WO2017141775A1 - Ionic liquid, lubricant, and magnetic recording medium - Google Patents

Abstract

The present invention relates to a lubricant containing an ionic liquid that has a conjugate base and a conjugate acid, wherein the conjugate acid has a group including a hydroxyl group and a group including a linear hydrocarbon group having six or more carbon atoms, and the acid that becomes the source for the conjugate base has a pKa value not higher than 10 in acetonitrile.

Description

Ionic liquid, lubricant and magnetic recording medium

The present invention relates to an ionic liquid, a lubricant containing the ionic liquid, and a magnetic recording medium using the same.

Conventionally, in a thin film magnetic recording medium, a lubricant is applied to the surface of the magnetic layer in order to reduce friction and wear on the magnetic head and the medium surface. The actual film thickness of the lubricant is at the molecular level in order to avoid adhesion such as stiction. Therefore, in thin film magnetic recording media, it is no exaggeration to say that the most important thing is the selection of a lubricant having excellent wear resistance under all circumstances.

In the life of a magnetic recording medium, it is important that the lubricant be present on the surface of the medium without causing desorption, spin-off, chemical degradation, and the like. The presence of the lubricant on the medium surface becomes more difficult as the surface of the thin film magnetic recording medium becomes smoother. This is because the thin film magnetic recording medium does not have a lubricant replenishment capability unlike the coating type magnetic recording medium.

In addition, if the adhesive force between the lubricant and the protective film on the magnetic layer surface is weak, the lubricant film thickness decreases during heating and sliding, which accelerates wear and requires a large amount of lubricant. It is said. A large amount of lubricant becomes a mobile lubricant and can have a function of replenishing the lost lubricant. However, the excess lubricant makes the film thickness of the lubricant larger than the surface roughness, causing problems related to adhesion, and in the fatal case, it becomes a stiction and causes drive failure. There is.

Further, as shown in FIG. 1, in Non-Patent Document 1, the increase rate of the in-plane recording density of the product hard disk drive has been decreasing for the past several years, but it has achieved an annual rate of 25%, which is one target of 4Tb. / In ^{2 is about} to arrive. As shown in FIG. 2, it can be seen that the distance between the head disk interfaces is decreasing with the increase in recording density, but there is always a need to improve the reliability. This is described, for example, in Non-Patent Documents 2 to 4 below.

The current recording density is about 1 Tb / in ² , the spacing is about 6 nm, and the lubricant thickness is 0.8 nm. At the future recording density of 4 Tb / in ² , the thickness of the lubricant must be reduced. Don't be. However, in the conventional PFPE lubricant, in order to reduce the film thickness, it is necessary to reduce the molecular weight, but there is a drawback that the thermal stability is deteriorated. It can be seen that these reliability problems are not sufficiently solved by conventional perfluoropolyether (PFPE) -based lubricants.

Especially in thin film magnetic recording media with high surface smoothness, a new lubricant is molecularly designed and synthesized in order to eliminate these trade-offs. Many reports on the lubricity of PFPE have been submitted. Thus, the lubricant is very important in the magnetic recording medium.

Table 1 shows the chemical structure of a typical PFPE lubricant.

Z-DOL in Table 1 is one of the commonly used lubricants for thin film magnetic recording media. In addition, Z-tetraol (ZTMD) is one in which a functional hydroxyl group is further introduced into the main chain of PFPE, and it has been reported that the reliability of the drive is improved while reducing the gap in the head media interface. There is a report that A20H suppresses decomposition of the PFPE main chain by Lewis acid or Lewis base and improves tribological properties. On the other hand, Mono has a report that the polymer main chain and the polar group are polynormalpropyloxy and amine, respectively, unlike the above-mentioned PFPE, and reduce the adhesion interaction in the near contact.

However, common solid lubricants, which have a high melting point and are considered to be thermally stable, interfere with the electromagnetic conversion process, which is very sensitive, and wear due to wear powder scraped by the head on the traveling track. The characteristics deteriorate. As described above, the liquid lubricant has mobility such that the lubricant removed by abrasion by the head moves from the adjacent lubricant layer and is replenished. However, due to this mobility, especially at high temperatures, the disk spins off during disk operation and lubricant is reduced, resulting in a loss of protection. For this reason, a high-viscosity and low-volatile lubricant is suitably used, and the evaporation rate can be suppressed and the life of the disk drive can be extended.

In view of these lubrication mechanisms, requirements for low friction and low wear lubricants used in thin film magnetic recording media are as follows.
(1) Low volatility.
(2) Low surface tension for the surface replenishment function.
(3) There is an interaction between the terminal polar group and the disk surface.
(4) High thermal and oxidative stability so that there is no decomposition or decrease during the period of use.
(5) It is chemically inert to metals, glass, and polymers and does not generate wear powder on the head or guide.
(6) There must be no toxicity or flammability.
(7) Excellent boundary lubrication characteristics.
(8) Dissolve in an organic solvent.

In recent years, ionic liquids are attracting attention as one of the environmentally friendly solvents for synthesizing organic and inorganic materials in power storage materials, separation technologies, and catalyst technologies. Ionic liquids fall into the large category of low melting point molten salts, but generally, those having a melting point of 100 ° C. or lower among them. Important characteristics of ionic liquids used as lubricants include low volatility, lack of flammability, thermal stability, and excellent dissolution performance.

For example, friction and wear on the metal or ceramic surface may be reduced by using a certain ionic liquid as compared with a conventional hydrocarbon-based lubricant. For example, an imidazole cation-based ionic liquid substituted with a fluoroalkyl group is synthesized, and alkyl imidazolium tetrafluoroborate or hexafluorophosphate can be used for steel, aluminum, copper, single crystal SiO ₂ , silicon, sialon ceramics ( When used for Si—Al—O—N), it has been reported that it exhibits superior tribological properties over cyclic phosphazene (X-1P) and PFPE. In addition, there is a report that the friction of the ammonium-based ionic liquid is lower than that of the base oil in the boundary lubrication region from the elastic fluid. In addition, ionic liquids have been investigated for their effect as additives to base oils, and chemical and tribochemical reactions have been studied to understand the lubrication mechanism. However, there are few application examples as a magnetic recording medium that requires the above. For example, Non-Patent Document 5 reports an imidazole-based tris (pentafluoroethyl) trifluorophosphate ionic liquid, but only shows the possibility, and does not mention specific tribological characteristics.

Among them, perfluorooctanoic acid alkylammonium salt is a protonic ionic liquid (PIL), but it has been reported that it has a remarkable effect of reducing friction of magnetic recording media as compared with Z-DOL described above. (For example, see Patent Documents 1 and 2 and Non-Patent Documents 6 to 8).
However, these perfluorocarboxylic acid ammonium salts have a weak cation-anion interaction in the reaction shown in the following reaction formula (A), and the equilibrium is on the left at high temperatures due to Le Chatelier's law. , It becomes a dissociated neutral compound and the thermal stability is deteriorated. That is, proton transfer occurs at a high temperature, and the equilibrium moves to a neutral substance and dissociates (see, for example, Non-Patent Document 9). That is, the thermal stability at a high temperature is deteriorated.

By the way, the limit of the surface recording density of the hard disk is said to be 1-2.5 Tb / in ² . At present, the limit is approaching, but energetic development of high-capacity technology has been continued on the premise of miniaturization of magnetic particles. Technologies for increasing the capacity include reduction of effective flying height, introduction of single write (BMP), and the like.

Further, as a next generation recording technology, there is “heat assisted magnetic recording”. FIG. 3 shows an outline of the heat-assisted magnetic recording. In FIG. 3, reference numeral 1 indicates laser light, reference numeral 2 indicates near-field light, reference numeral 3 indicates a recording head (PMR element), and reference numeral 4 indicates a reproducing head (TMR element). . As a problem of this technique, since the recording portion is heated by a laser at the time of recording / reproducing, deterioration of durability due to evaporation or decomposition of the lubricant on the surface of the magnetic layer can be mentioned. Thermally assisted magnetic recording is likely to be exposed to high temperatures said to be 400 ° C. or more for a short time, and is generally used as a lubricant perfluoropolyether for thin film magnetic recording media such as Z-DOL and Z -For TETRAOL, there is concern about its thermal stability.

The protic ionic liquid is generally a substance having high thermal stability in order to form ions as described above. The equilibrium is shown in the following Scheme 1.

Here, HA represents a Bronsted acid and B represents a Bronsted base. The acid (HA) and the base (B) react to form a salt (A ⁻ HB ⁺ ) as shown in Scheme 1.
At this time, the dissociation constants K _a1 and K _b2 of the acid and the base can be expressed as the following Scheme 2 in a form including the concentration.

Since K _a1 and K _b2 vary greatly depending on the substance and in some cases have a large number of digits, which is inconvenient to handle, it is often expressed as a negative common logarithm. That is, as shown in the following Scheme 3, -log ₁₀ K _a1 = pK _a1 is defined, and an acid having a clearly smaller pK _a1 has a stronger acidity.
Here, the difference ΔpKa in acid dissociation constant between acid and base will be discussed. The acid / base reaction is influenced by the acidity / basicity of each other (or the acidity of the conjugate acid), and the acidity difference ΔpKa can be expressed together in the following Scheme 3.

It can be seen that ΔpKa increases as the salt concentration [A ⁻ HB ⁺ ] increases with respect to the acid concentration and the base concentration.

Among them, Yoshizawa et al. Are prone to proton transfer when the difference in acid and base pKa (ΔpKa) is 10 or more.
[AH] + [B] ⇔ [A ⁻ HB ⁺ ]
It has been reported that the equilibrium of the above equation shifts to the ion side (right side) and the stability is further increased (for example, see Non-Patent Document 9). In addition, Watanabe et al. Strongly depend on ΔpKa for proton mobility and thermal stability of a protic ionic liquid, and DBU (1,8-diazabicyclo [5,4,0] unde-7-cene) is used as a base. It has been reported that the thermal stability of an ionic liquid is greatly improved by using an acid having a pKa difference (ΔpKa) of 15 or more when used (see Non-Patent Document 10). Kondo et al. Have reported that perfluorooctane sulfonate octadecyl ammonium salt-based protic ionic liquid having a large ΔpKa improves the durability of the magnetic recording medium (see Non-Patent Document 11 and Patent Document 3). . In addition, a recent report by Kondo et al. Regarding the heat resistance of ionic liquids reports that the decomposition temperature rises to a certain extent, but the decomposition temperature does not increase so much even if ΔpKa is increased beyond that. (See Non-Patent Documents 12 and 13). In addition, it has been reported that a pyrrolidinium-based ionic liquid having a geminal dication may improve heat resistance as compared with a normal monocation ionic liquid (see Non-Patent Document 13). However, as described in Non-Patent Document 14, the relationship between the molecular structure constituting the structure and physical or chemical properties is not well understood. The combination of cation and anion greatly affects the physical or chemical properties of the ionic liquid. The anion moiety is rich in variability, but the relationship is not clear unless it is a structurally similar cation (see, for example, Non-Patent Document 15). For example, the stronger the hydrogen bonding force of halogen (Cl>Br> I), the more viscous the liquid. However, the method for increasing the viscosity is not limited to this, and it is possible, for example, by changing the alkyl chain of imidazole. Similarly, it affects melting point, surface tension, and thermal stability, but the effect of its anion has not been studied extensively. Therefore, it is possible to change these physical or chemical properties by a combination of cation and anion, but it is difficult to predict.

In consideration of the hard disk lubricant shown in Table 1, a polar group such as a hydroxyl group is introduced at the end in order to enhance the interaction with the media surface. Such a hydroxyl group reacts with the surface of the medium and is fixed by heat treatment to improve thermal stability, and also has an effect of lowering the polar term component of the surface energy by bonding with the hydroxyl group (Non-patent Document 16). ).

Also, the ionic liquid lubricant preferably has a lower melting point when considering uses other than hard disks.

Japanese Patent No. 2581090 Japanese Patent No. 2629725 International Publication No. 2014/104342 Pamphlet

The present invention has been proposed in view of such a conventional situation, and has an excellent lubricity even at a high temperature and can be lowered in melting point, so that it can be applied to various purposes. The present invention provides a lubricant that has excellent lubricity even at a high temperature and can be applied to various purposes because of a low melting point, and a magnetic recording medium having excellent practical characteristics.

<1> containing an ionic liquid having a conjugate base and a conjugate acid,
The conjugate acid has a group containing a hydroxyl group and a group containing a linear hydrocarbon group having 6 or more carbon atoms;
The lubricant is characterized in that the pKa in acetonitrile of the acid which is the base of the conjugate base is 10 or less.
<2> The conjugate acid according to <1>, wherein the conjugate acid is represented by any one of the following general formula (A), the following general formula (B), the following general formula (C), and the following general formula (D). Lubricant.

