JP2023135795A - Fatty acid ester mixture - Google Patents

Abstract

To provide a novel fatty acid ester mixture.SOLUTION: The mixture contains a fatty acid ester (A) with a pour point FA, and a fatty acid ester (B) with a pour point FB equal to or less than FA, and has a pour point FT less than FA. The hydroxyl value HA of the fatty acid ester (A) and the hydroxyl value HB of the fatty acid ester (B) are both equal to or less than 45.SELECTED DRAWING: None

Description

The present invention relates to fatty acid ester mixtures and the like.

Pour point depressants are known to lower the pour point of lubricating oil compositions containing ester base oils and widen the applicable temperature range of the lubricating oil compositions (see, for example, Patent Document 1). . However, in the method of lowering the pour point by adding a pour point depressant to fatty acid ester, there is a possibility that performance other than the pour point may be adversely affected, and the pour point depressant may react with other additives and cause sludge. Since there is a risk of the formation of additives, it was necessary to use different additives depending on the base oil.

JP 2021-20993 Publication

An object of the present invention is to provide a novel fatty acid ester mixture.

In order to solve the above problems, the present inventors have repeatedly conducted numerous trials and errors and conducted intensive research. By selecting fatty acid esters to be mixed based on specific conditions (indicators), the present inventors have succeeded in improving the flow rate in the mixture. They discovered that it is possible to lower the pour point (at least lower than the pour point of the fatty acid ester which has the maximum pour point), conducted further intensive research, and completed the present invention.

The present invention relates to the following inventions, etc.
[1]
A mixture containing a fatty acid ester (A) having a pour point FA and (one or more) fatty acid esters (B) having a pour point FB less than or equal to FA, and having a pour point FT less than FA (fatty acid ester mixture) A mixture in which the hydroxyl value HA of the fatty acid ester (A) and the hydroxyl value HB of the fatty acid ester (B) are both below a predetermined value (for example, 45 or less).
[2]
The mixture according to [1], wherein both HA and HB are 42 or less.
[3]
The mixture according to [1] or [2], wherein the absolute value of the difference between HA and HB (HA-HB) is 40 or less.
[4]
Total hydroxyl value (hydroxyl value of the entire mixture, hydroxyl value of the total amount of fatty acid ester (A) and fatty acid ester (B), hydroxyl value of the entire fatty acid ester) HT is 40 or less, any of [1] to [3] A mixture as described in Crab.
[5]
The mixture according to any one of [1] to [4], wherein the difference between FA and FB (FA-FB) is 32°C or less.
[6]
Total hydroxyl number of fatty acid ester (A) and fatty acid ester (B) [the number of hydroxyl groups in the alcohol that constitutes the fatty acid ester (A) (the alcohol that is the raw material for the fatty acid ester) is X, and the number of hydroxyl groups that constitute the fatty acid ester (B) The mixture according to any one of [1] to [5], wherein the total number of X and Y is 5 or more, where Y is the number of hydroxyl groups in the alcohol (alcohol serving as a raw material for fatty acid ester).
[7]
The mixture according to any one of [1] to [6], wherein FT is less than FB.
[8]
The mixture according to any one of [1] to [7], wherein the difference between FA and FT (FA-FT) is 1° C. or more.
[9]
HA and HB are both 35 or less,
The absolute value of the difference between HA and HB is 30 or less,
Total hydroxyl value HT is 25 or less,
The difference between FA and FB is 30℃ or less,
The total hydroxy number of the fatty acid ester (A) and the fatty acid ester (B) is 5 or more,
The difference between FB and FT (FB-FT) is 1°C or more,
The mixture according to any one of [1] to [8], wherein the difference between FA and FT (FA-FT) is 2°C or more.
[10]
The mixture according to any one of [1] to [9], wherein both HA and HB are 25 or less, the total hydroxyl value HT is 15 or less, and the difference between FA and FB is 25° C. or less.
[11]
The mixture according to any one of [1] to [10], which is a lubricating oil (for lubricating oil).
[12]
An additive that is mixed with a fatty acid ester (A) having a pour point FA and a hydroxyl value HA of 45 or less to make the pour point FT of the mixture less than FA,
An additive (pour point depressant) composed of a fatty acid ester (B) having a pour point FB of FA or lower and a hydroxyl value HB of 45 or lower.
[13]
A method for reducing the pour point FT of a mixture containing a fatty acid ester (A) having a pour point FA and a hydroxyl value HA of 45 or less, comprising:
A fatty acid ester (B) [an additive (pour point depressant) composed of] having a pour point FB of FA or lower and a hydroxyl value HB of 45 or lower is mixed with the fatty acid ester (A). A method of mixing (adding) B).
[14]
The absolute value of the difference between HA and HB (HA-HB) is 40 or less,
The total hydroxyl value HT is 40 or less, the difference between FA and FB (FA-FB) is 32°C or less,
The agent or method according to [12] or [13], wherein the fatty acid ester (A) and the fatty acid ester (B) have a total hydroxy number of 5 or more.
[15]
The agent or method according to any one of [12] to [14], wherein FT is less than FB and the difference between FA and FT (FA-FT) is 1° C. or more.
[16]
HA and HB are both 35 or less,
The absolute value of the difference between HA and HB is 30 or less,
Total hydroxyl value HT is 25 or less,
The difference between FA and FB is 30℃ or less,
The total hydroxy number of fatty acid ester (A) and fatty acid ester (B) is 5 or more,
The difference between FB and FT (FB-FT) is 1°C or more,
The agent or method according to any one of [12] to [15], wherein the difference between FA and FT (FA-FT) is 2°C or more.

According to the present invention, a novel fatty acid ester mixture can be provided.
In such a fatty acid ester mixture, the pour point of the mixture can be efficiently lowered by selecting the fatty acid esters to be mixed (combined) under specific conditions and indicators.

The pour point of a mixture is usually lower than the maximum pour point of the fatty acid esters making up the mixture, and below the minimum pour point of the fatty acid esters making up the mixture (especially at a temperature below the minimum pour point) It can also be lowered to .

Since the fatty acid ester mixture of the present invention can be composed of fatty acid esters, the pour point can be lowered without using components other than fatty acid esters such as pour point depressants.
Therefore, the pour point can be lowered while efficiently maintaining (exhibiting) the performance (function) as a fatty acid ester, which is useful.
Furthermore, since they are fatty acid esters, they are useful in that there are relatively few restrictions on their combinations.

