JP7270877B1 - Compositions for metalworking oils - Google Patents

Abstract

A metal working oil composition having a low kinematic viscosity and a high flash point is provided. Kind Code: A1 The present invention contains an ester of a fatty acid and an alcohol represented by the following formula (1) and/or an alcohol represented by the following formula (2), and the constituent fatty acid of the entire ester is oleic acid. is 20% by mass or more and less than 75% by mass, and the ratio of ester (b) whose constituent fatty acid is saturated fatty acid is more than 0% by mass and 6% by mass or less composition. In the following formula (1), m1 is an integer of 0-8. n1 is an integer from 0 to 8; p1 is an integer from 1 to 9; However, m1+n1+p1 is nine. In the following formula (2), m2 is an integer of 0-9. n2 is an integer of 0-9. p2 is an integer from 1 to 10; However, m2+n2+p2 is ten. JPEG0007270877000013.jpg44122 [Selection] None

Description

The present invention relates to compositions for metalworking oils.

In Patent Document 1, ester-containing compositions A to C obtained by performing an esterification reaction of a fatty acid mixture having an oleic acid content of 75% by mass or more and a C12/C13 mixed alcohol in Examples 1 to 3 have low It is disclosed that kinematic viscosity, high flash point and low pour point can all be achieved at high levels. In addition, from the relationship between the flash point, kinematic viscosity and pour point of Example Compositions A to C described in Table 2 of Patent Document 1, a fatty acid mixture containing oleic acid and a monovalent primary having 1 branch number It can be read that the lower the kinematic viscosity of the ester-containing composition with alcohol, the lower the flash point and the lower the pour point.

Non-Patent Document 1 discloses that whether the fatty acid constituting the ester is a saturated fatty acid or an unsaturated fatty acid does not affect the viscosity of the ester (Table 3 of Non-Patent Document 1). Therefore, it was thought that changing the ratio of saturated fatty acid and unsaturated fatty acid in the fatty acid constituting the ester would not affect the viscosity of the ester.

On the other hand, recently, the demand for low kinematic viscosity, more preferably low kinematic viscosity and high flash point, in metal working oil compositions is increasing.

Japanese Patent Application Laid-Open No. 2021-42352

Trends in Biodegradable Ester Hydraulic Fluids pp. 407-412 Tribologist Vol.59 No.7 2014

SUMMARY OF THE INVENTION It is an object of the present invention to provide a metal working oil composition with low kinematic viscosity. Preferably, it is an object of the present invention to provide a metal working oil composition with low kinematic viscosity and high flash point.

Considering the relationship between the kinematic viscosity, flash point and pour point of the ester-containing composition of the fatty acid mixture containing oleic acid and the monohydric primary alcohol having one branch number, described in the above background art, Patent Document 1 The lowest kinematic viscosity of 11.9 mm ² / s (composition C) (measurement temperature 40 ° C.) lower kinematic viscosity (measurement temperature 40 ° C.), a fatty acid mixture containing oleic acid and a monovalent If an attempt was made to make an ester-containing composition with a primary alcohol, it was expected that the ester-containing composition would have a flash point lower than that of composition C (254° C.) of US Pat. Therefore, it is difficult to prepare an ester-containing composition of a fatty acid mixture containing oleic acid and a monohydric primary alcohol having one branch, which has a kinematic viscosity of 11.9 mm ² /s or less and a flash point of over 254°C. It was considered.

As a result of extensive research, the present inventors have found that by using an ester of a fatty acid containing a specific ratio of oleic acid and saturated fatty acid and an alcohol having a specific molecular structure, a low kinematic viscosity, more preferably a highly flammable The present inventors have completed the present invention by discovering that a composition for metal working oil can be obtained.

（式（１）中、ｍ１は、０～８の整数である。ｎ１は、０～８の整数である。ｐ１は、１～９の整数である。但し、ｍ１＋ｎ１＋ｐ１は９である。）

（式（２）中、ｍ２は、０～９の整数である。ｎ２は、０～９の整数である。ｐ２は、１～１０の整数である。但し、ｍ２＋ｎ２＋ｐ２は１０である。） The invention made to solve the above problems contains an ester of a fatty acid and an alcohol represented by the following formula (1) and / or an alcohol represented by the following formula (2), and the composition of the ester as a whole The proportion of the ester (a) whose fatty acid is oleic acid is 20% by mass or more and less than 75% by mass, and the proportion of the ester (b) whose constituent fatty acid is a saturated fatty acid is more than 0% by mass and 6% by mass or less. It is a composition for metal working oil.

(In formula (1), m1 is an integer of 0 to 8. n1 is an integer of 0 to 8. p1 is an integer of 1 to 9. However, m1+n1+p1 is 9.)

(In formula (2), m2 is an integer of 0 to 9. n2 is an integer of 0 to 9. p2 is an integer of 1 to 10. However, m2 + n2 + p2 is 10.)

The metal working oil composition comprises, for example, a mixed fatty acid containing 20% by mass or more and less than 75% by mass of oleic acid and 0% by mass or more and 6% by mass or less of saturated fatty acid, an alcohol represented by the above formula (1), and / Or, it can be produced by subjecting it to an esterification reaction with the alcohol represented by the above formula (2).