However, the general formula (A), R _1, and R ₂ represents independently a hydrogen atom, and one of the group carbon atoms containing 6 or more straight chain hydrocarbon radical, n Represents an integer of 1 or more. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
However, in said general formula (B), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
However, in said general formula (C), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
However, the general formula (D), R represents a group containing a straight chain hydrocarbon group having 6 or more carbon atoms, R _1, and R ₂ are each independently a hydrogen atom, and hydrocarbon Represents one of hydrogen groups, and n represents an integer of 1 or more.
<3> The lubricant according to any one of <1> to <2>, wherein the conjugate base is represented by any one of the following general formula (X) and the following general formula (Y).

However, in said general formula (X), l represents an integer of 1-12.
However, in said general formula (Y), l represents the integer of 1-12.
<4> A magnetic material comprising a nonmagnetic support, a magnetic layer on the nonmagnetic support, and the lubricant according to any one of <1> to <3> on the magnetic layer. It is a recording medium.
<5> having a conjugate base and a conjugate acid,
The conjugate acid has a group containing a hydroxyl group and a group containing a linear hydrocarbon group having 6 or more carbon atoms;
It is an ionic liquid characterized in that the pKa in acetonitrile of the acid that is the base of the conjugate base is 10 or less.
<6> The conjugate acid according to <5>, wherein the conjugate acid is represented by any one of the following general formula (A), the following general formula (B), the following general formula (C), and the following general formula (D). It is an ionic liquid.

However, the general formula (A), R _1, and R ₂ represents independently a hydrogen atom, and one of the group carbon atoms containing 6 or more straight chain hydrocarbon radical, n Represents an integer of 1 or more. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
However, in said general formula (B), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
However, in said general formula (C), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
However, the general formula (D), R represents a group containing a straight chain hydrocarbon group having 6 or more carbon atoms, R _1, and R ₂ are each independently a hydrogen atom, and hydrocarbon Represents one of hydrogen groups, and n represents an integer of 1 or more.
<7> The conjugated liquid according to any one of <5> to <6>, wherein the conjugate base is represented by any one of the following general formula (X) and the following general formula (Y).

However, in said general formula (X), l represents an integer of 1-12.
However, in said general formula (Y), l represents the integer of 1-12.

According to the present invention, an ionic liquid that has excellent lubricity even at a high temperature and can be applied to various purposes because it can have a low melting point, has an excellent lubricity even at a high temperature, and low Since the melting point can be increased, it is possible to provide a lubricant that can be applied to various purposes and a magnetic recording medium having excellent practical characteristics.

FIG. 1 is a graph showing the transition and prediction of the in-plane recording density of a hard disk drive. FIG. 2 is a road map of head media spacing (HMS) with respect to the in-plane recording density of the hard disk. FIG. 3 is a schematic diagram showing heat-assisted magnetic recording. FIG. 4 is a cross-sectional view showing an example of a hard disk according to an embodiment of the present invention. FIG. 5 is a cross-sectional view showing an example of a magnetic tape according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail in the following order with reference to the drawings.
1. 1. Lubricant and ionic liquid 2. Magnetic recording medium Example

<1. Lubricant and ionic liquid>
The lubricant shown as one embodiment of the present invention contains an ionic liquid having a conjugate acid and a conjugate base.
The ionic liquid shown as one embodiment of the present invention has a conjugate acid and a conjugate base.
In the ionic liquid, the conjugate acid has a group containing a hydrocarbon group. The hydrocarbon group is a linear hydrocarbon group having 6 or more carbon atoms. Here, the “linear hydrocarbon group having 6 or more carbon atoms” may be a partially fluorinated hydrocarbon group in which a part of hydrogen atoms bonded to carbon is substituted with a fluorine atom.
In the ionic liquid, the conjugate acid has a group containing a hydroxyl group.
In the ionic liquid, the pKa in acetonitrile of the acid serving as the base of the conjugate base is 10 or less.

The ionic liquid in this embodiment has a conjugate acid and a conjugate base, and the pKa in acetonitrile of the acid that is the base of the conjugate base is 10 or less, and therefore exhibits excellent thermal stability. be able to. Since the cationic part has a group containing a hydrocarbon group having 6 or more carbon atoms, it can have excellent lubricating properties. Moreover, since a hydroxyl group was introduced into the cation moiety, the heat resistance and solubility in a fluorinated solvent were improved, and the melting point was lowered. Some compounds have improved solubility in CF ₃ (CHF) ₂ CF ₂ CF ₃ , which is often used as a fluorinated solvent in hard disk lubricant coating processes, resulting in explosion-proof production lines for magnetic recording media There is no need to make specifications.
Here, the lubricant containing the ionic liquid may be used at a concentration of about 0.05% by mass of the ionic liquid. Therefore, the solubility of the ionic liquid in the fluorine-based solvent is preferably 0.05% by mass or more. Further, depending on the use situation, higher solubility may be required. Furthermore, the use of lubricants conditions, when considering the changes in the storage status, or 0.1 wt% _{[CF 3 (CHF) 2 CF 2} CF 3 ionic liquid 0.1 parts by mass or more with respect to 100 parts by weight ] May be required.

The pKa is a strong acid of 10 or less, and preferably 6.0 or less.
The lower limit of the pKa is not particularly limited and may be appropriately selected depending on the intended purpose. However, the pKa is preferably −5.0 or more.

Here, pKa in the present specification is an acid dissociation constant, which is an acid dissociation constant in acetonitrile.

<< Conjugate base >>
The conjugate base is not particularly limited as long as the pKa in acetonitrile of the original acid is 10 or less, and can be appropriately selected according to the purpose. For example, the conjugate base is represented by the following general formula (X). A conjugate base represented by the following general formula (Y), a conjugate base represented by the following general formula (U), a conjugate base represented by the following general formula (V), and the following general formula (W) And the conjugate base represented. Among these, the conjugate base represented by the following general formula (X) and the conjugate base represented by the following general formula (Y) are preferable in that the solubility of the ionic liquid in the solvent can be increased.

However, in the general formula (X), l represents an integer of 1 to 12 and is preferably an integer of 1 to 6.
However, in the said general formula (Y), l represents the integer of 1-12, and an integer of 1-6 is preferable.

Examples of the acid (HA) that is the base of the conjugate base include bis ((perfluoroalkyl) sulfonyl) imide [(C _l F _{21 + 1} SO ₂ ) ₂ NH] (pKa = 0 to 0.3), perfluorocyclopropane Sulfonimide (pKa = −0.8), perfluoroalkylsulfonic acid (C _m F _{2m + 1} SO ₃ H) (pKa = 0.7), tris (perfluoroalkanesulfonyl) methide compound [(CF ₃ SO ₂ ) ₃ CH] (pKa = -3.7), tricyanomethane (pKa = 5.1), inorganic acid [nitric acid (pKa = 9.4), sulfuric acid (pKa = 8.7), etc.], tetrafluoroboric acid ( pKa = 1.8), and Bronsted acid positioned as a super acid such as hexafluorophosphoric acid is preferable. These pKas are described, for example, in J. Org. Org. Chem. Vol. 76, No2, p. 394.

<< Conjugated acid >>
The conjugate acid has a group containing a linear hydrocarbon group having 6 or more carbon atoms, and further has a group containing a hydroxyl group.

The method for introducing a hydroxyl group into the conjugate acid is not particularly limited. For example, there is a method of introducing via a linear alkylene chain. One example of this method employs a method of alkylating a nitrogen atom of a conjugate acid using a halide as described in the following examples. Therefore, the introduction method is completely different from Z-DOL and Z-Tetraol, which are general perfluoropolyether lubricants, and the method is not helpful.

The conjugate acid has a group containing a linear hydrocarbon group having 6 or more carbon atoms.
The number of carbon atoms of the hydrocarbon group is not particularly limited as long as it is 6 or more, and can be appropriately selected according to the purpose, but is preferably 10 or more.

The upper limit of the carbon number of the linear hydrocarbon group having 6 or more carbon atoms is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of procurement of raw materials, the carbon number Is preferably 30 or less, more preferably 25 or less, and particularly preferably 20 or less. When the hydrocarbon group is a long chain, the friction coefficient can be reduced and the lubrication characteristics can be improved.
The group containing a linear hydrocarbon group having 6 or more carbon atoms is preferably a linear hydrocarbon group having 6 or more carbon atoms.
However, since the solubility in a solvent tends to decrease when the number of carbon atoms is too large, the carbon number of the hydrocarbon group is determined in consideration of the effect of reducing the friction coefficient and the solubility in a solvent.

The hydrocarbon group may be linear, and may be either a saturated hydrocarbon group, an unsaturated hydrocarbon group partially having a double bond, or an unsaturated branched hydrocarbon group partially having a branch. Good. Among these, an alkyl group which is a saturated hydrocarbon group is preferable from the viewpoint of wear resistance. Moreover, it is also preferable that it is a linear hydrocarbon group which does not have a branch in part. Of course, it may be a partially branched hydrocarbon group.

Examples of the hydrocarbon group include a group represented by the following general formula (I) and a group represented by the following general formula (II).
— (CH ₂ ) ₁ —CH ₃ General Formula (I)
— (CH ₂ ) _m — (CF ₂ ) _n —CF ₃ General Formula (II)
In the general formula (I), l represents an integer of 5 or more, preferably an integer of 9 to 29, more preferably an integer of 9 to 24, and particularly preferably an integer of 9 to 19.
In the general formula (II), m represents an integer of 1 to 6, and n represents an integer of 3 to 20. However, m + n is 7 or more. m is preferably an integer of 1 to 3, and n is preferably an integer of 5 to 10.

The conjugate acid has a group containing a hydroxyl group. Examples of the group containing a hydroxyl group include a group represented by the following general formula (IV).
— (CH ₂ ) _n —OH Formula (IV)
In the general formula (IV), n is an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

As the conjugate acid, a conjugate acid represented by the following general formula (A), a conjugate acid represented by the following general formula (B), a conjugate acid represented by the following general formula (C), and the following general formula ( The conjugate acid represented by D) is preferable in terms of heat resistance and lubrication characteristics.

However, the general formula (A), R _1, and R ₂ represents independently a hydrogen atom, and one of the group carbon atoms containing 6 or more straight chain hydrocarbon radical, n Represents an integer of 1 or more. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
However, in said general formula (B), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
However, in said general formula (C), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
However, the general formula (D), R represents a group containing a straight chain hydrocarbon group having 6 or more carbon atoms, R _1, and R ₂ are each independently a hydrogen atom, and hydrocarbon Represents one of hydrogen groups, and n represents an integer of 1 or more.

The R ₁ and R _{2 in} the general formula (A), the R in the general formula (B), the R in the general formula (C), and the hydrocarbon group in the R in the general formula (D). As long as it is 6 or more, there is no restriction | limiting in particular, Although it can select suitably according to the objective, 10 or more is preferable.
The upper limit of the carbon number of the hydrocarbon group is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of procurement of raw materials, the carbon number is preferably 30 or less, and 25 or less. More preferred is 20 or less. When the hydrocarbon group is a long chain, the friction coefficient can be reduced and the lubrication characteristics can be improved.
As said R < ₁ >, said R < ₂ >, and said R, the said C6 or more linear hydrocarbon group is preferable.
However, since the solubility in a solvent tends to decrease when the number of carbon atoms is too large, the carbon number of the hydrocarbon group is determined in consideration of the effect of reducing the friction coefficient and the solubility in a solvent.

The R ₁ and R _{2 in} the general formula (A), the R in the general formula (B), the R in the general formula (C), and the hydrocarbon group in the R in the general formula (D). May be a straight chain, and may be a saturated hydrocarbon group, an unsaturated hydrocarbon group partially having a double bond, or an unsaturated branched hydrocarbon group partially having a branch. Among these, an alkyl group which is a saturated hydrocarbon group is preferable from the viewpoint of wear resistance. Moreover, it is also preferable that it is a linear hydrocarbon group which does not have a branch in part.

Examples of the R ₁ and R _{2 in} the general formula (A), the R in the general formula (B), the R in the general formula (C), and the R in the general formula (D) include: Examples include groups represented by the following general formula (III).
— (CH ₂ ) ₁ —CH ₃ General Formula (III)
In the general formula (III), l represents an integer of 5 or more, preferably an integer of 9 or more and 29 or less, and more preferably an integer of 9 or more and 19 or less.

When R ₁ and R ₂ in the general formula (D) are hydrocarbon groups, the carbon number thereof is not particularly limited and may be appropriately selected depending on the intended purpose. 10 is preferable, and 1 to 6 carbon atoms is more preferable.

N is an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

Examples of the conjugate acid represented by the general formula (A) include conjugate acids represented by the following general formula (A-1).

In the general formula (A-1), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, and n represents an integer of 1 or more.

