hereinafter collectively referred to as "BTC").
One or more alcohols selected from the group consisting of the aliphatic alcohols or alicyclic alcohols represented by the general formula (3) and the phenols represented by the general formula (4) are usually used. Prepared by esterification according to.

[0013]

[Chemical 7] [In the formula, R ¹⁰ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group, or a saturated or unsaturated alicyclic hydrocarbon group. AO represents alkylene having 2 to 3 carbon atoms. m represents an integer of 0 to 100. ]

[0014]

[Chemical 8] [In the formula, R ¹¹ represents a hydrogen atom or an aromatic hydrocarbon group.
AO represents alkylene having 2 to 3 carbon atoms. n is 0 to 10
Represents an integer of 0. ]

As the BTCs, BTC alone may be used, or BTC monoanhydride or dianhydride may be used.

As the aliphatic alcohol represented by the general formula (3), a linear or branched saturated or unsaturated aliphatic alcohol having 1 to 36 carbon atoms is recommended. Alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol,
Hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eico Sil alcohol, heneicosyl alcohol,
Examples thereof include saturated alcohols such as docosyl alcohol and dimerized alcohols of aliphatic alcohols having 8 to 18 carbon atoms, allyl alcohol, unsaturated alcohols such as oleyl alcohol and fish oil alcohol, and alkylene oxide adducts thereof.

The number of carbon atoms of alcohol is not particularly problematic in terms of performance even if it is more than this, but it is difficult to obtain because it is industrially undesirable.

Examples of the alicyclic alcohol represented by the general formula (3) include cyclohexyl alcohol, cyclohexenyl alcohol, sidecanol, hydrogenated sideanol and their alkylene oxide adducts.

Examples of the phenols represented by the general formula (4) include phenol, benzyl alcohol, methylbenzyl alcohol, and alkylene oxides of phenol compounds having an alkyl group having 1 to 18 carbon atoms such as cresol, xylenol and nonylphenol. An adduct is illustrated.

Examples of the alkylene oxide include ethylene oxide (EO), propylene oxide (PO), butylene oxide and the like, and examples of the adduct include individual adducts and co-adducts thereof.

When a mixed ester is desired, two or more kinds of predetermined raw material alcohols may be used together at the time of charging, or if necessary, another raw material alcohol is added after partial esterification. It may be esterified. When BTC monoanhydride or dianhydride is selected for the partial esterification reaction, it is often effective in terms of operation and performance during production.

The present ester having at least one non-hydrocarbon group has ethylene glycol, diethylene glycol, triethylene glycol as an alcohol component,
It is prepared by esterification using a poly or oligo alkylene oxide such as tetraethylene glycol or by addition reaction of the alkylene oxide directly to the carboxyl group. The ester exhibits a self-emulsifying property.

The type of alcohol selected in preparing the ester is determined by the desired properties.

For example, if importance is attached to the viscosity index, it is preferable to select a long-chain alcohol. This is because the viscosity index tends to depend on the longest distance between ester molecules.
However, a branched alcohol is preferable when a room temperature liquid lubricating oil is required because an ester prepared from a linear higher alcohol may be solid.

Further, if importance is attached to sludge resistance, it is preferable to use an alcohol having a large addition mole number of alkylene oxide (for example, an addition product of about 5 to 100 moles).

If a base oil having good biodegradability is required, it is preferable to select an aliphatic alcohol having 1 to 20 mol of alkylene oxide added. On the other hand, if a base oil that does not rancid is required, it is preferable to select an alcohol to which an alkylene oxide is not added.

As a lubricating oil used for a refrigerating machine which uses a CFC containing no chlorine as a refrigerant, an alcohol having a high branching degree or an alcohol having a small addition mole number of alkylene oxide (for example, an adduct of about 1 to 5 moles) is used. It is preferable to select it.

The present ester is used alone as a base oil for a lubricating oil, and a general-purpose mineral oil, other synthetic oils, and various additives can be appropriately used in combination depending on the performance to be emphasized.

Here, examples of the mineral oil include those generally known as lubricating base oils such as naphthenic and paraffinic oils.

As synthetic oils, polyolefin, various diesters, hindered esters, polyphenyl ethers,
Examples thereof include polyalkylene glycol, phosphoric acid ester, silicic acid ester, silicone oil and fluoroester.