More specifically, the present invention relates to the following inventions and the like.
[1] Ester (a ) is 20% by mass or more and less than 75% by mass, and the ratio of the ester (b) whose constituent fatty acid is a saturated fatty acid is more than 0% by mass and 6% by mass or less.
[2] The composition according to [1] above, wherein the ratio of the ester (a) to the entire ester is 30% by mass or more and less than 70% by mass.
[3] The composition according to [1] or [2] above, wherein the proportion of the ester (b1) in which the saturated fatty acid is stearic acid is 4% by mass or less relative to the entire ester.
[4] The composition according to any one of [1] to [3] above, wherein the total iodine value of the constituent fatty acids is 125 or more.
[5] The composition according to any one of [1] to [4] above, wherein the proportion of the ester (b2) in which the saturated fatty acid is palmitic acid is 2% by mass or less with respect to the entire ester.
[6] (A) Mixed fatty acid containing 20% by mass or more and less than 75% by mass of oleic acid and 0% by mass or more and 6% by mass or less of saturated fatty acid and (B) an ester of an alcohol represented by the above formula (1) ( i) and/or an ester (ii) of the mixed fatty acid and the alcohol represented by the above formula (2).
[7] The composition according to [6] above, wherein the mixed fatty acid contains 30% by mass or more and less than 70% by mass of oleic acid.
[8] The composition according to [6] or [7] above, wherein stearic acid in the mixed fatty acid is 4% by mass or less.
[9] The composition according to any one of [6] to [8] above, wherein the mixed fatty acid has an iodine value of 125 or more.
[10] The composition according to any one of [6] to [9] above, wherein the mixed fatty acid contains 2% by mass or less of palmitic acid.

The metal working oil composition of the present invention has a low kinematic viscosity (for example, a kinematic viscosity of 11.9 mm ² /s or less at 40° C.). Preferably, the metal working oil composition of the present invention has a low kinematic viscosity and a high flash point (for example, a kinematic viscosity of 11.9 mm ² /s or less at 40° C. and a flash point of greater than 254° C.). More preferably, in addition to the above, the pour point is low (eg -30° C. or lower). Therefore, the composition of the present invention can be suitably used as a metalworking oil or the like.

<Composition for metal working oil>
The composition contains an ester of a fatty acid and an alcohol represented by the above formula (1) and/or an alcohol represented by the above formula (2), and an ester whose constituent fatty acid is oleic acid with respect to the whole ester. Even if the ratio of (a) is 20% by mass or more and less than 75% by mass, and the ratio of the ester (b) whose constituent fatty acid is a saturated fatty acid to the entire ester is more than 0% by mass and 6% by mass or less good. The composition may contain optional components other than the ester as long as the effects of the present invention are not impaired.
In addition, the composition is an ester (i) of a mixed fatty acid containing 20% by mass or more and less than 75% by mass of oleic acid and 0% by mass or more and 6% by mass or less of a saturated fatty acid, and an alcohol (1), and / or It may contain an ester (ii) of the mixed fatty acid and the alcohol (2). The composition may contain optional components other than the ester (i) and/or the ester (ii) as long as the effects of the present invention are not impaired.
The composition can be used as a metal working oil composition such as cutting oil and lubricating oil.

Each component will be described below.

[Ester (a)]
In the ester (a), the constituent fatty acid is oleic acid, and the constituent alcohol is an alcohol represented by the above formula (1) (hereinafter also referred to as "alcohol (1)") and / or represented by the above formula (2) (hereinafter also referred to as “alcohol (2)”). “Oleic acid” means (Z)-9-octadecenoic acid. With respect to the entire ester contained in the composition, The proportion of the ester (a) is 20% by mass or more and less than 75% by mass, for example 20% by mass or more, 25% by mass or more, 30% by mass or more, 34% by mass or more, less than 75% by mass, 70% by mass or less, By selecting any dose from less than 70% by mass, 60% by mass or less, and 55% by mass or less and appropriately combining them, it is possible to apply the dose within a preferable range. is 25% by mass or more and 70% by mass or less, 30% by mass or more and less than 70% by mass, 30% by mass or more and 60% by mass or less, 34% by mass or more and 55% by mass or less, and the like.

(Alcohol (1))
Alcohol (1) is a compound represented by the following formula (1). Alcohol (1) is a monohydric primary alcohol having 12 carbon atoms and one branch. The "branch number" of alcohol refers to, for example, the number of branches in an alkyl chain, and is calculated by subtracting 1 corresponding to the terminal methyl group of the main chain from the number of methyl groups obtained by ¹ H-NMR analysis of alcohol. be able to.

In the above formula (1), m1 is an integer of 0-8. n1 is an integer from 0 to 8; p1 is an integer from 1 to 9; However, m1+n1+p1 is nine.

m1 is preferably from 1 to 8, more preferably from 2 to 8, and even more preferably from 4 to 8.

n1 is preferably 0 to 6, more preferably 0 to 5, even more preferably 0 to 3.

p1 is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

Examples of alcohol (1) include
Compounds in which p1 in the above formula (1) is 1, such as 2-methylundecan-1-ol, 2-ethyldecan-1-ol, 2-butyloctan-1-ol, and 2-pentylheptan-1-ol;
Compounds in which p1 in the above formula (1) is 2, such as 3-methylundecan-1-ol, 3-ethyldecan-1-ol, 3-butyloctan-1-ol, and 3-pentylheptan-1-ol;
4-methylundecane-1-ol, 4-ethyldecan-1-ol, 4-butyloctan-1-ol, 4-pentylheptan-1-ol, and the like, wherein p1 in the above formula (1) is 3, etc. mentioned.

Alcohol (1) can be produced, for example, by oxo reaction and hydrogenation of an α-olefin having 11 carbon atoms. As alcohol (1), one or a mixture of two or more thereof can be used.

(Alcohol (2))
Alcohol (2) is a compound represented by the following formula (2). Alcohol (2) is a monohydric primary alcohol having 13 carbon atoms and one branch.