<< Preferred example of ionic liquid >>
As the ionic liquid, an ionic liquid represented by the following general formula (1), an ionic liquid represented by the following general formula (2), an ionic liquid represented by the following general formula (3), and the following general formula (4) The ionic liquid represented by this is preferable.

However, in the general formula (1), A ⁻ represents a conjugate base, and R ₁ and R ₂ each independently represent a hydrogen atom and a linear hydrocarbon group having 6 or more carbon atoms. Any one of the groups to be included, and n represents an integer of 1 or more. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
However, the general formula (2), A ^- represents a conjugate base, R represents the number of carbon atoms represents a group containing 6 or more straight chain hydrocarbon group, n is an integer of 1 or more .
Provided that said Chu general formula (3), A ^- represents a conjugate base, R represents the number of carbon atoms represents a group containing 6 or more straight chain hydrocarbon group, n is an integer of 1 or more .
However, in the general formula (4), A ⁻ represents a conjugate base, R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, and R ₁ and R ₂ are respectively Independently, it represents either a hydrogen atom or a hydrocarbon group, and n represents an integer of 1 or more.

As the ionic liquid represented by the general formula (1), an ionic liquid represented by the following general formula (1-1) and an ionic liquid represented by the following general formula (1-2) are preferable.

However, in the general formula (1-1), R ₁ and R ₂ each independently represent either a hydrogen atom or a group containing a linear hydrocarbon group having 6 or more carbon atoms. , N represents an integer of 1 or more, and l represents an integer of 1 to 12. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
However, in the general formula (1-2), R ₁ and R ₂ each independently represent either a hydrogen atom or a group containing a linear hydrocarbon group having 6 or more carbon atoms. , N represents an integer of 1 or more, and l represents an integer of 1 to 12. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.

As the ionic liquid represented by the general formula (2), an ionic liquid represented by the following general formula (2-1) and an ionic liquid represented by the following general formula (2-2) are preferable. Among these, an ionic liquid represented by the following general formula (2-2) is more preferable from the viewpoint of excellent solubility in a fluorine-based solvent.

In the general formula (2-1), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, n represents an integer of 1 or more, and l represents 1 to 12 Represents the following integers:
In the general formula (2-2), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, n represents an integer of 1 or more, and l represents 1 or more and 12 Represents the following integers:

Examples of the ionic liquid represented by the general formula (3) include an ionic liquid represented by the following general formula (3-1) and an ionic liquid represented by the following general formula (3-2). It is preferable at the point which is excellent in the solubility to.

In the general formula (3-1), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, n represents an integer of 1 or more, and l represents 1 or more and 12 Represents the following integers:
In the general formula (3-2), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, n represents an integer of 1 or more, and l represents 1 or more and 12 Represents the following integers:

Examples of the ionic liquid represented by the general formula (4) include an ionic liquid represented by the following general formula (4-1) and an ionic liquid represented by the following general formula (4-2). It is preferable at the point which is excellent in the solubility to.

However, in the general formula (4-1), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, and R ₁ and R ₂ are each independently a hydrogen atom, And n represents an integer of 1 or more, and l represents an integer of 1 or more and 12 or less.
In the general formula (4-2), R represents a group containing a linear hydrocarbon group having 6 or more carbon atoms, and R ₁ and R ₂ are each independently a hydrogen atom, And n represents an integer of 1 or more, and l represents an integer of 1 or more and 12 or less.

The preferable range of R in the general formula of the ionic liquid is the same as the preferable range of R in the general formula of the corresponding conjugate acid.
R ₁ and R ₂ in the ionic liquid represented by the general formula (1), the ionic liquid represented by the general formula (1-1), and the ionic liquid represented by the general formula (1-2) are preferable. The range is the same as the preferable range of R ₁ and R ₂ of the conjugate acid represented by the corresponding general formula (A).
R ₁ and R ₂ in the ionic liquid represented by the general formula (4), the ionic liquid represented by the general formula (4-1), and the ionic liquid represented by the general formula (4-2) are preferable. The range is the same as the preferable range of R ₁ and R ₂ of the conjugate acid represented by the corresponding general formula (D).
The preferable range of n in the general formula of the ionic liquid is the same as the preferable range of n of the corresponding general formula of the conjugate acid.
The preferable range of l in the general formula of the ionic liquid is the same as the preferable range of l of the corresponding general formula of the conjugate base.

There is no restriction | limiting in particular as the synthesis | combining method of the said ionic liquid, According to the objective, it can select suitably, For example, various said ionic liquids are synthesize | combined by referring to the method as described in the following Example. be able to.

As the lubricant in the present embodiment, the above-described ionic liquid may be used alone or in combination with a conventionally known lubricant. For example, it can be used in combination with long chain carboxylic acid, long chain carboxylic acid ester, perfluoroalkyl carboxylic acid ester, carboxylic acid perfluoroalkyl ester, perfluoroalkyl carboxylic acid perfluoroalkyl ester, perfluoropolyether derivative, etc. Is possible.

In order to maintain the lubricating effect under severe conditions, an extreme pressure agent may be used in combination at a mass ratio of about 30:70 to 70:30. The extreme pressure agent acts to prevent friction and wear by forming a reaction product film by reacting with the metal surface due to frictional heat generated when metal contact occurs partially in the boundary lubrication region. Is. As the extreme pressure agent, for example, any of a phosphorus extreme pressure agent, a sulfur extreme pressure agent, a halogen extreme pressure agent, an organometallic extreme pressure agent, a composite extreme pressure agent, and the like can be used.

Moreover, you may use a rust preventive together as needed. The rust inhibitor may be any rust inhibitor that can be used as a rust inhibitor for this type of magnetic recording medium. For example, phenols, naphthols, quinones, heterocyclic compounds containing nitrogen atoms, oxygen atoms And heterocyclic compounds containing sulfur atoms, and the like. The rust preventive agent may be used as a lubricant, but a magnetic layer is formed on a nonmagnetic support, a rust preventive layer is applied thereon, and then a lubricant layer is applied. Thus, it may be applied in two or more layers.

In addition, as the solvent for the lubricant, for example, alcohol solvents such as isopropyl alcohol (IPA) and ethanol can be used alone or in combination. For example, it can be used by mixing a hydrocarbon solvent such as normal hexane or a fluorine solvent.
As the solvent, a fluorine-based solvent is preferable. Examples of the fluorine-based solvent include hydrofluoroethers [for example, C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ , CF ₃ (CHF) ₂ CF ₂ CF ₃ ], etc., and alcohols such as IPA, ethanol or methanol may be used in combination.
The fluorinated solvent may be a commercially available product. Examples of the commercially available products include Novec ^™ 7000, 7100, 7200, 7300, 71IPA manufactured by 3M, Vertrel XF, X-P10 manufactured by Mitsui DuPont Fluorochemical Co., Ltd., and the like.

<2. Magnetic recording media>
Next, a magnetic recording medium using the above-described lubricant will be described. A magnetic recording medium shown as an embodiment of the present invention has at least a magnetic layer on a nonmagnetic support, and the magnetic layer contains the above-mentioned lubricant.

The lubricant in the present embodiment can be applied to a so-called metal thin film type magnetic recording medium in which a magnetic layer is formed on the surface of a nonmagnetic support by a technique such as vapor deposition or sputtering. The present invention can also be applied to a magnetic recording medium having a configuration in which an underlayer is interposed between a nonmagnetic support and a magnetic layer. Examples of such a magnetic recording medium include a magnetic disk and a magnetic tape.

FIG. 4 is a cross-sectional view showing an example of a hard disk. This hard disk has a structure in which a substrate 11, an underlayer 12, a magnetic layer 13, a carbon protective layer 14, and a lubricant layer 15 are sequentially laminated.

FIG. 5 is a cross-sectional view showing an example of a magnetic tape. This magnetic tape has a structure in which a backcoat layer 25, a substrate 21, a magnetic layer 22, a carbon protective layer 23, and a lubricant layer 24 are sequentially laminated.

In the magnetic disk shown in FIG. 4, the nonmagnetic support corresponds to the substrate 11 and the underlayer 12, and in the magnetic tape shown in FIG. 5, the nonmagnetic support corresponds to the substrate 21. When a rigid substrate such as an Al alloy plate or a glass plate is used as the nonmagnetic support, an oxide film such as an alumite treatment or Ni-P film may be formed on the substrate surface to harden the surface. Good.

The magnetic layers 13 and 22 are formed as a continuous film by a technique such as plating, sputtering, vacuum deposition, or plasma CVD. The magnetic layers 13 and 22 include metals such as Fe, Co, Ni, Co—Ni alloys, Co—Pt alloys, Co—Ni—Pt alloys, Fe—Co alloys, Fe—Ni alloys, In-plane magnetization recording metal magnetic film made of Fe—Co—Ni alloy, Fe—Ni—B alloy, Fe—Co—B alloy, Fe—Co—Ni—B alloy, etc., Co—Cr alloy Examples thereof include perpendicular magnetic recording metal magnetic thin films such as thin films and Co—O thin films.

In particular, when an in-plane magnetization recording metal magnetic thin film is formed, a nonmagnetic material such as Bi, Sb, Pb, Sn, Ga, In, Ge, Si, or Tl is previously formed on the nonmagnetic support as the underlayer 12. In addition, metal magnetic materials are vapor-deposited or sputtered from the vertical direction, and these non-magnetic materials are diffused in the magnetic metal thin film to eliminate orientation and ensure in-plane isotropy and improve coercive force. You may do it.

Further, hard protective layers 14 and 23 such as a carbon film, a diamond-like carbon film, a chromium oxide film, and a SiO ₂ film may be formed on the surfaces of the magnetic layers 13 and 22.

As a method of retaining the above-mentioned lubricant in such a metal thin film type magnetic recording medium, as shown in FIG. 4 and FIG. 5, the top surface of the magnetic layers 13 and 22 or the surface of the protective layers 14 and 23 is used. The method of coating is mentioned. The coating amount of the lubricant is preferably 0.1 mg / m ² to 100 mg / m ² , more preferably 0.5 mg / m ² to 30 mg / m ² , and 0.5 mg / m ² to Particularly preferred is 20 mg / m ² .

Further, as shown in FIG. 5, in the metal thin film type magnetic tape, in addition to the metal magnetic thin film as the magnetic layer 22, a back coat layer 25 may be formed as necessary.

The back coat layer 25 is formed by adding a carbon-based fine powder for imparting conductivity to the resin binder and an inorganic pigment for controlling the surface roughness. In the present embodiment, the aforementioned lubricant may be added to the back coat layer 25 by internal addition or top coat. Further, the above-described lubricant may be added to both the magnetic layer 22 and the back coat layer 25 by internal addition or top coat.

As another embodiment, the lubricant can be applied to a so-called coating type magnetic recording medium in which a magnetic coating film is formed as a magnetic layer by applying a magnetic paint to the surface of a nonmagnetic support. is there. In the coating-type magnetic recording medium, any conventionally known magnetic powder, resin binder and the like constituting the nonmagnetic support, the magnetic coating film, and the like can be used.

For example, as the nonmagnetic support, for example, a polymer support formed of a polymer material typified by polyesters, polyolefins, cellulose derivatives, vinyl resins, polyimides, polyamides, polycarbonates and the like. Examples thereof include metal substrates made of aluminum alloy, titanium alloy, etc., ceramics substrates made of alumina glass, etc., glass substrates, and the like. Moreover, the shape is not limited at all, and any shape such as a tape shape, a sheet shape, or a drum shape may be used. Further, the non-magnetic support may be subjected to a surface treatment so as to form fine irregularities in order to control the surface property.

Examples of the magnetic powder include ferromagnetic iron oxide particles such as γ-Fe ₂ O ₃ and cobalt-coated γ-Fe ₂ O ₃ , ferromagnetic chromium dioxide particles, metals such as Fe, Co, Ni, and the like. Examples thereof include ferromagnetic metal particles made of an alloy containing hexagonal plate-like ferrite fine particles.

Examples of the resin binder include vinyl chloride, vinyl acetate, vinyl alcohol, vinylidene chloride, acrylic acid ester, methacrylic acid ester, styrene, butadiene, acrylonitrile, or a combination of these two or more, polyurethane Resins, polyester resins, epoxy resins and the like are exemplified. In these binders, a hydrophilic polar group such as a carboxylic acid group, a carboxyl group or a phosphoric acid group may be introduced in order to improve the dispersibility of the magnetic powder.

In addition to the magnetic powder and the resin binder, a dispersant, an abrasive, an antistatic agent, an antirust agent, and the like may be added to the magnetic coating film as an additive.

Examples of a method for retaining the lubricant in such a coating type magnetic recording medium include a method of internally adding the magnetic layer constituting the magnetic coating film formed on the nonmagnetic support, There is a method of top-coating the surface of the layer, or a combination of both. When the lubricant is internally added to the magnetic coating film, it is added in the range of 0.2 to 20 parts by mass with respect to 100 parts by mass of the resin binder.