[Fatty acid ester mixture (composition)]
The fatty acid ester mixture (hereinafter sometimes simply referred to as a mixture) of the present invention includes a fatty acid ester (A) and a fatty acid ester (B).

Here, the fatty acid ester (A) is one type of fatty acid ester, and its pour point (hereinafter referred to as FA) is the highest among the fatty acid esters contained in the fatty acid ester mixture (usually 1 fatty acid esters).

On the other hand, fatty acid ester (B) is a fatty acid ester different from fatty acid ester (A). In addition, the pour point (hereinafter referred to as FB etc.) of the fatty acid ester (B) may be such that the pour point of the fatty acid ester (A) is the maximum (that is, it may be FM or less), and as described below, , may indicate a specific pour point in relation to the FA.

That is, the fatty acid ester (B) may be selected depending on the relationship with the fatty acid ester to be combined, and is not uniformly determined by the chemical species of the fatty acid ester.

For example, depending on the fatty acid ester combined, it can become fatty acid ester (A) [For example, when combined with a fatty acid ester having a lower pour point, it becomes fatty acid ester (A) (fatty acid ester having a lower pour point) becomes fatty acid ester (B)].

In addition, when combining fatty acid esters having the same pour point, any fatty acid ester may be used as the fatty acid ester (A).

In addition, the fatty acid ester (B) may be one type or two or more types as long as it has FB less than FA. That is, in the fatty acid ester mixture, the number of constituent fatty acid esters may be two or more, or three or more.

In the mixture of the present invention, fatty acid esters constituting the mixture can be selected based on specific indicators and conditions.

First, in the mixture, the hydroxyl value of the fatty acid ester (A) (hereinafter referred to as HA etc.) and the hydroxyl value of the fatty acid ester (B) (hereinafter referred to as HB etc.) may be usually specified. Note that the hydroxyl value is defined as the number of mg of potassium hydroxide (mgKOH/g) corresponding to hydroxyl groups in 1 g of sample.

For example, both HA and HB may be 45 or less (HA is 45 or less and HB is 45 or less). In such a case, both HA and HB (each) may be 45 or less, preferably 43 or less (e.g., 42 or less), preferably 40 or less (e.g., 38 or less, 37 or less), and more preferably 36 or less. (for example, 35 or less), 32 or less (for example, 30 or less, 28 or less, 27 or less, 26 or less, 25 or less, 22 or less, 20 or less, 18 or less, 16 or less, 15 or less, 13 or less , 12 or less, 10 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less), etc.

Note that the lower limit of the hydroxyl value (HA and HB, respectively) is not particularly limited, and may be 0, or a finite value (for example, 0.05, 0.1, 0.3, 0.5, 0 .8, 1.0, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, etc.).

In addition, when there are two or more types of fatty acid esters (B), even if the hydroxyl value of any one type of fatty acid ester (B) or the hydroxyl value of all fatty acid esters (B) satisfies the above range. good. Preferably, the hydroxyl values of all the fatty acid esters (B) may satisfy the above range, although it depends on the proportion of the fatty acid ester (B) in the mixture.

Fatty acid esters (A) and (B) may be selected from those having little difference in hydroxyl value. In such a case, the absolute value of the difference between HA and HB (HA-HB) is, for example, 44 or less (for example, 43 or less, 42 or less), preferably 40 or less (for example, 38 or less, 37 or less, 36 or less). ), more preferably 35 or less (for example, 33 or less, 32 or less), 30 or less (for example, 30 or less, 28 or less, 27 or less, 26 or less, 25 or less, 22 or less, 20 or less, 18 or less , 16 or less, 15 or less, 13 or less, 12 or less, 10 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less), etc.

The lower limit of the absolute value of the difference between HA and HB (HA-HB) is not particularly limited, and may be 0, or a finite value (for example, 0.05, 0.1, 0.2, 0. 3, 0.5, 1.0, 1.2, 1.5, 1.8, 2, etc.).

In addition, when there are two or more types of fatty acid esters (B), the hydroxyl value of any one type of fatty acid ester (B) or the hydroxyl value of all fatty acid esters (B) (the absolute value of the difference between HA and HB) ) may satisfy the above range. Preferably, the hydroxyl values of all the fatty acid esters (B) may satisfy the above range, although it depends on the proportion of the fatty acid ester (B) in the mixture.

In addition, when there are two or more types of fatty acid esters with the highest pour point in the mixture, any of them may be used as the fatty acid ester (A), and some index [for example, the one with the highest hydroxyl value, the one with the lowest hydroxyl value, The fatty acid ester (A) may be determined using other indicators (for example, the largest or smallest hydroxyl number described below).

The hydroxyl value (total hydroxyl value, hereinafter sometimes referred to as HT, etc.) of the mixture (or the whole fatty acid ester (A) and fatty acid ester (B)) may also be adjusted so as not to be too large. In such a case, the total hydroxyl value (HT) may be selected from a range of, for example, 45 or less (e.g., 44 or less), 43 or less (e.g., 42 or less), preferably 40 or less (e.g., 38 or less). , 37 or less, 36 or less), more preferably 35 or less (e.g., 32 or less), 30 or less (e.g., 28 or less, 27 or less, 26 or less, 25 or less, 22 or less, 20 or less, 18 or less , 16 or less, 15 or less, 13 or less, 12 or less, 10 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1.5 or less, 1 or less), etc. can.

The lower limit value of HT is not particularly limited, and may be 0, or a finite value (for example, 0.05, 0.1, 0.2, 0.3, 0.5, 1.0, 1.2 , 1.5, 1.8, 2, 2.5, 3, etc.).

Note that HT can be measured as a mixture (or the whole fatty acid ester (A) and fatty acid ester (B)), but it is a value calculated based on the hydroxyl value and mixing ratio (mass ratio) of each fatty acid ester contained in the mixture. It may be.

In addition, when a synthesized fatty acid ester is used, the hydroxyl value (further, pour point, etc.) can be adjusted by adjusting the charging ratio of raw materials (alcohol, acid, etc.).