In the above formula (2), m2 is an integer of 0-9. n2 is an integer of 0-9. p2 is an integer from 1 to 10; However, m2+n2+p2 is ten.

m2 is preferably from 1 to 9, more preferably from 2 to 9, and even more preferably from 4 to 9.

n2 is preferably 0 to 6, more preferably 0 to 5, even more preferably 0 to 3.

p2 is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

Examples of alcohol (2) include
Compounds in which p2 in the above formula (2) is 1, such as 2-methyldodecan-1-ol, 2-ethylundecane-1-ol, 2-butylnonan-1-ol, and 2-pentyloctan-1-ol;
Compounds in which p2 in the above formula (2) is 2, such as 3-methyldodecan-1-ol, 3-ethylundecane-1-ol, 3-butylnonan-1-ol, and 3-pentyloctan-1-ol;
Compounds such as 4-methyldodecan-1-ol, 4-ethylundecane-1-ol, 4-butylnonan-1-ol, and 4-pentyloctan-1-ol where p2 in the above formula (2) is 3, etc. mentioned.

Alcohol (2) can be produced, for example, by oxo reaction and hydrogenation of an α-olefin having 12 carbon atoms. As alcohol (2), one or a mixture of two or more thereof can be used.

Ester (a) can be obtained, for example, by subjecting alcohol (1) and/or alcohol (2) and oleic acid to an esterification reaction using tin oxide or the like as a catalyst.

The composition may contain one or more of them as the ester (a).

[Ester (b)]
In the ester (b), the constituent fatty acid is a saturated fatty acid, and the constituent alcohol is alcohol (1 and/or alcohol (2). The ratio of the ester (b) to the total ester contained in the composition is 0 More than 6% by mass and 5.2% by mass or less, and more than 0% by mass and 5.2% by mass or less are preferable because a low pour point can be achieved at a higher level.

(saturated fatty acid)
The "saturated fatty acid" preferably has 14 to 22 carbon atoms, more preferably 16 to 18 carbon atoms. The lower limit of the ratio of the ester (b) to the entire ester contained in the composition may be more than 0% by mass, may be 0.1% by mass or more, 1.0% by mass or more, 1 .4% by mass or more, or 1.5% by mass or more. By setting the ester (b) within the above range, it is preferable in that a low kinematic viscosity and a high flash point can be achieved at a higher level. The saturated fatty acid may be linear saturated fatty acid or branched saturated fatty acid, but linear saturated fatty acid is preferred. Specific examples of such straight-chain saturated fatty acids include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like, with palmitic acid and stearic acid being preferred. Examples of branched saturated fatty acids include isostearic acid, 2,2-dimethyloctanoic acid, 3-methylbutanoic acid, and the like.

(stearic acid)
By "stearic acid" is meant octadecanoic acid. When the composition contains an ester (hereinafter also referred to as ester (b1)) in which the saturated fatty acid is stearic acid, the content of ester (b1) with respect to the total ester contained in the composition is preferably It is 4.0% by mass or less, more preferably 3.7% by mass or less. The lower limit of the content of the ester (b1) with respect to the entire ester contained in the composition may be 0.1% by mass or more, 1.0% by mass or more, 1.4% by mass or more, and 1.0% by mass or more. 5 mass % or more may be sufficient. By setting the ester (b1) within the above range, it is preferable in that a low kinematic viscosity and a high flash point can be achieved at a higher level.

(palmitic acid)
"Palmitic acid" means hexadecanoic acid. When the composition contains an ester (hereinafter also referred to as ester (b2)) in which the saturated fatty acid is palmitic acid, the upper limit of the content of ester (b2) with respect to the entire ester contained in the composition is , preferably less than 3.0% by mass, more preferably 2.5% by mass or less, still more preferably 2.0% by mass or less, and particularly preferably 1.5% by mass or less. The lower limit of the content of the ester (b2) with respect to the entire ester contained in the composition may be 0.1% by mass or more, may be 0.5% by mass or more, or may be 1.0% by mass. % or more. By setting the ester (b2) within the above range, it is preferable in that a low kinematic viscosity and a high flash point can be achieved at a higher level.

Ester (b) can be obtained, for example, by subjecting alcohol (1) and/or alcohol (2) and saturated fatty acid to an esterification reaction using tin oxide or the like as a catalyst.

The composition may contain one or more of them as the ester (b).

The lower limit of the total content of ester (a) and / or ester (b) is preferably more than 20% by mass, more preferably 25% by mass or more, and 35% by mass or more, based on the total ester content in the composition. is more preferable, and 36% by mass or more is particularly preferable. The upper limit of the total content of ester (a) and/or ester (b) relative to the total ester content in the composition is, for example, 80% by mass or less, preferably 60% by mass or less.

[Ester (i)]
Ester (i) is an ester of an alcohol represented by formula (1) and a mixed fatty acid containing 20% by mass or more and less than 75% by mass of oleic acid and more than 0% by mass and 6% by mass or less of saturated fatty acid.

(oleic acid)
The content of oleic acid in the mixed fatty acid is 20% by mass or more and less than 75% by mass. % or less, less than 70% by mass, 60% by mass or less, or 55% by mass or less, and by appropriately combining them, it is possible to apply a dose within a preferable range. Specific examples of such a range include 25% by mass or more and 70% by mass or less, 30% by mass or more and less than 70% by mass, 30% by mass or more and 60% by mass or less, 34% by mass or more and 55% by mass or less. be done. Examples of commercially available products of mixed fatty acids containing oleic acid at the above content include "TFA-125" (trade name), "TFA-145WF" (trade name) (manufactured by Tsuno Foods Industry Co., Ltd.), " HARTALL (product name) FA-1 (manufactured by Harima Kasei Group Co., Ltd.) and the like.