Further, when the lubricant is top-coated on the surface of the magnetic layer, the coating amount is preferably 0.1 mg / m ² to 100 mg / m ² , and 0.5 mg / m ² to 20 mg / m ^{2. 2} is more preferable. In addition, as a deposition method when the lubricant is top-coated, an ionic liquid is dissolved in a solvent, and the obtained solution is applied or sprayed, or a magnetic recording medium is immersed in this solution.

The magnetic recording medium to which the lubricant in the present embodiment is applied exhibits excellent running performance, wear resistance, durability, and the like due to the lubricating action, and can further improve the thermal stability.

<3. Example>
Hereinafter, specific examples of the present invention will be described. In this example, an ionic liquid was synthesized to produce a lubricant containing the ionic liquid. First, the solubility in Bertrell [CF ₃ (CHF) ₂ CF ₂ CF ₃ ], which is a fluorine-based solvent, was examined. The lubricant solution was applied to the surfaces of a magnetic disk and a magnetic tape, and the disk durability and tape durability were evaluated, respectively. The production of the magnetic disk, the disk durability test, the production of the magnetic tape, and the tape durability test were performed as follows. The present invention is not limited to these examples.

<Manufacture of magnetic disks>
For example, in accordance with International Publication No. 2005/068589, a magnetic thin film was formed on a glass substrate to produce a magnetic disk as shown in FIG. Specifically, a chemically strengthened glass disk made of aluminum silicate glass with an outer diameter of 65 mm, an inner diameter of 20 mm, and a disk thickness of 0.635 mm is prepared, and the surface is polished so that Rmax is 4.8 nm and Ra is 0.43 nm. did. The glass substrate was subjected to ultrasonic cleaning in pure water and isopropyl alcohol (IPA) having a purity of 99.9% or more for 5 minutes each, left in IPA saturated vapor for 1.5 minutes and then dried. did.

On this substrate 11, a NiAl alloy (Ni: 50 mol%, Al: 50 mol%) thin film is formed as a seed layer by DC magnetron sputtering, and a CrMo alloy (Cr: 80 mol%, Mo: 20 mol) is used as the underlayer 12. %) A thin film having a thickness of 8 nm and a CoCrPtB alloy (Co: 62 mol%, Cr: 20 mol%, Pt: 12 mol%, B: 6 mol%) as a magnetic layer 13 were sequentially formed to a thickness of 15 nm.

Next, a carbon protective layer 14 made of amorphous diamond-like carbon is formed to 5 nm by plasma CVD, and the disk sample is ultrasonicated in isopropyl alcohol (IPA) having a purity of 99.9% or more for 10 minutes in a cleaner. Cleaning was performed to remove impurities on the disk surface, and then drying was performed. After that, the lubricant layer 15 was formed to have a thickness of about 1 nm by applying it to the disk surface by a dip coating method using a mixed solvent of ionic liquid n-hexane and ethanol in an environment of 25 ° C. and 50% relative humidity (RH).

<Thermal stability measurement>
In TG / DTA measurement, EXSTAR6000 manufactured by Seiko Instruments Inc. is used, and measurement is performed in a temperature range of 30 ° C-600 ° C at a temperature increase rate of 10 ° C / min while introducing air at a flow rate of 200 ml / min. went.
The endothermic peak temperature in the measurement was taken as the melting point.

<Disk durability test>
Using a commercially available strain gauge type disk friction and wear tester, after mounting the hard disk on the rotating spindle with a tightening torque of 14.7 Ncm, the center of the air bearing surface on the inner circumference side of the hard disk of the head slider is A head slider was mounted on the hard disk so as to be 17.5 mm from the center, and a CSS durability test was conducted. The head used in this measurement is an IBM 3370 type inline head, the material of the slider is Al ₂ O ₃ —TiC, and the head load is 63.7 mN. In this test, the maximum value of the frictional force was monitored for each CSS (Contact, Start, Stop) in an environment of clean cleanliness 100 and 25 ° C. 60% RH. The number of times the friction coefficient exceeded 1.0 was taken as the result of the CSS durability test. In the result of the CSS endurance test, when it exceeded 50,000 times, “> 50,000” was displayed. Moreover, in order to investigate heat resistance, the CSS durability test after performing the heat test for 3 minutes at the temperature of 200 degreeC was similarly done.

<Manufacture of magnetic tape>
A magnetic tape having a cross-sectional structure as shown in FIG. 5 was produced. First, Co was deposited on a substrate 21 made of a Toray Mikutron (aromatic polyamide) film having a thickness of 5 μm by an oblique deposition method to form a magnetic layer 22 made of a ferromagnetic metal thin film having a thickness of 100 nm. Next, a carbon protective layer 23 made of 10 nm diamond-like carbon was formed on the surface of the ferromagnetic metal thin film by plasma CVD, and then cut to a width of 6 mm. An ionic liquid dissolved in IPA was applied onto the carbon protective layer 23 so as to have a film thickness of about 1 nm to form a lubricant layer 24, thereby preparing a sample tape.

<Tape durability test>
About each sample tape, the still durability under a temperature of -5 ° C and a temperature of 40 ° C and 30% RH, and the friction coefficient and shuttle durability under a temperature of -5 ° C and a temperature of 40 ° C and 90% RH. Measurements were made. For the still durability, the decay time until the output in the pause state decreased by -3 dB was evaluated. Shuttle durability was evaluated by the number of shuttles until the output decreased by 3 dB after repeatedly running the shuttle for 2 minutes each time. Moreover, in order to investigate heat resistance, the durability test after performing the heat test for 10 minutes at the temperature of 100 degreeC was similarly done.

The ionic liquid in the present embodiment has a conjugate base and a conjugate acid, and the pKa in acetonitrile of the acid serving as the base of the conjugate base is 10 or less. Furthermore, it is preferable that the conjugate acid (cation moiety) has a group containing a hydrocarbon group having 6 or more carbon atoms and a hydroxyl group. The influence on the thermal stability of such an ionic liquid and the durability of a magnetic recording medium using the ionic liquid was investigated. Furthermore, the solubility in a fluorinated solvent was examined.

Example 1A
<Synthesis of Nonafluorobutanesulfonic Acid-1- 'Hydroxypropyl-3-octadecylimidazolium>
Synthesis of nonafluorobutanesulfonic acid-1-3′hydroxylpropyl-3-octadecylimidazolium was performed according to the following scheme.

1-octadecyl imidazole was obtained by dissolving 3 g of imidazole in 100 mL of acetonitrile, adding 14.9 g of octadecyl bromide and 2.51 g of potassium hydroxide, heating the mixture with stirring, and refluxing for 4 hours. After removing the solvent, the mixture was extracted with dichloromethane and purified by column chromatography. When analyzed by gas chromatography, the purity was 98.5% or more.

6.13 g of 1-octadecylimidazole and 3.66 g of 3-bromopropanol were added to the flask and heated at 120 ° C. for 5.5 hours. After returning to normal temperature, ethyl acetate was added for crystallization. The crystals were recrystallized from ethyl acetate to obtain 7.66 g of colorless crystals of 1-3'hydroxylpropyl-3-octadecylimidazolium bromide. Yield 87.1%.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.843 (t / J = 6.8 Hz, 3H), 1.160-1.350 (m, 30H), 1.830-1.940 (m, 2H) ), 2.095-2.140 (m, 2H), 3.626 (t / J = 5.6 Hz, 2H), 4.276 (t / J = 7.6 Hz, 2H), 4.510 (t /J=6.4 Hz, 2H), 7.262-7.271 (m, 1H), 7.566-7.575 (m, 1H), 10.225 (s, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.080, 22.647, 26.259, 28.962, 29.326, 29.479, 29.623, 29.671, 30.208, 31.844 , 32.392, 47.179, 50.245, 57.135, 121.502, 122.480, 137.381

From these spectra, the product was identified as 1-3'hydroxylpropyl-3-octadecylimidazolium bromide.

1-3 'hydroxylpropyl-3-octadecylimidazolium bromide 3.16 g was dissolved by heating water, and an aqueous solution of 2.33 g of potassium nonafluorobutanesulfonate was added. After stirring at room temperature for 1 hour, heating under reflux was performed for 1 hour. After cooling, the reaction solution was extracted with dichloromethane and washed thoroughly with water until the silver nitrate test was negative. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed to obtain 4.32 g of colorless crystalline nonafluorobutanesulfonic acid-1-3'hydroxylpropyl-3-octadecylimidazolium. Yield 92.6%.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SO ₂ bind to 1133cm ^-1, symmetric stretching vibration of CF ₂ to 1255cm ^-1, antisymmetric stretching vibration of SO ₂ bind to 1352cm ^-1, bending vibration of CH ₂ in 1469cm ^-1, 1566cm ^-1 C = N symmetric stretching vibration, 2851 cm ⁻¹ CH ₂ symmetric stretching vibration, 2920 cm ⁻¹ CH ₂ inverse symmetric stretching vibration, 3150 cm ⁻¹ imidazole ring CH stretching vibration, and 3481 cm ⁻¹ OH stretching vibration. Vibration was seen.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.852 (t / J = 6.8 Hz, 3H), 1.170-1.320 (m, 30H), 1.780-1.880 (m, 2H) ), 2.058-2.088 (m, 2H), 3.613 (t / J = 6.0 Hz, 2H), 4.158 (t / J = 7.6 Hz, 2H), 4.373 (t /J=6.0 Hz, 2H), 7.218-7.226 (m, 1H), 7.422-7.431 (m, 1H), 9.091 (s, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.070, 22.656, 26.173, 28.885, 29.326, 29.470, 29.671, 30.644, 31.894, 32.153 , 47.265, 50.149, 57.950, 121.780, 122.643, 136.461

From these spectra, it was identified that the product was nonafluorobutanesulfonic acid 1-3′hydroxylpropyl-3-octadecylimidazolium.
The pKa in acetonitrile of the acid (nonafluorobutanesulfonic acid) that is the base of the conjugate base in nonafluorobutanesulfonic acid-1-3′hydroxylpropyl-3-octadecylimidazolium is 0.7.

(Example 2A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide 1-3'hydroxylpropyl-3-octadecylimidazolium>
Synthesis of bis (nonafluorobutanesulfonyl) imide 1-3′hydroxylpropyl-3-octadecylimidazolium was performed according to the following scheme.

3.07 g of 1-3′hydroxylpropyl-3-octadecylimidazolium bromide synthesized in Example 1A was dissolved in heated pure water, and 4.22 g of potassium bis (nonafluorobutanesulfonyl) imide was mixed with water and ethanol. What was dissolved in the solvent was added. The mixture was heated to reflux for 1 hour, cooled and extracted with dichloromethane. The organic layer was washed with pure water until the AgNO ₃ test was negative. After drying over anhydrous sodium sulfate, the solvent was removed to obtain 5.20 g of bis (nonafluorobutanesulfonyl) imide 1-3′hydroxylpropyl-3-octadecylimidazolium as a colorless liquid. Yield 81.1%.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SO ₂ binding to 1077 cm ^-1, symmetric stretching vibration of CF ₂ to 1236cm ^-1, antisymmetric stretching vibration of SO ₂ bind to 1354cm ^-1, bending vibration of CH ₂ in 1466cm ^-1, 1565cm ^-1 C = N symmetrical stretching vibration, 2856cm ⁻¹ CH ₂ symmetric stretching vibration, 2927cm ⁻¹ CH ₂ reverse symmetric stretching vibration, 3152cm ⁻¹ imidazole ring CH stretching vibration, 3553cm ⁻¹ OH stretching vibration Vibration was seen.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.855 (t / J = 6.8 Hz, 3H), 1.180-1.330 (m, 30H), 1.780-1.880 (m, 2H) ), 2.057-2.086 (m, 2H), 3.655 (t / J = 6.0 Hz, 2H), 4.138 (t / J = 7.6 Hz, 2H), 4.345 (t /J=6.0 Hz, 2H), 7.211-7.235 (m, 1H), 7.357-7366 (m, 1H), 8.794 (s, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.070, 22.666, 26.106, 28.847, 29.288, 29.335, 29.450, 29.556, 29.671, 30.073 , 31.904, 31.980, 47.341, 50.235, 58.323, 121.838, 122.777, 135.857

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide 1-3′hydroxylpropyl-3-octadecylimidazolium.
The pKa in acetonitrile of the acid [bis (nonafluorobutanesulfonyl) imide], which is the base of the conjugate base in bis (nonafluorobutanesulfonyl) imide 1-3′hydroxylpropyl-3-octadecylimidazolium, in the acetonitrile is 0. 0.