The method for measuring the hydroxyl value is not particularly limited, and a conventional method (for example, JIS K0070-1992) may be used. Specifically, the hydroxyl value may be measured by the method described below.

By combining fatty acid esters (A) and (B) so that the hydroxyl value as described above is obtained, the pour point of the mixture can be easily lowered efficiently. Although the reason for this is not clear, it is thought that, for example, the fact that it is easier to reduce the influence of hydrogen bonds (and in turn, it is easier to suppress crystallization, and the influence on lowering the pour point can be reduced) is also a factor.

The mixture (fatty acid ester (A), fatty acid ester (B)) may satisfy a specific range (value) under different conditions than the hydroxyl value.

In particular, in addition to satisfying the hydroxyl value as described above (for example, at least when HA and HB are each below a specific value), by satisfying such a specific range, flow can be achieved even more efficiently. In some cases, the pour point of the mixture may be lowered [for example, the pour point of the mixture may be lowered not only below FA, but also below FB (particularly below FB)].

For example, in the mixture, the difference (FA-FB) between the pour point FA of the fatty acid ester (A) and the pour point FB of the fatty acid ester (B) is 50°C or less (for example, 48°C, 45°C or less, 42°C 40°C or less (e.g., 38°C or less), preferably 36°C or less (e.g., 35°C or less, less than 35°C, 34°C or less, 33°C or less), and Preferably, the temperature may be 32°C or lower (for example, 31°C or lower), 30°C or lower (for example, 28°C or lower, 26°C or lower, 25°C or lower, 24°C or lower, 23°C or lower, 22°C or lower, 21°C or lower). ℃ or less, 20℃ or less, 19℃ or less, 18℃ or less, 17℃ or less, 16℃ or less, 15℃ or less, 14℃ or less, 13℃ or less, 12℃ or less, 11℃ or less, 10℃ or less, 9℃ or less , 8°C or lower, 7°C or lower, 6°C or lower, 5°C or lower, etc.).

The lower limit of FA-FB is not particularly limited, and may be 0°C (that is, the pour points of fatty acid esters (A) and (B) are the same), or a finite value (for example, 0.05°C, 0°C). .1℃, 0.2℃, 0.3℃, 0.5℃, 1.0℃, 1.2℃, 1.5℃, 1.8℃, 2℃, 2.5℃, 3℃, 3.5°C, 4°C, 4.5°C, 5°C, 5.5°C, 6°C, 6.5°C, 7°C, etc.).

In addition, when there are two or more types of fatty acid esters (B), the pour point (difference from FA-FB) of any one type of fatty acid ester (B) or all of the fatty acid esters (B) falls within the above range. may be satisfied. Preferably, the pour point FB of all the fatty acid esters (B) may satisfy the above range, although it depends on the proportion of the fatty acid ester (B) in the mixture.

The method for measuring pour point is not particularly limited, and a conventional method may be used. Specifically, the pour point may be measured by the method described below (method using an automatic pour point/cloud point tester MPC-6 type (manufactured by Tanaka Scientific Instruments Manufacturing Co., Ltd.)).

By combining fatty acid esters (A) and (B) so that the pour point difference as described above is achieved, it is easy to efficiently lower the pour point of the mixture. Although the reason for this is not clear, it is thought that one of the factors is that, for example, it becomes easier to suppress crystallization.

In addition, in the mixture, the total number of hydroxyl groups in the fatty acid ester (A) and the fatty acid ester (B) [the number of hydroxyl groups in the alcohol constituting the fatty acid ester (A) (the alcohol that is the raw material for the fatty acid ester) is X, the fatty acid ester ( When the number of hydroxyl groups in the alcohol constituting B) (alcohol serving as a raw material for fatty acid ester) is Y, the total number of X and Y (X+Y, hereinafter simply referred to as the total number of hydroxyl, etc.) is: The number may be selected from a range of 3 or more (for example, 4 or more), preferably 5 or more (for example, 6 or more, 7 or more, etc.).

The upper limit of the total hydroxyl number is not particularly limited, and depends on the number of fatty acid esters (B), etc., but for example, 40, 38, 35, 32, 30, 28, 25, 24, 22, 20, 18, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, etc. may be used.

In addition, when there are two or more types of fatty acid esters (B), the total number of hydroxyl groups includes the number of hydroxyl groups of alcohols constituting each fatty acid ester (B). For example, when the fatty acid ester (B) is of two types, fatty acid ester (B1) and fatty acid ester (B2), the total hydroxy number is This is the total number (X+Y1+Y2) of the number Y1 and the number Y2 of hydroxyl groups in the alcohol constituting the fatty acid ester (B2).

In addition, when there is a plurality of alcohols constituting the fatty acid ester (A) or (B), X or Y is the number (average number) of hydroxy groups calculated according to the ratio (number ratio, molar ratio). ). For example, in the alcohol constituting a certain fatty acid ester (B), alcohol with 3 hydroxy groups accounts for 30 mol% of the total alcohol, and alcohol with 4 hydroxy groups accounts for 70 mol% of the total alcohol. In this case, Y may be “3.7” (3×0.3+4×0.7).

By combining the fatty acid esters (A) and (B) so that the total hydroxyl number is as described above, it is easy to efficiently lower the pour point of the mixture. Although the reason for this is not clear, it is thought that one of the factors is that, for example, it becomes sterically bulky or the fatty acid ester becomes more likely to become entangled in a complicated manner, thereby making it easier to suppress crystallization.

The pour point (hereinafter sometimes referred to as FT, etc.) of the mixture of the present invention (or the total amount of fatty acid ester (A) and fatty acid ester (B)) is usually lower than the pour point FA of fatty acid ester (A).

In such a case, the difference between FA and FT (FA-FT) may be more than 0°C, and depends on the difference between FA and FB, the proportion of fatty acid ester (B) in the mixture, etc., but is, for example, 0. The temperature may be 1°C or higher (for example, 0.3°C or higher), preferably 0.5°C or higher (for example, 0.8°C or higher), and more preferably 1°C or higher (for example, 1.5°C or higher). , 2°C or higher (for example, 2.5°C or higher, 3°C or higher, 3.5°C or higher, 4°C or higher, 4.5°C or higher, 5°C or higher, 6°C or higher, 7°C or higher, 8°C or higher, 9 ℃ or higher, 10℃ or higher, 11℃ or higher, 12℃ or higher, etc.).