(saturated fatty acid)
The saturated fatty acid content in the mixed fatty acid is more than 0% by mass and 6% by mass or less, preferably 5.2% by mass or less. By setting the saturated fatty acid content in the mixed fatty acid to 5.2% by mass or less, it is preferable in that a low pour point can be achieved at a higher level. The lower limit of the saturated fatty acid content in the mixed fatty acid may be more than 0% by mass, may be 0.1% by mass or more, 1.0% by mass or more, 1.4% by mass or more, It may be 1.5% by mass or more. By setting the saturated fatty acid within the above range, it is preferable in that a low kinematic viscosity and a high flash point can be realized at a higher level.

(mixed fatty acid)
"Mixed fatty acid" is a mixture containing two or more fatty acids, and contains at least 20% by mass or more and less than 75% by mass of oleic acid and more than 0% by mass and 6% by mass or less of saturated fatty acid. Mixed fatty acids, for example, can also be referred to as fatty acid mixtures. Fatty acids other than oleic acid and saturated fatty acids contained in mixed fatty acids are not particularly limited, but examples thereof include linoleic acid and linolenic acid. When linoleic acid is included in the mixed fatty acid, the content of linoleic acid is not particularly limited, but the upper limit is 60.0% by mass or less, 57.0% by mass or less, 56.5% by mass or less, and the like. may When the mixed fatty acid contains linoleic acid, the lower limit may be 20.0% by mass or more, 30.0% by mass or more, 33.0% by mass or more, or 33.1% by mass or more. When the mixed fatty acid contains linolenic acid, the content of linolenic acid is not particularly limited, but the upper limit is 12.5% by mass or less, 12.0% by mass or less, 10.0% by mass or less. It may be 0% by mass or less, 7.5% by mass or less, or the like. The lower limit when the mixed fatty acid contains linolenic acid is 0.1% by mass or more, 1.0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, 6.0% by mass or more, It may be 7.0% by mass or more. Moreover, it is preferable that the mixed fatty acid as a whole has an iodine value of 125 or more. Preferable commercial products of mixed fatty acids include, for example, "TFA-125" (trade name), "TFA-145WF" (trade name) (manufactured by Tsuno Foods Industry Co., Ltd.), and "Hartall HARTALL" (trade name). product number FA-1 (manufactured by Harima Kasei Group Co., Ltd.).

Ester (i) can be obtained, for example, by subjecting alcohol (1) and mixed fatty acid to an esterification reaction using tin oxide or the like as a catalyst.

The lower limit of the content of the ester (i) is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the entire composition. . The upper limit of the content of the ester (i) is preferably less than 100% by mass, more preferably 99% by mass or less, still more preferably 98% by mass or less, and particularly preferably 90% by mass or less, relative to the entire composition. . By setting the content of the ester (i) within the above range, a low kinematic viscosity, preferably a high flash point can be achieved at a higher level.

The composition may contain one or more of them as ester (i).

[Ester (ii)]
Ester (ii) is an ester of alcohol (2) with the above mixed fatty acids.

The ester (ii) can be obtained, for example, by subjecting the alcohol (2) and the mixed fatty acid to an esterification reaction using tin oxide or the like as a catalyst.

The lower limit of the content of the ester (ii) is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, and 30% by mass or more, relative to the entire composition. Especially preferred. The upper limit of the content of the ester (ii) is preferably 99% by mass or less, more preferably 90% by mass or less, further preferably 75% by mass or less, and particularly preferably 60% by mass or less, relative to the entire composition. . By setting the content of the ester (ii) within the above range, a low kinematic viscosity, preferably a high flash point can be achieved at a higher level.

The composition may contain one or more as ester (ii).

Alcohols containing alcohol (1) and/or alcohol (2) are preferably α-olefin-derived alcohols, that is, alcohols produced from α-olefins by oxo reaction, hydrogenation, or the like. Alcohols derived from butene or alcohols derived from propylene, that is, alcohols produced by oxo reaction, hydrogenation, etc. from olefins obtained by polymerization of butene or propylene usually have a branch number of 1.5 to 2.9. Alcohol. Such an ester of a multi-branched alcohol having more than 1 branch and the above-mentioned constituent fatty acid or the above-mentioned mixed fatty acid increases the kinematic viscosity of the composition and lowers the flash point.

Examples of commercially available alcohol products containing alcohol (1) and alcohol (2) include “ISALCHEM”, “ISOFOL”, and “SAFOL” (manufactured by SASOL).

(iodine value)
The iodine value refers to the amount of halogen absorbed by 100 g of fat and oil expressed in grams of iodine. The higher the proportion of unsaturated fatty acids, the higher the iodine value. The iodine value can be measured, for example, according to "2.3.4.1-1996 Iodine value (Wiiss-cyclohexane method)" of "Standard oil analysis test method (edited by Japan Oil Chemistry Society)". The iodine value of all the constituent fatty acids or the iodine value in the mixed fatty acid is not particularly limited, but may be, for example, 125 or more, preferably 128 or more. By setting the iodine value within the above range, it is preferable in that a low kinematic viscosity and a high flash point can be achieved at a higher level.

When the metal working oil composition contains ester (i) and ester (ii), the ratio of ester (i) and ester (ii) is ester (i) / ester (ii) (mass ratio) The lower limit of the . The upper limit of ester (i) / ester (ii) (mass ratio) is preferably 99.9/0.1 or less, more preferably 99/1 or less, further preferably 95/5 or less, and particularly 90/10 or less. preferable. By setting the ratio of the ester (i) to the ester (ii) within the above range, a low kinematic viscosity, preferably a high flash point can be achieved at a higher level.

The lower limit of the total content of ester (i) and/or ester (ii) is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more, relative to the total ester content in the composition. is more preferable, and 95% by mass or more is particularly preferable. The upper limit of the total content of ester (i) and/or ester (ii) relative to the total ester content in the composition is, for example, 100% by mass or less, preferably 99% by mass or less. By "ester" is meant an ester of an alcohol with a fatty acid.