(Example 3A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide-N-3'hydroxylpropyl-N-octadecylpyrrolidinium>
Bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N-octadecylpyrrolidinium was synthesized according to the following scheme.

Bromooctadecane 52.4 g and potassium hydroxide 8.75 g were added to acetonitrile, and pyrrolidine 11.09 g was added. Thereafter, heating under reflux was performed for 24 hours. After filtering the crystals, the solvent of the organic layer was removed and the residue was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate to obtain 44.05 g of octadecylpyrrolidine. The purity by gas chromatography was 99.0% or more.

Octadecylpyrrolidine (6.00 g) and 3-bromopropanol (3.23 g) were added to the flask and heated at 120 ° C. for 3.0 hours. After returning to room temperature, ethyl acetate was added for crystallization to obtain 7.77 g of N-3'hydroxylpropyl-N-octadecylpyrrolidinium bromide. Yield 90.5%.

In addition, the peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated methanol is shown below.
¹ H-NMR (CD ₃ OD, δ ppm); 0.875 (t / J = 7.0 Hz, 3H), 1.190-1.440 (m, 30H), 1.670-1.790 (m, 2H), 1.860-1.950 (m, 2H), 2.130-2230 (m, 4H), 3.250-3.292 (m, 2H), 3.356-3.397 ( m, 2H), 3.537 (t / J = 7.2 Hz, 4H), 3.637 (t / J = 5.8 Hz, 2H)
¹³ C-NMR (CD ₃ OD, δ ppm); 14.454, 22.830, 23.740, 24.219, 27.333, 27.506, 30.266, 30.477, 30.292, 30. 649, 30.793, 33.073, 55.104, 58.477, 59.301, 61.132, 64.122

From these spectra, the product was identified as N-3'hydroxylpropyl-N-octadecylpyrrolidinium bromide.

2.77 g of N-3′hydroxylpropyl-N-octadecylpyrrolidinium bromide is dissolved by heating pure water, and 3.88 g of potassium bis (nonafluorobutanesulfonyl) imide is heated in a mixed solvent of pure water and ethanol. And dissolved. Heating under reflux was performed for 1 hour. The precipitate was extracted with dichloromethane, and the organic layer was thoroughly washed with pure water until the AgNO ₃ test was negative. After drying over anhydrous sodium sulfate, the solvent was removed to obtain 5.52 g of a colorless liquid of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N-octadecylpyrrolidinium. Yield 97.4%.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SO ₂ binding to 1140 cm ^-1, symmetric stretching vibration of CF ₂ to 1237cm ^-1, antisymmetric stretching vibration of SO ₂ bind to 1354m ^-1, bending vibration of CH ₂ bound to 1467cm ^-1, 2857cm ^- symmetric stretching vibration of CH ₂ bound to ^1, antisymmetric stretching vibration of CH ₂ bound to 2928cm ^-1, the stretching vibration of the OH bond to 3553cm ^-1 were observed.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.855 (t / J = 7.0 Hz, 3H), 1.170-1.360 (m, 30H), 1.640-1.740 (m, 2H) ), 1.850-1.940 (m, 2H), 2.140-2.290 (m, 4H), 2.623 (brs, 1H), 3.110-3.190 (m, 2H), 3.340-3.410 (m, 2H), 3.420-3.580 (m, 4H), 3.707 (t / J = 5.4 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.080, 21.708, 22.666, 23.289, 26.173, 26.240, 29.010, 29.335, 29.393, 29.546 , 29.680, 31.904, 57.643, 58.333, 60.384, 63.095

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N-octadecylpyrrolidinium.
In addition, pKa in acetonitrile of the acid [bis (nonafluorobutanesulfonyl) imide], which is the base of the conjugate base in bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N-octadecylpyrrolidinium, 0.0.

(Example 4A)
<Synthesis of nonafluorobutanesulfonic acid-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium>
Nonafluorobutanesulfonic acid-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium was synthesized according to the following scheme.

6-Octadecyl-1,8-diazabicyclo [5.4.0] -7-undecene is a non-patent document [N. Matsumura, H.M. Nishiguchi, M. Okada, and S. Yoneda, J.A. Heterocyclic Chem. Pp. 885-887, Vol / 23. Synthesized according to Issue 3 (1986)].

6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium 5.71 g and 3-bromopropanol 3.23 g were added to the flask and heated at 120 ° C. for 3.0 hours. After returning to normal temperature, ethyl acetate was added to dissolve the reaction product, which was then crystallized in a freezer. The crystals were quickly filtered at a low temperature and then vacuum-dried to obtain 6.60 g of 6-octadecyl-8-3'-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide. Yield 81.9%.

6.30 g of 6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide is dissolved by heating pure water, and potassium nonafluorobutanesulfonate An aqueous solution in which 2.99 g of pure water was dissolved by heating was added, reacted at room temperature for 1 hour, and then heated to reflux for 1 hour. After cooling, the reaction solution was extracted with dichloromethane, and the organic layer was washed with pure water until the AgNO ₃ test became negative. After removing the solvent, 6.00 g of nonafluorobutanesulfonic acid-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium was obtained as a pale yellow liquid. Yield 99.4%.

The FTIR absorption of the product and its attribution are shown below.
1134 cm ⁻¹ is a SO ₂ -bonded symmetric stretching vibration, 1255 cm ⁻¹ is a CF ₂ symmetric stretching vibration, 1352 cm ⁻¹ is an SO ₂ -bonded symmetric stretching vibration, 1466 cm ⁻¹ is a CH ₂ bending vibration, 1609 cm ⁻¹ C = N stretching vibration, 2855 cm ⁻¹ symmetric CH ₂ stretching vibration, 2926 cm ⁻¹ CH ₂ inverse symmetric stretching vibration, and 3479 cm ⁻¹ hydroxyl group stretching vibration.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.849 (t / J = 6.8 Hz, 3H), 1.140-1.480 (m, 34H), 1.520-1.940 (m, 8H) ), 1.960-2.140 (m, 2H), 2.423 (brs, 1H), 2.770-2.860 (m, 1H), 3.160-3.610 (m, 6H), 3.610-3.710 (m, 2H) 3.760-3.940 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.089, 20.433, 22.033, 22.656, 25.646, 26.528, 27.179, 27.419, 29.335, 29.412 , 29.680, 30.945, 31.894, 38.631, 47.562, 50.833, 51.337, 54.059, 58.534, 168.122

These spectra identified the product as nonafluorobutanesulfonic acid-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium.
In addition, nonafluorobutanesulfonic acid-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium is a base acid for the conjugate base (nonafluorobutanesulfonic acid). PKa in acetonitrile is 0.7.

(Example 5A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide-6-octadecyl-8-3'-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium>
Bis (nonafluorobutanesulfonyl) imide-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium was synthesized according to the following scheme.

6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide (2.04 g) synthesized in Example 4A was dissolved by heating pure water, A solution in which 3.07 g of potassium bis (nonafluorobutanesulfonyl) imide was dissolved by heating pure water and ethanol was added, reacted at room temperature for 1 hour, and then heated to reflux for 1 hour. After cooling, the reaction solution was extracted with dichloromethane, and the organic layer was washed with pure water until the AgNO ₃ test became negative. After removing the solvent, 3.42 g of a pale yellow liquid of bis (nonafluorobutanesulfonyl) imide-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium was added. Obtained. Yield 87.3%.

The FTIR absorption of the product and its attribution are shown below.
1074 cm ⁻¹ is an anti-symmetric stretching vibration of SNS bond, 1232 cm ⁻¹ is a symmetrical stretching vibration of CF ₂ , 1352 cm ⁻¹ is an anti-symmetric stretching vibration of SO ₂ bond, 1468 cm ⁻¹ is an angular vibration of CH ₂ , 1608 cm ⁻¹ C = N stretching vibration, 2854 cm ⁻¹ CH ₂ symmetrical stretching vibration, 2924 cm ⁻¹ CH ₂ antisymmetric stretching vibration, and 3479 cm ⁻¹ hydroxyl group stretching vibration.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.854 (t / J = 7.2 Hz, 3H), 1.130-1.340 (m, 34H), 1.520-1.910 (m, 8H) ), 1.960-2.140 (m, 2H), 2.770-2.860 (m, 1H), 3.380-3.600 (m, 6H), 3.610-3.715 (m , 2H) 3.740-3.940 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.080, 19.197, 20.299, 21.947, 22.666, 26.518, 27.409, 29.307, 29.345, 29.412 , 29.508, 29.537, 29.585, 29.642, 29.690, 30.715, 31.904, 38.640, 47.389, 50.858, 51.068, 54.011, 58 .592, 168.228

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium It was done.
In addition, bis (nonafluorobutanesulfonyl) imide-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium is a base acid of a conjugate base [bis ( PKa in acetonitrile of nonafluorobutanesulfonyl) imide] is 0.0.

(Example 6A)
<Synthesis of nonafluorobutanesulfonic acid-1-dodecyl-2-undecyl-3-3'hydroxypropylimidazolium>
Synthesis of nonafluorobutanesulfonic acid-1-dodecyl-2-undecyl-3-3′hydroxypropylimidazolium was performed according to the following scheme.

For 1-dodecyl-2-undecylimidazole, 17.76 g of 2-undecylimidazole was dissolved in 100 mL of toluene, and 20.00 g of dodecyl bromide and 7.75 g of potassium hydroxide were added and heated with stirring. Obtained by refluxing for 8 hours. After removing the solvent, the mixture was extracted with dichloromethane and purified by silica gel column chromatography using a solution of n-hexane: ethyl acetate = 9: 1 (volume ratio). When analyzed by gas chromatography, the purity was 98.9% or more.

7.04 g of 1-dodecyl-2-undecylimidazole and 3.84 g of 3-bromopropanol were added to the flask and heated at 120 ° C. for 4 hours. After returning to normal temperature, the precipitated crystals were recrystallized from ethyl acetate to obtain 8.00 g of colorless crystals 1-dodecyl-2-undecyl-3-3-3'hydroxylimidazolium bromide. Yield 83.8%.

The FTIR absorption of the product and its attribution are shown below.
1470 cm ⁻¹ is CH ₂ bending vibration, 1526 cm ⁻¹ is C = N symmetric stretching vibration, 2851 cm ⁻¹ is CH ₂ symmetric stretching vibration, 2919 cm ⁻¹ is CH ₂ inverse symmetric stretching vibration, 3086, 3123 cm ^{−. An} imidazole ring CH stretching vibration was observed in ¹ and an OH stretching vibration was observed in 3317 cm ⁻¹ .

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.835 (t / J = 6.8 Hz, 6H), 1.160-1.440 (m, 34H), 1.571 (quint / J = 8.0 Hz) , 2H), 1.760-1.860 (m, 2H), 2.115 (quant / J = 6.0 Hz, 2H), 3.083 (t / J = 8.2 Hz, 2H), 3.596 (T / J = 5.4 Hz, 2H), 4.094 (t / J = 7.8 Hz, 2H), 4.347 (t / J = 7.0 Hz, 2H), 7.434 (d / J = 2.0Hz, 1H), 7.831 (d / J = 2.0Hz, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.051, 22.608, 26.422, 27.888, 29.000, 29.067, 29.259, 29.297, 29.460, 29.498 , 29.527, 30.006, 31.808, 32.038, 45.348, 48.606, 57.020, 121.138, 122.154, 146.609

From these spectra, the product was identified as 1-dodecyl-2-undecyl-3-3'hydroxyl imidazolium bromide.

1.60 g of 1-dodecyl-2-undecyl-3-3'hydroxyl imidazolium bromide was dissolved by heating in water and a small amount of ethanol, and an aqueous solution of 2.80 g of potassium nonafluorobutanesulfonate was added. After stirring at room temperature for 1 hour, heating under reflux was performed for 1 hour. After cooling, the reaction solution was extracted with dichloromethane and washed thoroughly with water until the silver nitrate test was negative. The organic layer was dried over anhydrous sodium sulfate and then the solvent was removed, followed by vacuum drying at 100 ° C. for 20 hours to obtain colorless liquid nonafluorobutanesulfonic acid-1-dodecyl-2-undecyl-3-3-3′hydroxypropylimidazolium 4 .80 g was obtained. Yield 94.3%.