As mentioned above, FT is usually less than FA, but in the present invention, it is also possible to satisfy the pour point FB or less (particularly less than FB) of the fatty acid ester (B).

In such a case, the difference between FB and FT (FB-FT) may be more than 0°C, and depends on the difference between FA and FB, the proportion of fatty acid ester (B) in the mixture, etc., but is, for example, 0. The temperature may be 1°C or higher (for example, 0.3°C or higher), preferably 0.5°C or higher (for example, 0.8°C or higher), and more preferably 1°C or higher (for example, 1.5°C or higher). , 2°C or higher (for example, 2.5°C or higher, 3°C or higher, 3.5°C or higher, 4°C or higher, 4.5°C or higher, 5°C or higher, 6°C or higher, 7°C or higher, 8°C or higher, 9 ℃ or higher, 10℃ or higher, 11℃ or higher, 12℃ or higher, etc.).

In addition, when there are two or more types of fatty acid esters (B), the pour point (difference from FB-FT) of any one type of fatty acid ester (B) or all of the fatty acid esters (B) is within the above range. may be satisfied. Preferably, the pour point FB of all the fatty acid esters (B) may satisfy the above range, although it depends on the proportion of the fatty acid ester (B) in the mixture.

FA (furthermore, FB, FT) is not particularly limited and can be selected depending on the type of fatty acid ester (A) or (B), their combination or proportion in the mixture, the use of the mixture, etc., but for example, FA ( Furthermore, FB, FT) may be selected from a range of approximately 30°C or lower (for example, 25°C or lower, 20°C or lower), and preferably 18°C or lower (for example, 15°C or lower, 12°C or lower). The temperature may be 10°C or lower (for example, 8°C or lower), more preferably 5°C or lower (for example, 3°C or lower, 2°C or lower, 1°C or lower), etc., and 0°C or lower (for example, lower than 0°C, - 3°C or lower, -5°C or lower, -8°C or lower, -10°C or lower, -12°C or lower, -15°C or lower, -18°C or lower, -20°C or lower, -22°C or lower, etc.) .

Note that the lower limit value of FA (and furthermore, FB, FT) is not particularly limited, but in view of the necessity of lowering the pour point, for example, -150°C, -120°C, -110°C, -100°C, -90°C, ℃, -80℃, -75℃, -70℃, -65℃, -60℃, -55℃, -50℃, -45℃, -40℃, -35℃, -30℃, -25℃, The temperature may be -20°C, -15°C, -10°C, etc.

In the mixture, the proportion of the fatty acid ester may be selected depending on the range in which the pour point can be lowered as described above, the desired pour point, etc. Furthermore, the proportion of the fatty acid ester (A) to be selected, the combination It may be appropriately selected depending on the type and number of fatty acid esters (B), and is not particularly limited.

For example, in the mixture, the ratio of fatty acid ester (A) [or fatty acid ester (B) (if there are two or more, the total amount)] (ratio to the total amount of fatty acid ester (A) and fatty acid ester (B)) may be selected from a range of, for example, 1% by mass or more (for example, 3% by mass or more), 5% by mass or more (for example, 8% by mass or more), 10% by mass or more (for example, 12% by mass or more). ), 15% by mass or more (for example, 18% by mass or more), 20% by mass or more (for example, 22% by mass or more), etc., and less than 100% by mass [for example, 99% by mass or less (for example, 97% by mass) % or less)], 95% by mass or less (e.g., 92% by mass or less), 90% by mass or less (e.g., 88% by mass or less), 85% by mass or less (e.g., 82% by mass or less), 80% by mass or less (e.g. , 78% by mass or less).

When there are two or more types of fatty acid esters (B), the ratio of each fatty acid ester (B) may also be selected from the above range, but depending on the number of fatty acid esters (B), The proportion of ester (B) may be selected (adjusted) (for example, if the number of fatty acid esters (B) is two and the proportion of fatty acid ester (B) is 1 to 80% by mass, each fatty acid The proportion of ester (B) is 0.5 to 40% by mass (proportion divided by 2), etc.).

When there are two or more types of fatty acid esters (B), the proportion of one type of fatty acid ester (B) is in the range of about 1% by mass or more (for example, 3% by mass or more) with respect to the whole fatty acid ester (B). May be selected from: 5% by mass or more (for example, 8% by mass or more), 10% by mass or more (for example, 12% by mass or more), 15% by mass or more (for example, 18% by mass or more), 20% by mass or more (for example, 22% by mass or more), less than 100% by mass [for example, 99% by mass or less (for example, 97% by mass or less)], 95% by mass or less (for example, 92% by mass or less), 90% by mass or less It may be 85% by mass or less (for example, 82% by mass or less), 80% by mass or less (for example, 78% by mass or less), or the like.

In addition, when there are two or more kinds of fatty acid esters (B), the number may be two or more, for example, 20 or less, 18 or less, 16 or less, 15 or less, 12 or less, 10 or less, 8 or less, 7 or less. , 6 or less, 5 or less, 4 or less, 3 or less, 2, etc.

As mentioned above, fatty acid esters (fatty acid ester (A) and fatty acid ester (B)) are usually esters of alcohol and fatty acid, but the type of alcohol, the type of fatty acid, the combination thereof, the degree of esterification ( Whether it is a total ester or a partial ester, and if it is a partial ester, the degree of esterification, etc.) is a mixture as described above (for example, HA and HB are both 45 or less). There is no particular limitation as long as it constitutes (in other words, it can be selected so as to form a mixture as described above), but for example, the following can be exemplified.

First, alcohols (alcohols constituting esters and alcohols serving as raw materials for esters) include, for example, aliphatic alcohols (including alicyclic alcohols) and non-aliphatic alcohols (e.g., aromatic alcohols). , especially aliphatic alcohols.

The alcohol may be a monool (monohydric alcohol) or a polyol (polyhydric alcohol). The alcohol may be primary, secondary, tertiary, chain (linear, branched), cyclic, etc., and may be saturated or unsaturated. (In particular, it may be saturated).