The lower limit of the total content of ester (a) and / or ester (b) or the total content of ester (i) and / or ester (ii) is 30% by mass or more with respect to the entire composition. is preferred, 50% by mass or more is more preferred, 70% by mass or more is even more preferred, 80% by mass or more is particularly preferred, 90% by mass or more is particularly preferred, and 95% by mass or more is most preferred. The upper limit of the content of the total ester (a) and/or ester (b) or the total ester (i) and/or ester (ii) with respect to the entire composition is, for example, 100% by mass or less. , 99% by mass or less.

The respective ratios of the constituent fatty acid and the constituent alcohol of the ester can be confirmed by hydrolyzing the ester to separate it into a fatty acid mixture and an alcohol mixture, and then analyzing each by gas chromatography. In addition, when all of the raw material fatty acids (including each fatty acid in the mixed fatty acid) are considered to have been used in the esterification reaction, and when the ester contained in the composition is only the ester obtained by the reaction Alternatively, the ratio of the constituent fatty acids of the ester in the composition may be the same as the ratio of each fatty acid in the raw material. Moreover, the ratio of the constituent fatty acids of the ester can be confirmed by the mixing ratio of the esters (a), (b), and (c), which will be described later. Using the above ratio, the ratio of each ester (e.g., esters (a), (b), (c), (i), (ii) described later, (iii) described later, etc.) to the entire ester, the composition The ratio of each ester (for example, esters (a), (b), (c), (i), (ii) described later, (iii) described later, etc.) to the whole can be derived.

[Optional component]
Optional components include, for example, esters other than ester (i) and/or ester (ii) (hereinafter referred to as ester (iii)), or esters other than ester (a) and/or ester (b) (hereinafter referred to as Also referred to as "ester (c)"), additives and the like. The composition can contain one or more optional ingredients.

(Ester (iii))
Esters (iii) include, for example, esters of branched dodecyl alcohol or linear dodecyl alcohol having more than 1 branch and mixed fatty acid, branched tridecyl alcohol or linear tridecyl alcohol having more than 1 branch and mixed fatty acid, and esters of alcohols other than alcohol (1) and alcohol (2) such as esters of fatty acids.

When the composition contains ester (iii), the upper limit of the content of ester (iii) is preferably 50% by mass or less, more preferably 30% by mass or less, relative to the total ester in the composition. , is more preferably 10% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of ester (iii) is, for example, 0.1% by mass or more with respect to the entire ester in the composition.

When the composition contains the ester (iii), the upper limit of the content of the ester (iii) is preferably 50% by mass or less, more preferably 20% by mass or less, and 5% by mass with respect to the entire composition. % or less is more preferable, and 5% by mass or less is particularly preferable. The lower limit of the content of the ester (iii) is, for example, 0.1% by mass or more with respect to the entire composition.

(Ester (c))
Examples of the ester (c) include esters of alcohol (1) with fatty acids other than oleic acid and saturated fatty acids, esters of alcohol (2) with fatty acids other than oleic acid and saturated fatty acids, alcohols (1) and alcohols ( Examples include esters of alcohols other than 2) with fatty acids other than oleic acid and saturated fatty acids.

When the composition contains the ester (c), the upper limit of the content of the ester (c) is preferably less than 80% by mass, 70% by mass or less, and 65% by mass with respect to the entire ester in the composition. % or less. The lower limit of the content of the ester (c) is, for example, preferably more than 19% by mass, more than 20% by mass, 30% by mass or more, 40% by mass or more, etc. with respect to the entire ester in the composition. good.

When the composition contains the ester (c), the upper limit of the content of the ester (c) is preferably 80% by mass or less, 70% by mass or less, 55% by mass or less, etc. with respect to the entire composition. may be The lower limit of the content of the ester (c) is, for example, 0.1% by mass or more relative to the entire composition.

If the composition contains ester (iii) or ester (c), the sum of ester (i), ester (ii) and ester (iii) or ester (a), ester (b) and ester (c) The lower limit of the content is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more, relative to the entire composition. The upper limit of the total content of ester (i), ester (ii) and ester (iii) or ester (a), ester (b) and ester (c) is, for example, 100 mass with respect to the entire composition %, preferably 99.9% by mass or less, more preferably 99% by mass or less.

(Additive)
As additives, known additives can be used, for example, phenolic antioxidants; metal deactivators such as benzotriazole, thiadiazole and dithiocarbamate; acid scavengers such as epoxy compounds and carbodiimide; Phosphorus-based extreme pressure agents; pour point depressants such as polyalkyl methacrylates (eg, ACLUBE 132, ACLUBE 146, etc.);

When the composition contains an additive, the upper limit of the content of the additive is preferably 30% by mass or less, more preferably 10% by mass or less, and further 5% by mass or less, relative to the entire composition. preferable.

The composition may be substantially free of additives and consist substantially of esters. A composition "substantially free of additives" means, for example, that the total content of additives is less than 5% by mass. The composition "substantially consists of an ester" means, for example, that the total content of the ester (a), the ester (b) and the ester (c) is 95% by mass or more, or that the ester (i), It means that the total content of ester (ii) and ester (iii) is 95% by mass or more.

The upper limit of the kinematic viscosity of the composition at 40° C. is preferably less than 14.0 mm ² /s, more preferably less than 13.5 mm ² /s, less than 13.4 mm ² /s, and more preferably less than 13.0 mm ² /s. , less than 12.8 mm ² /s, less than 12.7 mm ² /s, less than 12.5 mm ² /s, less than 12.4 mm ² /s, less than 12.0 mm ² /s, less than 11.9 mm ² /s, 11 More preferably less than 0.9 mm ² /s. The lower limit of the kinematic viscosity of the composition at 40° C. is, for example, 8.0 mm ² /s or more, 10.0 mm ² /s or more, preferably 11.0 mm ² /s or more. By setting the kinematic viscosity of the composition within the above range, it is possible to further improve precision, cooling performance, and the like in metal working and the like.