The FTIR absorption of the product and its attribution are shown below.
1054cm ^-1 to symmetric stretching vibration of SO ₂ bond, 1134 and symmetric stretching vibration of 1255cm ^-1 to CF _2, antisymmetric stretching vibration of SO ₂ bind to 1351cm ^-1, bending vibration of CH ₂ in 1466cm ^-1, 1525cm ^-1 symmetric stretching vibration of C = N, symmetric stretching vibration of CH ₂ in 2857Cm ^-1, antisymmetric stretching vibration of CH ₂ in 2927cm ^-1, CH stretching vibration of the imidazole ring to 3134cm ^-1, to 3478Cm ^-1 OH Stretching vibration was observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.852 (t / J = 6.8 Hz, 6H), 1.160-1.440 (m, 34H), 1.573 (quint / J = 7.8 Hz) , 2H), 1.740-1.850 (m, 2H), 2.063 (quant / J = 5.8 Hz, 2H), 2.427 (brs, 1H), 3.009 (t / J = 8) .4 Hz, 2H), 3.588 (t / J = 5.8 Hz, 2H), 4.022 (t / J = 7.8 Hz, 2H), 4.242 (t / J = 7.0 Hz, 2H) 7.237 (d / J = 2.8 Hz, 1H), 7.470 (d / J = 2.0 Hz, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.070, 22.647, 26.422, 27.745, 28.990, 29.038, 29.268, 29.297, 29.326, 29.479 , 29.537, 29.565, 29.901, 31.847, 31.865, 45.204, 48.453, 57.518, 120.994, 121.684, 146.791

From these spectra, it was identified that the product was nonafluorobutanesulfonic acid-1-dodecyl-2-undecyl-3-3'hydroxylimidazolium.
The pKa in acetonitrile of the acid (nonafluorobutanesulfonic acid) that is the base of the conjugate base in nonafluorobutanesulfonic acid-1-dodecyl-2-undecyl-3-3′hydroxylpropylimidazolium is 0.7 It is.

(Example 7A)
<Synthesis of bis (nonafluorobutanesulfonyl) imido-1-dodecyl-2-undecyl-3-3'hydroxylpropyloctadecylimidazolium>
Synthesis of bis (nonafluorobutanesulfonyl) imido-1-dodecyl-2-undecyl-3-'hydroxylpropyloctadecylimidazolium was performed according to the following scheme.

1.64 g of 1-dodecyl-2-undecyl-3-3′hydroxylpropyloctadecylimidazolium bromide synthesized in Example 6A was dissolved in heated pure water and a small amount of ethanol solution to obtain lithium bis (nonafluorobutanesulfonyl). A solution prepared by dissolving 4.13 g of imide in water was added. The mixture was heated to reflux for 1 hour, cooled and extracted with dichloromethane. The organic layer was washed with pure water until the AgNO ₃ test was negative, dried over anhydrous sodium sulfate, and then the solvent was removed. Vacuum drying was carried out at 100 ° C. for 20 hours to obtain 6.80 g of a colorless liquid of bis (nonafluorobutanesulfonyl) imide-1-dodecyl-2-undecyl-3-3′hydroxylimidazolium. Yield 96.6%.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SNS at 1054 cm ⁻¹ , symmetrical stretching vibration of SO ₂ bond at 1134 cm ⁻¹ , symmetrical stretching vibration of CF ₂ at 1236 and 1255 cm ⁻¹ , reverse symmetrical stretching vibration of SO ₂ bond at 1352 cm ⁻¹ , 1466 cm ^{− 1} is CH ₂ bending vibration, 1525 cm ⁻¹ is C = N symmetric stretching vibration, 2857 cm ⁻¹ is CH ₂ symmetric stretching vibration, 2927 cm ⁻¹ is CH ₂ antisymmetric stretching vibration, 3134 cm ⁻¹ is an imidazole ring The CH stretching vibration of OH and the stretching vibration of OH at 3478 cm ⁻¹ were observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.852 (t / J = 7.0 Hz, 6H), 1.140-1.440 (m, 34H), 1.586 (quint / J = 8.0 Hz) , 2H), 1.750-1.850 (m, 2H), 2.045 (quant / J = 6.2 Hz, 2H), 2.963 (t / J = 8.2 Hz, 2H), 3.607. (T / J = 5.4 Hz, 2H), 4.000 (t / J = 7.8 Hz, 2H), 4.220 (t / J = 7.0 Hz, 2H), 7.195 (d / J = 2.0Hz, 1H), 7.335 (d / J = 2.0Hz, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.061, 22.647, 26.374, 27.659, 28.943, 28.971, 29.268, 29.297, 29.470, 29.527 , 29.556, 29.882, 31.616, 31.646, 45.109, 48.472, 57.691, 121.071, 121.531, 146.657

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imido-1-dodecyl-2-undecyl-3-3′hydroxylimidazolium.
It should be noted that bis (nonafluorobutanesulfonyl) imide-1-dodecyl-2-undecyl-3-'hydroxypropylimidazolium has a base acid conjugate acid [bis (nonafluorobutanesulfonyl) imide] in acetonitrile. pKa is 0.0.

(Example 8A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide-1- 3'hydroxypropyl-2-heptadecyl-3-octadecylimidazolium>
The synthesis of bis (nonafluorobutanesulfonyl) imide-1- 3'hydroxypropyl-2-heptadecyl-3-octadecylimidazolium was performed according to the following scheme.

1-octadecyl-2-heptadecylimidazole is prepared by dissolving 15.34 g of 2-heptadecylimidazole in 100 mL of toluene, adding 17.62 g of octadecyl bromide and 4.86 g of potassium hydroxide, and heating with stirring. And obtained by refluxing for 11 hours. After removing the solvent, the mixture was extracted with dichloromethane and purified by silica gel column chromatography using a solution of n-hexane: ethyl acetate 9: 1. Analysis by gas chromatography revealed a purity of 99.3% or more.

8.42 g of 1-octadecyl-2-heptadecylimidazole and 3.20 g of 3-bromopropanol were added to the flask and heated at 120 ° C. for 4 hours in a sealed state. After returning to room temperature, the precipitated crystals were recrystallized from ethyl acetate to obtain 9.75 g of colorless crystals of 1-3'hydroxylpropyl-2-heptadecyl-3-octadecylimidazolium bromide. Yield 92.7%.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.848 (t / J = 7.2 Hz, 6H), 1.140-1.460 (m, 58H), 1.580 (quint / J = 7.2 Hz) , 2H), 1.760-1.860 (m, 2H), 2.129 (quant / J = 6.0 Hz, 2H), 3.083 (t / J = 8.2 Hz, 2H), 3.618 (T / J = 5.4 Hz, 2H), 4.097 (t / J = 7.8 Hz, 2H), 4.356 (t / J = 6.8 Hz, 2H), 7.380 (d / J = 2.0 Hz, 1 H), 7.813 (d / J = 1.6 Hz, 1 H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.99, 22.666, 24.007, 26.470, 27.927, 29.038, 29.105, 29.335, 29.518, 29.642 , 29.680, 29.968, 31.894, 45.348, 48.683, 56.991, 120.994, 122.087, 146.829

From these spectra, it was identified that the product was 1-3'hydroxylpropyl-2-heptadecyl-3-octadecylimidazolium bromide.

3.15 g of 1-3 ′ hydroxylpropyl-2-heptadecyl-3-octadecylimidazolium bromide is dissolved in heated pure water and a small amount of ethanol solution, and 2.90 g of potassium bis (nonafluorobutanesulfonyl) imide is purified water. And a solution dissolved in a small amount of ethanol solution. The mixture was heated to reflux for 1 hour, cooled and extracted with dichloromethane. The organic layer was washed with pure water until the AgNO ₃ test was negative, dried over anhydrous sodium sulfate, and then the solvent was removed. Vacuum drying was performed at 100 ° C. for 20 hours to obtain 5.03 g of a bis (nonafluorobutanesulfonyl) imide 1-3′hydroxyl-2-heptadecyl-3-octadecylimidazolium colorless liquid. Yield 93.0%.

The FTIR absorption of the product and its attribution are shown below.
Symmetrical stretching vibration of SNS at 1076 cm ⁻¹ , symmetrical stretching vibration of SO ₂ bond at 1140 cm ⁻¹ , symmetrical stretching vibration of CF ₂ at 1216 and 1237 cm ⁻¹ , reverse symmetrical stretching vibration of SO ₂ bond at 1355 cm ⁻¹ , 1467 cm ^{− 1} CH ₂ bending vibration, 1525 cm ⁻¹ C = N symmetric stretching vibration, 2855 cm ⁻¹ CH ₂ symmetric stretching vibration, 2927 cm ⁻¹ CH ₂ inverse symmetric stretching vibration, 3146 cm ⁻¹ imidazole ring The CH stretching vibration of OH and the stretching vibration of OH at 3555 cm ⁻¹ were observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.855 (t / J = 6.6 Hz, 6H), 1.140-1.440 (m, 58H), 1.588 (quint / J = 8.0 Hz) , 2H), 1.740-1.850 (m, 2H), 2.049 (quant / J = 6.3 Hz, 2H), 2.966 (t / J = 8.2 Hz, 2H), 3.613 (T / J = 5.6 Hz, 2H), 4.003 (t / J = 7.8 Hz, 2H), 4.224 (t / J = 6.8 Hz, 2H), 7.193 (d / J = 2.0Hz, 1H), 7.335 (d / J = 2.0Hz, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.99, 22.675, 26.384, 27.668, 28.952, 28.990, 29.278, 29.355, 29.508, 29.652. , 29.690, 29.882, 31.597, 31.913, 45.118, 48.482, 57.700, 121.061, 121.531, 146.666.

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide 1-3′hydroxylpropyl-2-heptadecyl-3-octadecylimidazolium.
In addition, pKa in acetonitrile of the acid [bis (nonafluorobutanesulfonyl) imide] which is the base of the conjugate base in bis (nonafluorobutanesulfonyl) imide 1-3′hydroxyl-2-heptadecyl-3-octadecylimidazolium Is 0.0.

(Example 9A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide-N-3'hydroxypropyl-N, N-dimethyltetradecylammonium>
The synthesis of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxypropyl-N, N-dimethyltetradecylammonium was carried out according to the following scheme.

N, N-dimethyltetradecylamine 6.83 g and 3-bromopropanol 5.80 g were put in a closed flask and reacted at 90 ° C. for 5 hours. When the temperature was returned to room temperature after the completion of the reaction, it became a viscous liquid. When n-hexane was added thereto, a precipitate was deposited. Decanted and the supernatant was discarded. This operation was performed three times to purify the product, and 9.50 g of N, N-dimethyl-N-3'hydroxypropyltetradecylammonium bromide was obtained. Yield 89.2%.

The peak of proton ( ¹ H) NMR in deuterated chloroform of the product is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.852 (t / J = 6.4 Hz, 3H), 1.180-1.400 (m, 22H), 1.670-1.760 (m, 2H) ), 1.871 (brs, 1H), 2.005-2.090 (m, 2H), 3.276 (s, 6H), 3.330-3.410 (m, 2H) 3.700-3 .790 (m, 4H)

From these spectra, the product was identified as N, N-dimethyl-N-3'hydroxypropyltetradecyl bromide.

A solution prepared by dissolving 3.50 g of N, N-dimethyl-N-3′hydroxypropyltetradecylammonium bromide in heated pure water and dissolving 5.40 g of bis (nonafluorobutanesulfonyl) imide lithium in pure water. added. The mixture was heated to reflux for 1 hour, cooled and extracted with dichloromethane. The organic layer was washed with pure water until the AgNO ₃ test was negative, dried over anhydrous sodium sulfate, and then the solvent was removed. Vacuum drying was performed at 100 ° C. for 24 hours to obtain 7.90 g of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N, N-dimethyltetradecylammonium colorless liquid. Yield 97.5%.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SNS at 1075 cm ⁻¹ , symmetrical stretching vibration of SO ₂ bond at 1140 cm ⁻¹ , symmetrical stretching vibration of CF ₂ at 1199 and 1237 cm ⁻¹ , reverse symmetrical stretching vibration of SO ₂ bond at 1354 cm ⁻¹ , 1470 cm ^{− 1.} CH ₂ deformation vibration, 2858 cm ⁻¹ CH ₂ symmetrical stretching vibration, 2929 cm ⁻¹ CH ₂ inverse symmetric stretching vibration, and 3549 cm ⁻¹ OH stretching vibration were observed.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.842 (t / J = 6.8 Hz, 3H), 1.170-1.320 (m, 22H), 1.610-1.710 (m, 2H) ), 1.867- 1.937 (m, 2H), 2.538 (brs, 1H), 2.993 (s, 6H), 3.149-3.192 (m, 2H), 3.351 3.392 (m, 2H), 3.665 (t / J = 5.4 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.003, 22.628, 25.454, 26.097, 28.990, 29.297, 29.364, 29.527, 29.585, 29.613 , 31.865, 50.705, 58.266, 62.358, 64.887

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide-N-3′hydroxypropyl-N, N-dimethyltetradecylammonium.
It should be noted that pKa of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxypropyl-N, N-dimethyltetradecylammonium as the base of the conjugate base [bis (nonafluorobutanesulfonyl) imide] in acetonitrile Is 0.0.