Typical alcohols include, for example, aliphatic monools [e.g., methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, 2-ethylhexanol, alkanols such as amyl alcohol (e.g., C _1-40 alkanols, C _1-30 alkanol, C _2-20 alkanol, alkanol with 4 or more carbon atoms (even 6 or more, 8 or more, etc.)], monohydric alcohol such as aromatic monool (e.g. phenol); aliphatic Diols [e.g., alkanediols (e.g., _C2-20 alkanediols, _C2-10 alkanediols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexanediol, etc.), polyalkanediols (e.g., diethylene glycol, Dihydric alcohols such as polyethylene glycol, polypropylene glycol, polyC _2-10 alkanediol, polyC _2-6 alkanediol); alkane polyols [e.g. C _3-10 alkanetriols such as methylolpropane), alkanetetraols (e.g. C _4-10 alkane polyols such as pentaerythritol), etc.], condensates of alkane polyols [polyalkane tri-hexaols (e.g. diglycerin, Trivalent or higher (eg, trivalent to decavalent, trivalent to hexavalent) alcohols such as ditrimethylolpropane, dipentaerythritol, etc.) can be mentioned.

The molecular weight of the alcohol may be, for example, 500 or less, 400 or less, 300 or less (for example, 260 or less), etc., depending on whether it is a monool or polyol, whether it is a condensate, etc.

In addition, the number of alcohols that constitute the fatty acid ester may be one type, or two or more types may be combined.

In particular, the number of alcohols constituting the fatty acid ester (A) may be one.

Further, the alcohol constituting the fatty acid ester (A) and the alcohol constituting the fatty acid ester (B) may be the same or different.

In particular, the alcohol constituting the fatty acid ester (A) and the alcohol constituting the fatty acid ester (B) may be different.
In addition, in such a case, when there are two or more types of alcohols that constitute the fatty acid ester (B), it is sufficient that the alcohol as a whole is different from the alcohol that constitutes the fatty acid ester (A), for example, at least the fatty acid As long as it contains an alcohol different from the alcohol constituting the ester (A), it may contain the same alcohol as the alcohol constituting the fatty acid ester (A).

Typically, the fatty acid ester (A) is composed of one kind of alcohol, and the fatty acid ester (B) is composed of a different alcohol from the fatty acid ester (A).

Fatty acids (fatty acids constituting esters, fatty acids serving as raw materials for esters) may be monovalent or polyvalent. In addition, the fatty acid may be either chain (linear, branched), cyclic, etc., and may be saturated or unsaturated. In the unsaturated fatty acids, the number of unsaturated bonds (carbon-carbon double bonds, carbon-carbon triple bonds, etc.) is not particularly limited, and is, for example, 1 or more (for example, 1 to 21, 1 to 10, 1 to 5 , 1 to 4, 1 to 3, etc.).

The number of carbon atoms in the fatty acid is not particularly limited, but it may usually be 2 or more, and fatty acids having 4 or more carbon atoms (6 or more, 7 or more, 8 or more, etc.) may be preferably used. The upper limit of the number of carbon atoms in the fatty acid is not particularly limited, but may be, for example, 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 24 or less, 22 or less, 20 or less.

Specific fatty acids include, for example, butanoic acid (butyric acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), Decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid (pentadecylic acid), hexadecanoic acid (palmitic acid), 9-hexadecenoic acid (palmitoleic acid), heptadecanoic acid (margaric acid) , octadecanoic acid (stearic acid), cis-9-octadecenoic acid (oleic acid), 11-octadecenoic acid (vaccenic acid), cis,cis-9,12-octadecadienoic acid (linoleic acid), 9,12,15 -Octadecantrienoic acid ((9,12,15)-linolenic acid), 6,9,12-octadecatrienoic acid ((6,9,12)-linolenic acid), 9,11,13-octadecatrienoic acid (eleostearic acid), eicosanoic acid (arachidic acid), 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid (mead acid), 5,8,11-eicosatetraenoic acid (arachidonic acid) ), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), cis-15-tetracosanoic acid (nervonic acid), hexacosanoic acid (cerotic acid), octacosanoic acid (montanic acid), triacontanoic acid (melisic acid), etc. Examples include fatty acids [for example, saturated or unsaturated, straight-chain or branched fatty acids having 4 to 30 carbon atoms (preferably 18 to 22 carbon atoms)].

Furthermore, fatty acids include monomer acids, dimer acids, trimer acids, and the like.

For example, as an example of a fatty acid that is a combination of monomer acid, dimer acid, and trimer acid (an example of a commercially available product), Tsuno Dime 205 (monomer acid 10% by mass, dimer acid 76% by mass, trimer acid 10% by mass, trimer acid 76% by mass, Tsunodime 216 (monomer acid 7% by mass, dimer acid 77% by mass, trimer acid 14% by mass), Tsunodime 228 (monomer acid 5% by mass, dimer acid 81% by mass, trimer acid 14% by mass), Tsunodime 395 (monomer acid 3% by mass, dimer acid 94% by mass, trimer acid 3% by mass), Tsunodime 346 (monomer acid 2% by mass, dimer acid 28% by mass, trimer acid 70% by mass), and the like.

The fatty acid ester may be a total ester or a partial ester.

The fatty acid ester may be a commercially available product or a synthesized (manufactured) product. Examples of commercially available products include the TFE series (eg, TFE-47TM, TFE-30A, TFE-40A, TFE-100A, TFE-220A, etc.) manufactured by Tsukino Foods Co., Ltd.

In addition, the number of fatty acids constituting the fatty acid ester may be one type, or two or more types may be combined.

Furthermore, the fatty acids constituting the fatty acid ester (A) and the fatty acids constituting the fatty acid ester (B) may be the same or different.
In addition, when the alcohol constituting the fatty acid ester (A) and the alcohol constituting the fatty acid ester (B) are the same, the fatty acids constituting the fatty acid ester (A) and the fatty acids constituting the fatty acid ester (B) are different. Good too.
In addition, in such a case, when there are two or more types of fatty acids constituting the fatty acid ester (B), it is sufficient that the fatty acids as a whole are different from the fatty acids constituting the fatty acid ester (A), for example, at least the fatty acids The same fatty acid as the fatty acid composing the fatty acid ester (A) may be included as long as it contains a fatty acid different from the fatty acid composing the ester (A).

The combination of fatty acid ester (A) and fatty acid ester (B) is not particularly limited as long as it has the above-mentioned properties (for example, hydroxyl value, etc.); combinations (combinations having the above-mentioned characteristics), etc.