As various additives, antioxidants, detergents, extreme pressure agents, oiliness agents, rust inhibitors, viscosity index improvers, pour point depressants, antiwear agents, corrosion inhibitors, metal deactivators. , Various additives such as defoaming agents and emulsifiers can be appropriately added.

As the extreme pressure agent, chlorine-based paraffins, chlorinated fatty acid methyl esters, chlorinated fatty acids and other chlorine-based agents, sulfurized mineral oils, sulfurized oils and fats, sulfated oils and fats, sulfur compounds such as various disulfides, phosphates and phosphites. Phosphorus-based,
Examples thereof include organic metal compounds such as zinc thiophosphate, molybdenum thiophosphate and molybdenum carbamate, and solid lubricants such as graphite and molybdenum sulfide.

Examples of rust preventives include carboxylates such as oleate and benzoate, sulfonates, amines such as triethanolamine, oleic acid diethanolamide, alkenyl succinic acid amide, and adipic acid cyclohexylamide. Amides, organic rust inhibitors such as esters such as sorbitan monooleate, and inorganic rust inhibitors such as nitrite, phosphate, borate, molybdate, tungstate, carbonate, etc. You can

Examples of the non-ferrous metal anticorrosive agent include nitrogen compounds such as benzotriazole and imidazoline, sulfur nitrogen compounds such as thiodiazole polysulfide and alkylthioimidazole, and zinc dialkyldithiophosphate.

As the pour point depressant, glycols such as ethylene glycol and propylene glycol may be mentioned.

As the thickener, polyalkylene glycols, polyethyleneimines, HEC, HPC, CMC
Examples thereof include cellulose derivatives such as sodium polycarboxylate, polyvinylpyrrolidone, and alginic acid.

Examples of preservatives include phenolic compounds such as o-phenylphenol, tetrachlorophenol, p-chloro-m-xylenol, formaldehyde donors such as hexahydrotriazine, and mixtures of tribromosalicylanilide and dibromosalicylanilide. Can be raised.

As the defoaming agent, polyalkylene glycol, silicon emulsion, higher alcohol, fluorine compound and the like can be mentioned.

As the emulsifier, nonylphenol, higher alcohols, ethylene oxide adduct of hydrogenated castor oil,
Propylene oxide adducts, polyhydric alcohols such as sorbitan monofatty acid esters, nonionic surfactants such as alkylylamides such as fatty acid diethanolamides, fatty acid and fatty acid soaps, fatty acid derivatives such as naphthenic acid soaps, animal and vegetable oils, long Anionic surfactants such as sulfuric acid ester type such as chain alcohol sulfuric acid ester, phosphoric acid ester type such as long chain alcohol phosphoric acid ester, and sulfonic acid type such as petroleum sulfonate may be mentioned.

Further, it is effective to use an inorganic salt or amine salt of the present ester as one kind of anionic surfactant. In particular, the monoester, diester, triester and salts thereof relating to the present ester are also effective as a metal scavenger, so that they may be intentionally left as an unreacted mixture during the reaction.

The content of these additives is selected within the range that does not impair the object of the present invention and according to its use.

This ester is used as a general hydraulic oil.
Further, it can be widely used as a component of metal working oil such as rolling oil, grinding cutting oil, press oil, drawing oil, quenching oil and the like.

[0043]

EXAMPLES The present invention is described in detail below with reference to examples. The characteristics of this ester were measured and evaluated by the following methods.

Lubrication performance: Kinematic viscosity, viscosity index, and pour point were comprehensively evaluated and evaluated in four grades of excellent, ⊚, ◯, Δ, and ×.

Kinematic viscosity: JIS using a Ubbelohde viscometer
It was measured according to K 2283.

Viscosity index: Calculated according to JIS K 2284 from kinematic viscosities at 40 ° C and 100 ° C.

Pour point: measured according to JIS K 2269.

Compatibility with refrigerant: 0.2 g of a predetermined ester and a hydrogen-containing CFC refrigerant (HFC-134a) in a glass tube.
2.0 g was collected and enclosed. This glass tube was placed in a low temperature tank or a high temperature tank having a predetermined temperature, and the compatibility between the refrigerant and the predetermined ester was observed.

Sludge resistance: A predetermined ester is used as a lubricating oil in the driving part of a cylinder type liquid feed pump,
After operating for 0 hour, the lubricating oil was taken out and the generation of sludge therein was visually confirmed.