(Example 10A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide-N-3'hydroxypropyl-N, N-dimethyloctadecylammonium>
The synthesis of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxypropyl-N, N-dimethyloctadecylammonium was performed according to the following scheme.

N, N-dimethyloctadecylamine 8.71 g and 3-bromopropanol 4.19 g were placed in a closed flask and reacted at 120 ° C. for 2 hours. Crystals precipitated after returning to room temperature were recrystallized from a mixed solvent of ethyl acetate and ethanol to obtain 11.28 g of N-3'hydroxypropyl-N, N-dimethyloctadecylammonium bromide. Yield 88.2%.

The FTIR absorption of the product and its attribution are shown below.
Deformation vibration of CH ₂ in 1472cm ^-1, symmetric stretching vibration of CH ₂ in 2851cm ^-1, antisymmetric stretching vibration of CH ₂ in 2918cm ^-1, the stretching vibration of 3296Cm ^-1 hydroxyl seen.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.844 (t / J = 7.4 Hz, 3H), 1.170-1.400 (m, 30H), 1.670-1.760 (m, 2H) ), 2.008-2.077 (m, 2H), 3.277 (s, 6H), 3.350-3.420 (m, 2H) 3.700-3.790 (m, 4H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.080, 22.656, 22.800, 25.962, 26.298, 29.192, 29.326, 29.393, 29.460, 29.633 , 29.671, 31.84, 51.222, 58.208, 62.722, 64.657

From these spectra, it was identified that the product was N-3 ′ hydroxypropyl-N, N-dimethyloctadecyl ammonium bromide.

3.16 g of N, N-dimethyl-N-3′hydroxypropyloctadecylammonium bromide was dissolved in heated pure water, and 4.51 g of lithium bis (nonafluorobutanesulfonyl) imide was dissolved in pure water. It was. The mixture was heated to reflux for 1 hour, cooled and extracted with dichloromethane. The organic layer was washed with pure water until the AgNO ₃ test was negative, dried over anhydrous sodium sulfate, and then the solvent was removed. Vacuum drying was performed at 100 ° C. for 60 hours to obtain 6.59 g of a bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N, N-dimethyloctadecylammonium colorless liquid. Yield 97.1%.

The FTIR absorption of the product and its attribution are shown below.
Symmetrical stretching vibration of SNS at 1076 cm ⁻¹ , symmetrical stretching vibration of SO ₂ bond at 1140 cm ⁻¹ , symmetrical stretching vibration of CF ₂ at 1200 and 1237 cm ⁻¹ , reverse symmetrical stretching vibration of SO ₂ bond at 1354 cm ⁻¹ , 1469 cm ^{− 1.} CH ₂ deformation vibration, 2856 cm ⁻¹ symmetric CH ₂ stretching vibration, 2927 cm ⁻¹ CH ₂ reverse symmetric stretching vibration, and 3551 cm ⁻¹ OH stretching vibration were observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.854 (t / J = 7.0 Hz, 3H), 1.180-1.340 (m, 30H), 1.630-1.730 (m, 2H) ), 1.895-1.963 (m, 2H), 3.026 (s, 6H), 3.166-3.209 (m, 2H), 3.396-3.437 (m, 2H), 3.700 (t / J = 6.6 Hz, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.089, 22.666, 25.483, 26.010, 29.019, 29.307, 29.345, 29.393, 29.556, 29.680 , 31.904, 50.858, 58.323, 62.482, 64.935

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N, N-dimethyloctadecylammonium.
The pKa in acetonitrile of the acid [bis (nonafluorobutanesulfonyl) imide], which is the base of the conjugate base in bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N, N-dimethyloctadecylammonium, is , 0.0.

(Comparative Example 1A)
<Synthesis of nonafluorobutanesulfonic acid-1-octadecylimidazolium>
Nonafluorobutanesulfonic acid-1-octadecylimidazolium was synthesized according to the following scheme.

3.27 g of 1-octadecylimidazole synthesized in Example 1A was dissolved in 50 mL of ethanol, and an ethanol solution of 3.05 g of nonafluorobutanesulfonic acid was gradually added dropwise thereto, followed by stirring for 30 minutes after completion of the addition. Thereafter, the mixture was heated to reflux for 1 hour. After removing the solvent, recrystallization was performed using a mixed solvent of ethanol / n-hexane to obtain colorless nonafluorobutanesulfonic acid-1-octadecylimidazolium. Yield 95%.

The assignment of the FTIR spectrum of the product is shown below.
1134 cm ⁻¹ is SO ₂ symmetric stretching vibration, 1355 cm ⁻¹ is SO ₂ bond antisymmetric stretching vibration, 1246 cm ⁻¹ is CF ₂ symmetric stretching vibration, 1470 cm ⁻¹ is CH bond bending vibration, 2852 cm ⁻¹ symmetric stretching vibration of CH _2, antisymmetric stretching vibration of CH ₂ in 2920 cm ^-1, the stretching vibration of CH bond of the imidazole ring to 3158cm ^-1 were observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform of the product is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.847 (t, 3H, J = 7.2 Hz), 1.222-1.282 (m, 30H), 1.790-1.890 (m, 2H) ), 4.181 (t / J = 7.2 Hz, 2H), 7.189 (dd / J = 1.8 Hz, 3.8 Hz, 1H), 7.444 (dd / J = 1.8 Hz, 3.H). 8Hz, 1H), 8.866 (d / J = 1.8Hz, 3.8Hz, 1H), 13.200 (brs, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.055, 22.648, 26.113, 28.875, 29.272, 29.318, 29.440, 30.142, 31.882, 49.847 , 122.500, 122.851, 135.015

From the above, it was confirmed that nonafluorobutanesulfonic acid-1-octadecylimidazolium was synthesized.

(Comparative Example 2A)
<Synthesis of hexafluorocyclopropane-1,3-bis (sulfonyl) imido-1-butyl-3-n-octadecylimidazolium>
For comparison, synthesis of hexafluorocyclopropane-1,3-bis (sulfonyl) imido-1-butyl-3-n-octadecylimidazolium was performed according to the following scheme.

10.7-octadecylimidazole synthesized in Example 1A and 6.03 g of bromobutane were dissolved in acetonitrile, and heated to reflux for 5 hours. After removing the solvent, recrystallization was performed from a mixed solvent of n-hexane and ethanol to obtain 1-butyl-3-octadecylimidazolium bromide. 4.57 g of this bromide was dissolved in ethanol, and an ethanol solution of 3.31 g of potassium hexafluorocyclopropane-1,3-bis (sulfonyl) imide was added thereto and stirred to produce a colorless precipitate. This solution was heated to reflux for 1 hour, and the solvent was removed after cooling. The portion dissolved by adding dichloromethane was filtered, and the organic layer was washed with pure water until the AgNO ₃ test was negative. Dry and recrystallize from a mixed solvent of n-hexane and ethanol to obtain colorless crystalline hexafluorocyclopropane-1,3-bis (sulfonyl) imido-1-butyl-3-n-octadecylimidazolium 6.00 g Got. Yield 90%.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SO ₂ to 1091cm ^-1, symmetric stretching vibration of CF ₂ to 1161cm ^-1, antisymmetric stretching vibration of SO ₂ bind to 1356cm ^-1, deformation vibration of CH bond to 1470 cm ^-1, the 1560 cm ^-1 A stretching vibration peculiar to imidazole, a symmetrical stretching vibration of CH ₂ at 2850 cm ^−1, and an antisymmetric stretching vibration of CH ₂ at 2919 cm ⁻¹ were observed.

In addition, proton ( ¹ H) NMR and carbon ( ¹³ C) NMR peaks in deuterated chloroform and their attribution are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.850 (t, 3H, J = 7.2 Hz), 0.941 (t, 3H, J = 7.2 Hz), 1.170-1.410 (m , 32H), 1.835 (quant, 4H, J = 7.2 Hz), 4.160 (m, 4H), 7.267 (d, 1H, J = 2.1 Hz), 7.294 (d, 1H) , J = 2.1 Hz), 8.749 (s, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 13.254, 14.085, 19.351, 22.663, 26.113, 28.853, 29.303, 29.333, 29.448, 29.570 , 29.631, 29.677, 30.127, 31.898, 32.004, 49.977, 50.244, 122.179, 122.263, 135.473.

From these spectra, the product was identified as hexafluorocyclopropane-1,3-bis (sulfonyl) imido-1-butyl-3-n-octadecylimidazolium.
Hexafluorocyclopropane-1,3-bis (sulfonyl) imido-1-butyl-3-n-octadecylimidazolium, a base acid of a conjugate base [hexafluorocyclopropane-1,3-bis (sulfonyl) The pKa of the imide] in acetonitrile is -0.8.

(Comparative Example 3A)
<Synthesis of Heptadecafluorooctanesulfonate-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium>
For comparison, heptadecafluorooctane sulfonate-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium was synthesized according to the following scheme.

To an ethanol solution of 6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecene synthesized in Example 4A (4.04 g) was added 5.00 g of heptadecafluorooctanesulfonic acid, and the mixture was stirred at room temperature for 1 hour. Thereafter, heating under reflux was performed for 1 hour. After removing the solvent, it was dissolved in dichloromethane and washed thoroughly with water. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed. Recrystallization from a mixed solvent of n-hexane and ethanol gave 7.86 g of heptadecafluorooctanesulfonic acid-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium. Yield 86.9%

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SO ₂ to 1055cm ^-1, symmetric stretching vibration of CF ₂ to 1252cm ^-1, antisymmetric stretching vibration of SO ₂ bind to 1368cm ^-1, bending vibration of CH ₂ in 1467cm ^-1, to 1643cm ^-1 stretching vibration of C = N, symmetric stretching vibration of CH ₂ in 2851cm ^-1, antisymmetric stretching vibration of CH ₂ in 2920 cm ^-1, is NH stretching vibration 3296cm ^-1 were observed.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.843 (t, 3H, J = 6.6 Hz), 1.205-1.287 (m, 32H), 1.544-1.800 (m, 8H) ), 1.975-2.033 (m, 2H), 2.792-2.816 (m, 1H), 3.440-3.559 (m, 6H), 8.713 (brs, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.024, 19.336, 22.633, 25.121, 26.311, 27.181, 28.311, 29.028, 29.303, 29.425 , 29.532, 29.608, 29.654, 31.882, 38.491, 43.375, 49.725, 53.785, 168.029

These spectra identified the product as hepadecafluorooctane sulfonate-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium.
It should be noted that heptadecafluorooctanesulfonic acid-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium is a base acid of the conjugate base [heptadecafluorooctanesulfonic acid] in acetonitrile. pKa is 0.7.

(Comparative Example 4A)
<Synthesis of Hexafluorocyclopropane-1,3-bis (sulfonyl) imide-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium>
For comparison, hexafluorocyclopropane-1,3-bis (sulfonyl) imide-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium was synthesized according to the following scheme. It was.

6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecene synthesized in Example 4A was added to an ethanol solution of 2.18 g of hexafluorocyclopropane-1,3-bis (sulfonyl) imide (3.00 g). After stirring at room temperature for 1 hour, the mixture was heated to reflux for 1 hour. After removing the solvent, it was dissolved in dichloromethane and washed thoroughly with water. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed. Vacuum drying at 90 ° C. for 3 days gave 4 colorless crystals of hexafluorocyclopropane-1,3-bis (sulfonyl) imide-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium. .86 g was obtained. Yield 93.8%

The FTIR absorption of the product and its attribution are shown below.
Antisymmetric stretching vibration of SNS to 1042cm ^-1, symmetric stretching vibration of SO ₂ to 1091cm ^-1, symmetric stretching vibration of CF ₂ to 1164cm ^-1, antisymmetric stretching vibration of SO ₂ binding to 1360 cm ^-1, the 1633 cm ^-1 stretching vibration of C = N, symmetric stretching vibration of CH ₂ in 2848cm ^-1, antisymmetric stretching vibration of CH ₂ in 2920 cm ^-1, is NH stretching vibration 3387cm ^-1 were observed.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.869 (t, 3H, J = 6.6 Hz), 1.170-1.340 (m, 32H), 1.441-1.555 (m, 2H) ), 1.600-1.750 (m, 4H), 1.772-1.833 (m, 2H), 1.94-2.101 (m, 2H), 2.670-2.780 (m) , 1H), 3.413 (t / J = 6.6 Hz, 2H), 3.508 (t / J = 6.6 Hz, 2 Hz), 3.550-3.652 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.055, 19.260, 22.633, 26.052, 27.090, 28.524, 29.120, 29.226, 29.318, 29.364 , 29.486, 29.578, 29.608, 29.669, 31.867, 38.690, 43.177, 49.511, 53.861, 167.922

These spectra identified the product as hexafluorocyclopropane-1,3-bis (sulfonyl) imide-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium. .
The hexafluorocyclopropane-1,3-bis (sulfonyl) imide-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium acid that is the base of the conjugate base [hexafluorocyclopropane -1,3-bis (sulfonyl) imide] in acetonitrile is -0.8.