(1) Alcohol (AA) (one or more alcohols, especially one alcohol) constituting fatty acid ester (A) and alcohol (AB) (one or two alcohols constituting fatty acid ester (B)) The fatty acid (CA) (one or more fatty acids) that constitutes the fatty acid ester (A) and the fatty acid (CB) (one or more fatty acids) that constitutes the fatty acid ester (B) A combination of a fatty acid ester (A) and a fatty acid ester (B) (one or more fatty acid esters (B)), which are the same or different.

(2) Alcohol (AA) (one or more alcohols) constituting fatty acid ester (A) and alcohol (AB) (one or more alcohols) constituting fatty acid ester (B) are the same, and the fatty acid (CA) (one or more fatty acids) constituting the fatty acid ester (A) and the fatty acid (CB) (one or more fatty acids) constituting the fatty acid ester (B) A combination of a fatty acid ester (A) and a fatty acid ester (B) (one or more fatty acid esters (B)) that are different from each other (fatty acid).

In (1) and (2), one type of alcohol (AA) may be used, and one type or two or more types (for example, one type) of alcohol (AB) may be used.

Moreover, in (1) and (2), each of the fatty acids (CA) and (CB) may be one type or two or more types.

Note that the fatty acid ester (mixture) may contain components other than the ester (for example, alcohol, fatty acid, and other raw materials for the fatty acid ester or components derived from the production of the fatty acid ester).

Note that the mixture of the present invention may contain components other than the fatty acid ester (A) and the fatty acid ester (B), or may be composed only of the fatty acid ester.

The mixture of the present invention is not particularly limited as long as it contains the constituent components [fatty acid ester (A) and fatty acid ester (B)], but it can usually be produced by mixing the constituent components. Usually, fatty acid ester (A) and fatty acid ester (B)] are often mixed uniformly.

The mixing method is not particularly limited, and a conventional method can be used. For example, the mixing temperature may be selected depending on the melting point or pour point of the fatty acid ester, and may be, for example, 0 to 30°C (for example, 0 to 25°C), but is not particularly limited.

Further, the mixing may be performed under stirring, or may be performed at room temperature, under heating, under cooling, or the like. For stirring, known stirring bodies (including laboratory scale and factory scale ones) may be used.
The mixing (eg, stirring) time may be, for example, 5 to 60 minutes (eg, 10 to 30 minutes), but is not particularly limited.

Note that the mixing may be performed in stages {for example, some of the constituent components [for example, some of the fatty acid esters (for example, fatty acid esters (B) when there are two or more types of fatty acid esters (B))] may be mixed in advance}.

[Applications, etc. of fatty acid ester mixture]
The mixture (fatty acid ester mixture) of the present invention can be used for various purposes (eg, lubricating oil, metal working oil, rolling oil, metal cutting oil) depending on the type of fatty acid ester contained.

In particular, the mixture of the present invention has a pour point lower than the pour point (at least FA) of the constituent fatty acid ester, and is suitable for applications such as lubricating oil. In addition, in such applications, the fatty acid ester mixture may be applied by itself or may contain other components depending on the application (the mixture may be applied together with other components as appropriate). good).

In addition, in the present invention, by combining the fatty acid ester (A) and the fatty acid ester (B), the pour point FT of the mixture can be made lower than the FM (less than FT).

Then, it can be said that the fatty acid ester (B) functions as a pour point depressant (an agent for lowering the pour point) for the fatty acid ester (A).

Therefore, the present invention includes such an invention, that is, a fatty acid ester (A) having a pour point FA [for example, a fatty acid ester (A) having a pour point FA and a hydroxyl value HA of 45 or less]. (addition) to make the pour point FT of the mixture less than FA, the fatty acid ester (B) [e.g. , fatty acid ester (B)] (pour point depressant).

Furthermore, in the present invention, by combining fatty acid ester (A) and fatty acid ester (B), the pour point of the mixture can be lowered.

Therefore, the present invention includes such an invention, that is, a fatty acid ester (A) having a pour point FA [for example, a fatty acid ester (A) having a pour point FA and a hydroxyl value HA of 45 or less]. A method for making the pour point FT of a mixture (fatty acid ester mixture) lower than FA, comprising: a fatty acid ester (B) [e.g., having a pour point FB of FA or lower and having a hydroxyl value HB of 45 or lower; fatty acid ester (B)] (adding, mixing fatty acid ester (B) with fatty acid ester (A)).

In addition, in such inventions (inventions related to agents and methods), the fatty acid ester (A), the fatty acid ester (B), the relationship between them, etc. are all the same as those described in the section of the mixture.

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

1. Raw materials for fatty acid ester The raw materials used for the production of fatty acid ester are as follows.
(alcohol)
2-Ethylhexanol (2EH); Trade name: 2-ethylhexanol; Neopentyl glycol (NPG) manufactured by Mitsubishi Chemical Corporation; Trimethylolpropane (TMP) manufactured by Mitsubishi Gas Chemical Corporation; Pentaerythritol (manufactured by Mitsubishi Gas Chemical Corporation) PE); dipentaerythritol (DiPE) manufactured by Perstorp; glycerin (GL) manufactured by Perstorp; polyethylene glycol (PEG) manufactured by Sakamoto Pharmaceutical Co., Ltd.; manufactured by Aoki Yushi Kogyo Co., Ltd. (fatty acid)
Heptanoic acid (C7); Product name: OLERIS (registered trademark) n-heptanoic acid; Octanoic acid (C8), manufactured by Arkema Corporation; Product name: Lunac 8-98; Isononanoic acid (iC9), manufactured by Kao Corporation; Product name: Kyowanoic N; Decanoic acid (C10) manufactured by KH Neochem Co., Ltd.; Product name: Lunac 10-98; Stearic acid (C18) manufactured by Kao Corporation; Product name: STEARIC ACID 98%; Isostearic acid (manufactured by Miyoshi Oil Co., Ltd.) iC18); Isostearic acid is a monomer acid (for example, TFA-45, (manufactured by Tsukino Foods Co., Ltd.) by separating the branched fatty acids contained in the fatty acid.
Oleic acid (OL); Product name: SINAR-OL; TFA-47 manufactured by SOCI MAS; NAS-125N manufactured by Tsukino Foods Co., Ltd.; Dimer acid manufactured by Tsukino Foods Co., Ltd.; Product name: Td216; Tsukino Foods Trimer acid manufactured by Kogyo Co., Ltd.; Product name: Td346; manufactured by Tsukino Foods Co., Ltd.