Kinematic viscosity can be measured, for example, according to JIS K-2283.

The lower limit of the flash point of the composition is preferably 240°C or higher, more preferably 250°C or higher, still more preferably 254°C or higher, and particularly preferably 255°C or higher, 258°C or higher, and 264°C or higher. The upper limit of the flash point of the composition is, for example, 280° C. or lower, preferably 272° C. or lower. By setting the flash point of the composition within the above range, the safety can be further improved, and deterioration of the working environment such as stains and odor caused by volatile oil during use can be further improved.

The flash point can be measured, for example, by the Cleveland open cup method according to JIS K-2265.

The upper limit of the pour point of the composition is preferably -20°C or lower, more preferably -25°C or lower, still more preferably -30°C or lower, and particularly preferably -35°C or lower. The lower limit of the pour point of the composition is, for example, −60° C. or higher, preferably −50° C. or higher, and −40° C. or higher. By setting the pour point of the composition within the above range, it is more difficult to solidify even in a low-temperature environment, and heating equipment becomes unnecessary.

Pour point can be measured, for example, according to JIS K-2269.

Preferably, the composition has a low kinematic viscosity and a high flash point. Although there are no particular limitations on the combination of the values of the kinematic viscosity and the flash point, for example, the kinematic viscosity is 11.9 mm ² /s or less at 40°C, the flash point is about 254°C or higher, and the kinematic viscosity is 12 at 40°C. 0.8 mm ² /s or less and a flash point greater than about 264° C., or a kinematic viscosity at 40° C. of less than 12.4 mm ² /s and a flash point of about 258° C. or greater. More preferably, in addition to the above, the pour point is low (for example, −30° C. or lower). Considering the common general knowledge that when the kinematic viscosity of an ester-containing composition of a fatty acid mixture containing oleic acid and a monohydric primary alcohol having one branch is low, the flash point is low and the pour point is low. , the combination of the kinematic viscosity and the flash point, more preferably the combination of the kinematic viscosity, the flash point and the pour point can be said to have an unexpectedly remarkable effect from Patent Document 1.

The upper limit of the hydroxyl value of the composition is preferably 2 mgKOH/g, more preferably 1 mgKOH/g. The lower limit of the hydroxyl value of the composition is, for example, 0 mgKOH/g, preferably 0.1 mgKOH/g.

The "hydroxyl value" can be determined, for example, by a conventional method for measuring a hydroxyl value. It can also be determined by measuring the amount.

[Method for producing composition]
The composition can be produced, for example, by a production method comprising an esterification step of reacting alcohol (1) and/or alcohol (2) with a mixed fatty acid to obtain an ester.
In addition, the composition includes, for example, an esterification step of reacting alcohol (1) and/or alcohol (2) with oleic acid to obtain an ester, alcohol (1) and/or alcohol (2), and saturated It can be produced by a production method comprising an esterification step of reacting with a fatty acid to obtain an ester, and a mixing step of mixing the esters obtained in these steps.

The method for producing the composition may further include, after the esterification step, a step of removing low boiling point components from the obtained ester to obtain an esterified crude product (hereinafter also referred to as "low boiling point component removal step"). Preferably, after the step of removing low-boiling-point components, a step of treating the resulting crude esterification product with a treating agent (hereinafter also referred to as “treatment step”) may be further included.
After the esterification step, the raw material fatty acid may be in a state where it is considered that all the fatty acids have been used in the esterification reaction. In such a case, the ratio of each constituent fatty acid in the resulting ester may be the same as the ratio of each starting fatty acid.
Each step will be described below.

(Esterification step)
In this step, an alcohol component containing alcohol (1) and/or alcohol (2) is mixed with fatty acids such as mixed fatty acids, oleic acid, and saturated fatty acids, and if necessary, a catalyst is added and heated to produce The esterification reaction is carried out while removing water.

The equivalent ratio between the alcohol component and the fatty acid component is preferably 0.8 to 1.5 mol as the fatty acid component per 1 mol of the alcohol component, and 0.9 to 1.2 from the viewpoint of production efficiency and economy. Mole is more preferred. The number of moles of alcohol (1) and alcohol (2) in the alcohol component is determined by measuring the area ratio (GC%) of alcohol (1) and alcohol (2) by gas chromatography analysis of the alcohol component, and 2- It can be calculated by using the factor of butyl-1-octanol.

Examples of catalysts include acid catalysts such as sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid, and metal catalysts containing elements such as titanium, zirconium, hafnium, tin and zinc. The amount of the catalyst used is preferably 0.01 to 10% by mass, more preferably 0.05 to 1% by mass, based on the total amount of alcohol component and fatty acid component.

The lower limit of the esterification reaction temperature is preferably 160° C. or higher, more preferably 200° C. or higher, still more preferably 215° C. or higher, and particularly preferably 230° C. or higher. The upper limit of the temperature for the esterification reaction is, for example, 240° C. or lower, preferably 235° C. or lower.

The esterification reaction may be carried out under normal pressure or under reduced pressure, preferably under reduced pressure from the viewpoint of easy removal of generated water. The lower limit of the pressure during decompression is, for example, 1 Torr or more, preferably 10 Torr or more, and more preferably 50 Torr or more. The upper limit of the pressure during decompression is, for example, 200 Torr or less, preferably 150 Torr or less.