Resistance to rancidity: 0.1 ml of activated sludge, 0.2 ml of a predetermined ester, and a 2% aqueous solution of polypeptone were put in a test tube and cultured at 30 ° C. for 14 days under rich nutrition and aerobic conditions. Then, the solution in the test tube is extracted with hexane, and the amount of a predetermined ester is analyzed.

Easy biodegradability: The biodegradability was observed with an activated sludge concentration of 30 ppm and a predetermined ester of 100 ppm. No organic substances other than the above two are added, and an aqueous solution of potassium phosphate, sodium phosphate, ammonium chloride, magnesium sulfate, calcium chloride, and iron chloride is used as a basic culture solution.
It was cultured at 5 ° C for 28 days. The biodegradation rate (1) of a given ester is calculated from the oxygen absorption amount of the culture solution. Further, the filtrate of the culture broth is burned to measure the total oxygen requirement, and the biodegradation rate (2) of a given ester is calculated.

Example 1 The lubricating performance of a tetraester of BTC and n-octanol (this ester A) was evaluated. The results obtained are shown in Table 1. Also, when the acid rancidity of this product was evaluated, no change was observed in the amount. Furthermore, the biodegradation rate of this product was 1% or less.

Example 2 The lubricating performance of a tetraester of BTC and isostearyl alcohol (the present ester B) was comprehensively evaluated. The results obtained are shown in Table 1.

Example 3 The lubrication performance of a tetraester (main ester C) of BTC with an EO2 mol adduct of 2-ethylhexanol was evaluated. The results obtained are shown in Table 1. Further, the temperature range in which this compound was compatible with the refrigerant was -30 to 60 ° C.

Example 4 The lubrication performance of a tetraester (main ester D) of BTC with a 4-molar PO adduct of 2-ethylhexanol was evaluated. The results obtained are shown in Table 1. Further, the temperature range in which this compound was compatible with the refrigerant was −35 to 70 ° C.

Example 5 When the lubrication performance of a tetraester (main ester E) of BTC and EO6 mol adduct of lauryl alcohol was evaluated, the same level of performance as main ester C was obtained. In addition, when the sludge resistance of this product was evaluated, the formation of sludge was not recognized. Furthermore, the biodegradation rate (1) of this product was 95%, and the biodegradation rate (2) was 90%.

Example 6 When the lubrication performance of the tetraester (main ester F) of BTC and EO50 mol adduct of butyl alcohol was evaluated, the same level of performance as the main ester C was obtained. In addition, when the sludge resistance of this product was evaluated, the formation of sludge was not recognized.

Comparative Example 1 The lubricating performance of paraffinic mineral oil was evaluated. The results obtained are shown in Table 1. When the sludge resistance of this product was evaluated, the formation of sludge was recognized.

Comparative Example 2 The naphthenic mineral oil was not compatible with the refrigerant.

Comparative Example 3 The lactic acid resistance of butyl stearate was evaluated. as a result,
This one did not survive.

[0061]

EFFECT OF THE INVENTION By using the ester oil according to the present invention, it is possible to obtain a base oil for a novel metal oil agent having desired properties having chemical properties and physical properties in good balance with lubricity. You can Patent applicant Shin Nippon Rika Co., Ltd.

[Table 1]

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[Procedure amendment]

[Submission date] March 7, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

Comparative Example 3 The acid resistance of butyl stearate was evaluated. as a result,
This one did not survive.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshifumi Fujitani 13 Yakura-cho, Yashima-jima, Fushimi-ku, Kyoto-shi, Kyoto

Claims (1)

[Claims] 1. An oil agent composition for metals, comprising one or more esters represented by the general formula (1) or the general formula (2) as a base oil. [Chemical 1] [Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group or a saturated or unsaturated alicyclic hydrocarbon group. Represent However, R ¹ , R ² , R ³ and R ⁴ are not hydrogen atoms at the same time. ] [Chemical 2] [Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a linear or branched alkyl group or alkenyl group, a saturated or unsaturated alicyclic hydrocarbon group, or [Chemical 3] Represents a group represented by. R ⁹ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group, a saturated or unsaturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group. AO represents an oxyalkylene group having 2 to 4 carbon atoms. m represents an integer of 0 to 100. However, R ⁵ , R ⁶ , R
^At least one of ⁷ and R ⁸ has an oxyalkylene group. ]