2. Method for Measuring Pour Point Using an automatic pour point/cloud point tester MPC-6 type (manufactured by Tanaka Scientific Instruments Manufacturing Co., Ltd.), measure and evaluate the pour points of various fatty acid esters according to the method described in the instruction manual. I did it. This measurement method is in accordance with the American Standard (ASTM D6749-02 (2018) Standard Test Method for Pour Point (Automated Air Pressure Method) of Petroleum Products), and is in accordance with the Japanese Industrial Standard (JIS 2269:1987 Crude Oil and Petroleum This measurement method corresponds to the pour point of products and the cloud point test method for petroleum products. Specifically, various fatty acids are put into the measuring cell of the tester up to the marked line, preheated to 45°C, and then heated at 4°C/min until the expected point +40°C, and thereafter at 1°C/min until the end of the test. It was cooled at a rate of .

3. Method for measuring hydroxyl value Measured according to JIS K0070-1992.

4. Production of fatty acid ester Fatty acid ester was produced as follows.

[Fatty acid ester A]
In a 1 L four-necked flask equipped with a stirrer, thermometer, and Dean-Stark tube with condenser, 569 g (2.00 mol) of isostearic acid, 91 g (0.87 mol) neopentyl glycol, and tin oxide as a catalyst were added. was added in an amount of 0.05% by weight based on the total amount, 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 using a Dean-Stark tube. The reaction was terminated when the hydroxyl value became 5.0 mgKOH/g or less. After the reaction was completed, activated carbon and activated clay were added in an amount of 0.2% by weight based on the esterified crude material, and the mixture was stirred at 80° C. for 30 minutes and then for 1 hour under reduced pressure. Thereafter, the pressure was returned to normal, and they were removed by filtration. Next, excess acid and low boiling point components of the obtained esterified filtrate were distilled off using a thin film distiller to obtain ester A.

[Fatty acid ester B]
In a 1 L four-neck flask equipped with a stirrer, thermometer, and Dean-Stark tube with condenser, 424 g (0.50 mol) of Td346, 260 g (2.00 mol) of 2-ethylhexanol, and tin oxide as a catalyst were placed. was added in an amount of 0.1% by weight based on the total amount, 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 using a Dean-Stark tube. The reaction was terminated when the acid value became 1.0 mgKOH/g or less. After the reaction, 0.2% by weight of activated carbon and activated clay were added, stirred at 80° C. for 30 minutes, and then stirred under reduced pressure for 1 hour. Thereafter, the pressure was returned to normal, and they were removed by filtration. Next, excess alcohol and low boiling point components of the obtained esterified crude product were removed by thin film distillation to obtain ester B.

[Fatty acid ester C]
Ester C was obtained in the same manner as Ester A, except that 78 g (0.58 mol) of trimethylolpropane was used instead of neopentyl glycol and 565 g (2.00 mol) of oleic acid was used instead of isostearic acid. .

[Fatty acid ester D]
Ester D was obtained in the same manner as Ester A except that 78 g (0.58 mol) of trimethylolpropane was used instead of neopentyl glycol.

[Fatty acid ester E]
Same as ester A except that 101 g (0.75 mol) of pentaerythritol was used instead of neopentyl glycol, 324 g (2.24 mol) of octanoic acid and 215 g (1.25 mol) of decanoic acid were used instead of isostearic acid. Ester E was obtained by the method.

[Fatty acid ester F]
134 g (0.53 mol) of dipentaerythritol instead of neopentyl glycol, 37 g (0.29 mol) of heptanoic acid instead of isostearic acid, 33 g (0.23 mol) of octanoic acid, 469 g (2.97 mol) of isononanoic acid. ), Ester F was obtained in the same manner as Ester A except that 41 g (0.24 mol) of decanoic acid was used.

[Fatty acid ester G]
110 g (0.81 mol) of pentaerythritol instead of neopentyl glycol, 198 g (1.37 mol) of octanoic acid instead of isostearic acid, 164 g (1.04 mol) of isononanoic acid, 237 g (1.38 mol) of decanoic acid. Ester G was obtained in the same manner as Ester A except that Ester G was used.

[Fatty acid ester H]
Ester H was obtained in the same manner as Ester A, except that 121 g (0.48 mol) of dipentaerythritol was used instead of neopentyl glycol and 522 g (3.30 mol) of isononanoic acid was used instead of isostearic acid. .

[Fatty acid ester I]
Ester I was obtained in the same manner as Ester A except that 508 g (3.90 mol) of heptanoic acid was used instead of isostearic acid.

[Fatty acid ester J]
Ester J was obtained in the same manner as Ester A, except that 54 g (0.40 mol) of pentaerythritol was used instead of neopentyl glycol and 593 g (2.20 mol) of oleic acid was used instead of isostearic acid.

[Fatty acid ester K]
Same method as Ester A except that 121 g (0.90 mol) of trimethylolpropane, 337 g (1.19 mol) of isostearic acid, and 225 g (1.42 mol) of isononanoic acid were used instead of neopentyl glycol. Ester K was obtained.

[Fatty acid ester L]
In a 1L four-necked flask equipped with a stirrer, a thermometer, and a Dean-Stark tube with a condenser, 214 g (0.37 mol) of Td216, 315 g (1.11 mol) of oleic acid, and 101 g (0.75 mol) of trimethylolpropane were added. molar), 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 using a Dean-Stark tube. The reaction was terminated when the acid value became 5 mgKOH/g or less, and ester L was obtained.

[Fatty acid ester M]
Ester M was obtained in the same manner as Ester B, except that trimethylolpropane g (0.58 mol) was used instead of neopentyl glycol and 565 g (2.00 mol) of TFA-47 was used instead of isostearic acid. Ta.

[Fatty acid ester N]
Ester N was obtained in the same manner as Ester L, except that 300 g (0.52 mol) of Td216, 250 g (0.88 mol) of oleic acid, and 110 g (0.82 mol) of trimethylolpropane were used.