The lower limit of the esterification reaction time is preferably 10 minutes or longer, more preferably 30 minutes or longer, still more preferably 1 hour or longer, and particularly preferably 2 hours or longer. The upper limit of the esterification reaction time is preferably 24 hours or less, more preferably 12 hours or less, still more preferably 8 hours or less, and particularly preferably 5 hours or less.

The esterification reaction is preferably carried out, for example, while measuring the acid value of the reaction solution. 3 mgKOH/g or less is more preferable. The acid value can be measured, for example, according to JOCS (Japan Oil Chemistry Society) 2.3.1.

(Low boiling point component removal step)
In this step, low-boiling components are removed from the obtained ester to obtain an esterified crude product. The term "low boiling point component" as used herein includes free alcohol (1), free alcohol (2), and free fatty acid.

Specifically, in this step, low boiling point components are distilled off at a temperature of 170° C. to 230° C. under reduced pressure of more than 0 Torr and less than or equal to 100 Torr.

(Processing process)
In this step, the resulting esterified crude product is treated with a treating agent.

Examples of the treating agent include activated carbon and activated clay. The amount of the treating agent to be used is generally 0.01 to 5% by mass, preferably 0.1 to 1% by mass, relative to the crude esterification product.

As a treatment method, for example, a treatment agent is added to the esterified crude product, stirred at 50° C. to 100° C. for about 10 minutes to 2 hours, then stirred under reduced pressure for about 10 minutes to 2 hours, and then treated. A method of removing the agent by filtration, and the like.

In this disclosure, the terms "extent" and "about" are terms intended to include, for example, minor deviations. Such ranges are also included within experimental error inherent in standard methods used to measure and/or quantify a given value or range.

In order to remove excess free fatty acids in the esterified crude product, for example, a fatty acid neutralization and purification step with an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. may be performed. It doesn't have to be.

The present invention includes modes in which the above configurations are combined in various ways within the technical scope of the present invention as long as the effects of the present invention are exhibited.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples, and many modifications can be made in the art within the technical spirit of the present invention. It is possible by a person with ordinary knowledge.

The acid value of the reaction solution of the esterification reaction in the production of the compositions of Examples and Comparative Examples was measured according to JOCS (Japan Oil Chemistry Society) 2.3.1.

<Production of composition>
The “C12/C13 mixed alcohol” used in Examples 1 to 3 is a mixture of α-olefin-derived alcohol with 12 carbon atoms (alcohol (1)) and alcohol with 13 carbon atoms (alcohol (2)).
Table 1 shows the product name, iodine value, and content of constituent fatty acids of the "mixed fatty acids" used in Examples 1 to 3 and Comparative Examples 1 and 2.

Regarding the whole alcohol (mixture of 12 carbon atoms and 13 carbon atoms, C12/C13 mixed alcohol) used in the production of the compositions in Examples 1 to 3 and Comparative Examples 1 and 2, alcohol (1) and alcohol (2) The content ratio (GC %) was measured by gas chromatography analysis. GC measurement conditions are shown below. Moreover, the measurement results are shown in Table 2 below.

(GC measurement conditions)
Apparatus: "GC-2014" by Shimadzu Corporation
Column: "DB-1HT" from Agilent Technologies
Column temperature: 70°C (2 minutes) → heating rate 10°C/min → 350°C (5 minutes)
Sample volume: 1 μL
Carrier gas: helium (total flow rate 57.8 mL/min)
Injection condition: split (split ratio 50)
Injection temperature: 350°C
Detector: FID

[Example 1]
Mixed fatty acid (trade name “TFA-125”, manufactured by Tsuno Foods Industry Co., Ltd.) 380 g, C12/C13 mixed alcohol 313 were added to a 1 L four-necked flask equipped with a stirrer, a thermometer and a Dean-Stark tube with a condenser. 9 g and 0.1% by mass of tin oxide as a catalyst were added, and the temperature was raised to 230° C. in a nitrogen atmosphere. After reaching 230° C., the pressure was reduced, and the esterification reaction was carried out while removing the distilled water with a Dean-Stark tube. The reaction was terminated when the acid value became 1.0 mgKOH/g or less. After completion of the reaction, excess alcohol and low-boiling components were distilled off to obtain an esterified crude product. 0.2% by mass of activated carbon and activated clay were added to the resulting esterified crude product, and the mixture was stirred at 80° C. for 30 minutes and then stirred under reduced pressure for 1 hour. After that, the pressure was returned to normal pressure and filtered to remove them to obtain composition A.

[Example 2]
In a 1 L four-necked flask equipped with a stirrer, a thermometer and a Dean-Stark tube with a cooling tube, 380 g of the same mixed fatty acid as in Example 1 (trade name "TFA-125", manufactured by Tsuno Foods Industry Co., Ltd.), 2 300 g (1.61 mol) of -butyl-1-octanol, 6.0 g of C12/C13 mixed alcohol, and 0.1% by mass of tin oxide as a catalyst were added, and the temperature was raised to 230°C under a nitrogen atmosphere. . After reaching 230° C., the pressure was reduced, and the esterification reaction was carried out while removing the distilled water with a Dean-Stark tube. The reaction was terminated when the acid value became 1.0 mgKOH/g or less. After completion of the reaction, excess alcohol and low-boiling components were distilled off to obtain an esterified crude product. 0.2% by mass of activated carbon and activated clay were added to the resulting esterified crude product, and the mixture was stirred at 80° C. for 30 minutes and then stirred under reduced pressure for 1 hour. After that, the pressure was returned to normal pressure, and they were removed by filtration to obtain composition B.