[Fatty acid ester O]
Ester O was obtained in the same manner as Ester A except that 72 g (0.78 mol) of glycerin was used instead of neopentyl glycol and 626 g (2.20 mol) of stearic acid was used instead of isostearic acid.

[Fatty acid ester P]
Ester P was prepared in the same manner as Ester L, except that 342 g (0.84 mol) of polyethylene glycol was used instead of trimethylolpropane, and 350 g (1.23 mol) of NAS-125N was used instead of dimer acid and oleic acid. I got it.

[Fatty acid ester Q]
Ester Q was obtained in the same manner as Ester A, except that 129 g (0.96 mol) of trimethylolpropane was used instead of neopentyl glycol and 568 g (3.3 mol) of decanoic acid was used instead of isostearic acid. .

[Fatty acid ester R]
Ester R was obtained in the same manner as Ester B except that 435 g (1.53 mol) of isostearic acid was used instead of Td346.

5. Fatty acid ester A summary of the hydroxyl value, pour point, and number of hydroxy groups (hydroxy number) of the constituent alcohols of the fatty acid ester is shown in the table below.

5. Mixture (fatty acid ester mixture)
Fatty acid esters were mixed at the mass proportions shown in the table below to obtain a mixture (fatty acid ester mixture). The results of this mixture, including pour point, etc., are shown in the table below. The table also lists each fatty acid ester (unmixed) for reference.

In addition, in the table, "ester" corresponds to the type and mass ratio (mixing ratio) of mixed fatty acid esters. For example, "A/B = 25/75" means the mass ratio of ester A and ester B. It shows that it is a 25/75 mixture.
Moreover, in the table, the maximum hydroxyl value indicates the highest hydroxyl value among fatty acid esters.
Furthermore, if the number of fatty acid esters is 3 or more (2 or more fatty acid esters (B)), in the table, the absolute value of the difference in hydroxyl value and the difference in pour point are described for all fatty acid esters (B). ing.

As is clear from the results in the table above, by selecting the fatty acid ester according to specific indicators (conditions), it was possible to efficiently lower the pour point of the mixture.

For example, by setting the hydroxyl values of both fatty acid esters (A) and (B) to specific values (for example, 45 or less), the pour point FT of the mixture is made lower than the pour point FA of fatty acid ester (A). I was able to do that.

In particular, in addition to this index (condition), other indexes (conditions) such as setting the pour point difference (FA-FB) of fatty acid ester (A) to a specific value, or setting the total hydroxyl value to a specific value, etc. By selecting fatty acid esters so as to satisfy the following in combination, it was possible to more efficiently lower the pour point FT of the mixture [for example, lower than the pour point FB of fatty acid ester (B)].

On the other hand, if the hydroxyl value of either fatty acid ester (A) or (B) becomes sufficiently larger than a specific value (for example, 45), the pour point FT of the mixture may change depending on the mixing ratio. It has been found that there are cases where the pour point cannot be lowered efficiently, such as when the pour point cannot be lowered below the pour point FA of

According to the present invention, a novel fatty acid ester mixture can be provided. Such fatty acid ester mixtures can be used in various applications, such as lubricating oils, metal working oils, rolling oils, metal cutting oils, and the like.

Claims (16)

A mixture comprising a fatty acid ester (A) having a pour point FA and a fatty acid ester (B) having a pour point FB less than or equal to FA, the mixture having a pour point FT less than FA, wherein the hydroxyl value of the fatty acid ester (A) A mixture in which HA and fatty acid ester (B) each have a hydroxyl value HB of 45 or less. The mixture according to claim 1, wherein both HA and HB are 42 or less. The mixture according to claim 1 or 2, wherein the absolute value of the difference between HA and HB is 40 or less. The mixture according to any one of claims 1 to 3, having a total hydroxyl value HT of 40 or less. The mixture according to any one of claims 1 to 4, wherein the difference between FA and FB is 32°C or less. The mixture according to any one of claims 1 to 5, wherein the fatty acid ester (A) and the fatty acid ester (B) have a total hydroxy number of 5 or more. A mixture according to any of claims 1 to 6, wherein FT is less than FB. The mixture according to any one of claims 1 to 7, wherein the difference between FA and FT is 1°C or more. HA and HB are both 35 or less,
The absolute value of the difference between HA and HB is 30 or less,
Total hydroxyl value HT is 25 or less,
The difference between FA and FB is 30℃ or less,
The total hydroxy number of the fatty acid ester (A) and the fatty acid ester (B) is 5 or more,
The difference between FB and FT is 1℃ or more,
The mixture according to any one of claims 1 to 8, wherein the difference between FA and FT is 2°C or more. The mixture according to any one of claims 1 to 9, wherein both HA and HB are 25 or less, the total hydroxyl value HT is 15 or less, and the difference between FA and FB is 25°C or less. The mixture according to any of claims 1 to 10, which is a lubricating oil. An additive that is mixed with a fatty acid ester (A) having a pour point FA and a hydroxyl value HA of 45 or less to make the pour point FT of the mixture less than FA,
An additive composed of a fatty acid ester (B) having a pour point FB of FA or lower and a hydroxyl value HB of 45 or lower. A method for reducing the pour point FT of a mixture containing a fatty acid ester (A) having a pour point FA and a hydroxyl value HA of 45 or less, comprising:
A method of mixing a fatty acid ester (B) having a pour point FB of FA or lower and a hydroxyl value HB of 45 or lower. The absolute value of the difference between HA and HB is 40 or less,
Total hydroxyl value HT is 40 or less, difference between FA and FB is 32℃ or less,
The agent or method according to claim 12 or 13, wherein the total number of hydroxyl groups in the fatty acid ester (A) and the fatty acid ester (B) is 5 or more. The agent or method according to any one of claims 12 to 14, wherein FT is less than FB and the difference between FA and FT is 1°C or more. HA and HB are both 35 or less,
The absolute value of the difference between HA and HB is 30 or less,
Total hydroxyl value HT is 25 or less,
The difference between FA and FB is 30℃ or less,
The total hydroxy number of the fatty acid ester (A) and the fatty acid ester (B) is 5 or more,
The difference between FB and FT is 1℃ or more,
The agent or method according to any one of claims 12 to 15, wherein the difference between FA and FT is 2°C or more.