[Example 3]
Mixed fatty acid (trade name “TFA-145WF”, manufactured by Tsuno Foods Industry Co., Ltd.) 380 g, C12/C13 mixed alcohol 313 were added to a 1 L four-necked flask equipped with a stirrer, a thermometer and a Dean-Stark tube with a condenser. 9 g and 0.1% by mass of tin oxide as a catalyst were added, and the temperature was raised to 230° C. in a nitrogen atmosphere. After reaching 230° C., the pressure was reduced, and the esterification reaction was carried out while removing the distilled water with a Dean-Stark tube. The reaction was terminated when the acid value became 1.0 mgKOH/g or less. After completion of the reaction, excess alcohol and low-boiling components were distilled off to obtain an esterified crude product. 0.2% by mass of activated carbon and activated clay were added to the resulting esterified crude product, and the mixture was stirred at 80° C. for 30 minutes and then stirred under reduced pressure for 1 hour. After that, the pressure was returned to normal pressure, and they were removed by filtration to obtain composition C.

[Comparative Example 1]
380 g of mixed fatty acid (trade name “Evyap Oleo O-1875”, manufactured by Evyap) and 313.9 g of C12/C13 mixed alcohol were added to a 1 L four-necked flask equipped with a stirrer, a thermometer and a Dean-Stark tube with a condenser. , and tin oxide as a catalyst were charged in an amount of 0.1% by mass based on the total amount, and the temperature was raised to 230° C. in a nitrogen atmosphere. After reaching 230° C., the pressure was reduced, and the esterification reaction was carried out while removing the distilled water with a Dean-Stark tube. The reaction was terminated when the acid value became 1.0 mgKOH/g or less. After completion of the reaction, excess alcohol and low-boiling components were distilled off to obtain an esterified crude product. 0.2% by mass of activated carbon and activated clay were added to the resulting esterified crude product, and the mixture was stirred at 80° C. for 30 minutes and then stirred under reduced pressure for 1 hour. After that, the pressure was returned to normal pressure and filtered to remove them to obtain composition D.

[Comparative Example 2]
Composition E was obtained in the same manner as in Comparative Example 1, except that the product name "NAS-125" (manufactured by Tsuno Foods Industry Co., Ltd.) was used as the mixed fatty acid.

Ratio of ester (a) whose constituent fatty acid is oleic acid, ratio of ester (b1) whose constituent fatty acid is stearic acid, and ester whose constituent fatty acid is palmitic acid, in each composition of A to E, relative to the total ester The ratio of (b2), the ratio of ester (c1) whose constituent fatty acid is linoleic acid, and the ratio of ester (c2) whose constituent fatty acid is linolenic acid (all units are % by mass) were as shown in Table 3 below. .

<Evaluation>
Various analyzes of the compositions obtained in Examples and Comparative Examples were performed according to the following methods.

Kinematic viscosity: Measured according to JIS K-2283.
Flash point: Measured by the Cleveland open cup method according to JIS K-2265.
Pour point: Measured according to JIS K-2269.

The kinematic viscosity (mm ² /s), flash point (° C.) and pour point (° C.) of the compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 4 below.

As is clear from the results in Table 4, the compositions of Examples were able to achieve a high level of low kinematic viscosity. Furthermore, the compositions of Examples were able to achieve a high flash point at a high level.

The compositions of the present invention are useful as metalworking oils.

Claims (4)

The ratio of the ester (a) containing an ester of a fatty acid and an alcohol represented by the following formula (1) and an alcohol represented by the following formula (2), wherein the constituent fatty acid is oleic acid, relative to the entire ester is 34 % by mass or more and 60 % by mass or less , the ratio of the ester (b) whose constituent fatty acid is a saturated fatty acid is more than 0% by mass and 6% by mass or less, and the saturated fatty acid is stearic acid ( The ratio of b1) is 1.5% by mass or more and 4% by mass or less, the ratio of the ester (b2) in which the saturated fatty acid is palmitic acid is 1% by mass or more and less than 3% by mass, and the constituent fatty acid is linoleic acid. The ratio of a certain ester is 30% by mass or more and 56.5% by mass or less, the ratio of the ester whose constituent fatty acid is linolenic acid is 6% by mass or more and 8% by mass or less, and the formula of the constituent alcohol of the entire ester A composition for metal working oil , wherein the mass ratio of alcohol represented by (1)/alcohol represented by formula (2) is from 40/60 to 95/5.

(In formula (1), m1 is an integer of 0 to 8. n1 is an integer of 0 to 8. p1 is an integer of 1 to 9. However, m1+n1+p1 is 9.)

(In formula (2), m2 is an integer of 0 to 9. n2 is an integer of 0 to 9. p2 is an integer of 1 to 10. However, m2 + n2 + p2 is 10.) 2. The composition according to claim 1 _, wherein the total iodine value of the constituent fatty acids is 125 I2 g/100 g or more. (A) 34 % by mass to 60 % by mass of oleic acid based on the total amount of mixed fatty acids , 0% by mass to 6% by mass of saturated fatty acids , 1.5% by mass to 4% by mass of stearic acid, and palmitic acid A mixed fatty acid containing 1% by mass or more and less than 3% by mass, 30% by mass or more and 56.5% by mass or less of linoleic acid, and 6% by mass or more and 8% by mass or less of linolenic acid;
(B) an ester (i) with an alcohol represented by the following formula (1) and an ester (ii) between the mixed fatty acid and an alcohol represented by the following formula (2),
A composition for metal working oil , wherein the mass ratio of ester (i)/ester (ii) is from 40/60 to 95/5 .

(In formula (1), m1 is an integer of 0 to 8. n1 is an integer of 0 to 8. p1 is an integer of 1 to 9. However, m1+n1+p1 is 9.)

(In formula (2), m2 is an integer of 0 to 9. n2 is an integer of 0 to 9. p2 is an integer of 1 to 10. However, m2 + n2 + p2 is 10.) _4. The composition of claim 3 , wherein the mixed fatty acid has an iodine value of 125 I2 g/100 g or greater.