(Comparative Example 5A)
<Synthesis of octadecylammonium pentadecafluorooctanoate>
For comparison, synthesis of octadecyl ammonium pentadecafluorooctanoate was performed according to the following scheme.

4.14 g of pentadecafluorooctanoic acid and 2.69 g of octadecylamine were added to ethanol and refluxed with heating for 1 hour. After removing the solvent, recrystallization was performed from a mixed solvent of n-hexane and ethanol to obtain 6.23 g of colorless plate crystals. Yield 92.0%.

The FTIR absorption of the product and its attribution are shown below.
1141cm ^-1, 1201cm ^-1, and the symmetric stretching vibration of CF ₂ to 1232cm ^-1, bending vibration of CH ₂ in 1473cm ^-1, stretching vibration of C = O to 1677cm ^-1, to 2851cm ^-1 in CH ₂ symmetric stretching vibration, antisymmetric stretching vibration of CH ₂ in 2918cm ^-1, _NH ^{4 +} stretching vibration was observed at 3000-3325cm ^-1.

In addition, the peaks of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform are shown below.
¹ H-NMR (CD ₃ OD, δ ppm); 0.890 (t / J = 6.6 Hz, 3H), 1.214-1.408 (m, 30H), 1.590-1.690 (m, 2H), 2.896 (t / J = 7.5 Hz, 2H), 4.891 (brs)
¹³ C-NMR (CD ₃ OD, δ ppm); 14.444, 23.740, 27.464, 28.578, 30.242, 30.486, 30.516, 30.669, 30.791, 33. 081, 40.758

From these spectra, the product was identified as octadecyl ammonium pentadecafluorooctanoate.
In addition, pKa in acetonitrile of the acid [pentadecafluorooctanoic acid] which becomes the base of the conjugate base in octadecylammonium pentadecafluorooctanoate is 12.7.

(Comparative Example 6A)
<Synthesis of nonafluorobutanesulfonic acid-1-octadecyl-2-heptadecylimidazolium>
Nonafluorobutanesulfonic acid-1-octadecyl-2-heptadecylimidazolium was synthesized according to the following scheme.

4.45 g of 1-octadecyl-2-heptadecylimidazole synthesized in Example 8A was dissolved in ethanol, and 2.40 g of nonafluorobutanesulfonic acid dissolved in ethanol was gradually added dropwise thereto. . After completion of dropping, the mixture was stirred for 30 minutes and then heated to reflux for 1 hour. After removing the solvent, recrystallization was performed using a mixed solvent of ethanol / n-hexane to obtain 6.43 g of colorless nonafluorobutanesulfonic acid-1-octadecyl-2-heptadecylimidazole salt. Yield 93.9%.

The assignment of the FTIR spectrum of the product is shown below.
1135 cm ⁻¹ is a symmetric stretching vibration of SO ₂ , 1279 cm ⁻¹ is a symmetric stretching vibration of CF ₂ , 1357 cm ⁻¹ is a reverse symmetric stretching vibration of SO ₂ bond, 1472 cm ⁻¹ is a CH ₂ variable angle vibration, and 2851 cm ⁻¹ . symmetric stretching vibration of CH _2, antisymmetric stretching vibration of CH ₂ in 2918cm ^-1, is NH ⁺ stretching vibration 3152cm ^-1 were observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CDCl ₃ of the obtained compound is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.848 (t / J = 6.8 Hz, 6H), 1.171-1.307 (m, 58H), 1.702-1.817 (m, 4H) ), 2.908 (t / J = 7.5 Hz, 2H), 4.003 (t / J = 7.5 Hz, 2H), 7.139 (t / J = 2.0 Hz, 1H), 7.255. (T / J = 2.0Hz, 1H), 13.285 (brs, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.055, 22.648, 24.602, 26.326, 27.196, 28.952, 28.998, 29.333, 29.455, 29.516 , 29.562, 29.669, 30.051, 31.882, 47.725, 118.928, 120.866, 144.149.

From the above, it was confirmed that nonafluorobutanesulfonic acid-1-octadecyl-2-heptadecylimidazolium was synthesized.
The pKa in acetonitrile of the acid [nonafluorobutanesulfonic acid], which is the base of the conjugate base in the 1-octadecyl-2-heptadecylimidazolium nonafluorobutanesulfonate, is 0.7.

(Comparative Example 7A)
<Synthesis of hexafluorocyclopropane-1,3-bis (sulfonyl) imide-1-octadecyl-2-heptadecylimidazolium>
For comparison, hexafluorocyclopropane-1,3-bis (sulfonyl) imide-1-octadecyl-2-heptadecylimidazolium was synthesized according to the following scheme.

3.46 g of 1-octadecyl-2-heptadecylimidazole synthesized in Example 8A was dissolved in ethanol, and 1.82 g of hexafluorocyclopropane-1,3-bis (sulfonyl) imide was dissolved therein. Things were added slowly dropwise. After completion of dropping, the mixture was stirred for 30 minutes and then heated to reflux for 1 hour. After removing the solvent, recrystallization was performed using a mixed solvent of ethanol / n-hexane to obtain 5.05 g of colorless hexafluorocyclopropane-1,3-disulfonylimide-1-octadecyl-2-heptadecylimidazolium. Obtained. Yield 96%.

The assignment of the FTIR spectrum of the product is shown below.
1086 cm ⁻¹ is a symmetrical stretching vibration of SO ₂ , 1164 cm ⁻¹ is a symmetrical stretching vibration of CF ₂ , 1364 cm ⁻¹ is an anti symmetric stretching vibration of SO ₂ bond, 1469 cm ⁻¹ is a symmetric stretching vibration of C = N bond, 2851 cm ^{− 1} symmetric stretching vibration of CH _2, antisymmetric stretching vibration of CH ₂ in 2920 cm ^-1, in 3162 and 3289cm ^-1 are stretching vibration of NH bond were observed.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in deuterated chloroform of the product is shown below.
¹ H-NMR (CDCl ₃ , δ ppm); 0.853 (t, 6H, J = 6.8 Hz), 1.182-1.323 (m, 58H), 1.652-1.833 (m, 4H) ), 2.913 (t, 2H, J = 7.5 Hz), 4.007 (t, 2H, J = 7.5 Hz), 7.126 (t, 1H, J = 1.6 Hz), 7.274 (T, 1H, J = 1.6 Hz), 11.820 (brs, 1H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.065, 22.658, 24.666, 26.321, 27.420, 28.931, 29.297, 29.326, 29.450, 29.496 , 29.557, 29.633, 29.679, 30.015, 31.892, 47.888, 119.044, 120.891, 147.159

From these spectra, the product was identified as hexafluorocyclopropane-1,3-bis (sulfonyl) imide-1-octadecyl-2-heptadecylimidazolium.
Hexafluorocyclopropane-1,3-bis (sulfonyl) imide-1-octadecyl-2-heptadecylimidazolium, a base acid of a conjugate base [hexafluorocyclopropane-1,3-bis (sulfonyl) imide PKa in acetonitrile is -0.8.

(Comparative Example 8A)
<Synthesis of bis (nonafluorobutanesulfonyl) imide-octadecylammonium>
For comparison, the synthesis of bis (nonafluorobutanesulfonyl) imide-octadecylammonium was performed according to the following scheme.

Octadecylamine was dissolved in ethanol, and an equimolar amount of an ethanol solution of bis (nonafluorobutanesulfonyl) imide was added. Heating under reflux was performed for 1 hour, and the solvent was removed after cooling. The residue was extracted with dichloromethane and the organic layer was washed thoroughly with water. After drying over anhydrous sodium sulfate, the solvent is removed and recrystallization is performed from a mixed solvent of n-hexane and ethanol to obtain colorless crystals of bis (nonafluorobutanesulfonyl) imide-octadecylammonium. Yield 91.1%.

The FTIR absorption of the product and its attribution are shown below.
Antisymmetric stretching vibration of SNS coupled to 1031cm ^-1, symmetric stretching vibration of SO ₂ bind to 1088cm ^-1, 1141 and symmetric stretching vibration of 1200 cm ^-1 in CF _2, antisymmetric stretching vibration of SO ₂ binding to 1355 cm ^-1, 1473 cm ⁻¹ is CH ₂ bending vibration, 1616 cm ⁻¹ is NH ₃ ⁺ bending vibration, 2856 cm ⁻¹ is CH ₂ symmetric stretching vibration, 2926 cm ⁻¹ is CH ₂ antisymmetric stretching vibration, 3248 cm ⁻¹ NH ₃ ⁺ stretching vibration was observed.

The proton ( ¹ H) NMR and carbon ( ¹³ C) NMR peaks in deuterated methanol (CD ₃ OD) of the obtained compound are shown below.
¹ H-NMR (CD ₃ OD, δ ppm); 0.889 (t / J = 6.8 Hz, 3H), 1.225-1.400 (m, 30H), 1.635 (quint / J = 7. 5Hz, 2H), 2.896 (d / J = 7.5Hz, 2H), 4.867 (brs, 3H)
¹³ C-NMR (CD ₃ OD, δ ppm); 14.414, 23.709, 27.403, 28.563, 30.196, 30.471, 30.623, 30.766, 33.065, 40. 819

From these spectra, the product was identified as bis (nonafluorobutanesulfonyl) imide-octadecylammonium.
The pKa in acetonitrile of the acid [bis (nonafluorobutanesulfonyl) imide], which is the base of the conjugate base in bis (nonafluorobutanesulfonyl) imide-octadecylammonium, is 0.0.

(Comparative Example 9A)
<Synthesis of nonafluorobutanesulfonic acid-N, N, N-trimethyloctadecyl ammonium>
For comparison, nonafluorobutanesulfonic acid-N, N, N-trimethyloctadecyl ammonium was synthesized according to the following scheme.

5.51 g of trimethyloctadecyl ammonium bromide was dissolved in water, and 4.61 g of an aqueous solution of lithium nonafluorobutanesulfonate was added. Heating under reflux is performed for 1 hour, the precipitate deposited after cooling is extracted with dichloromethane, washed thoroughly with water until the washing solution becomes negative in the AgNO ₃ test, the organic layer is dried over anhydrous sodium sulfate, and then the solvent is removed. 8.14 g of nonafluorobutanesulfonic acid-trimethyloctadecyl ammonium colorless crystals were obtained. Yield 94.8%. Recrystallization was performed from a mixed solvent of n-hexane and ethanol.

The FTIR absorption of the product and its attribution are shown below.
Symmetric stretching vibration of SO ₂ bind to 1133cm ^-1, symmetric stretching vibration of CF ₂ to 1263cm ^-1, antisymmetric stretching vibration of SO ₂ bind to 1353cm ^-1, bending vibration of CH ₂ in 1485cm ^-1, 2852cm ^-1 symmetric stretching vibration of CH _2, the antisymmetric stretching vibration of CH ₂ in the 2920 cm ^-1 was observed in.

The peak of proton ( ¹ H) NMR and carbon ( ¹³ C) NMR in CD ₃ OD of the obtained compound is shown below.
¹ H-NMR (CD ₃ OD, δ ppm); 0.851 (t / J = 6.8 Hz, 3H), 1.170-1.340 (m, 30H), 1.640-1.730 (m, 2H), 3.181 (s, 9H), 3.291-3.334 (m, 2H)
¹³ C-NMR (CDCl ₃ , δ ppm); 14.089, 22.666, 23.068, 25.972, 29.067, 29.316, 29.335, 29.412, 29.565, 29.680 , 31.904, 53.043, 66.996

From these spectra, the product was identified as nonafluorobutanesulfonic acid-N, N, N-trimethyloctadecyl ammonium.
The pKa in acetonitrile of the acid (nonafluorobutanesulfonic acid) that is the base of the conjugate base in nonafluorobutanesulfonic acid-N, N, N-trimethyloctadecylammonium is 0.7.

The ionic liquids synthesized in the above examples and comparative examples are summarized below.

(Examples 1B to 5B, and Comparative Examples 1B to 5B, Comparative Example 10B, and Comparative Example 11B)
<Measurement results of solubility in fluorine-based solvents>
Vertrel XF [CF ₃ (CHF) ₂ CF ₂ CF manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.] as a fluorinated solvent for the ionic liquids synthesized in each Example and each Comparative Example, and Z-DOL and Z-TETRAOL ₃ ] was used to conduct a solubility test.
An ionic liquid, Z-DOL and Z-TETRAOL were added to a predetermined mass of Bertrell XF, respectively, irradiated with ultrasonic waves for 5 minutes, and allowed to stand for 1 day, and its solubility was visually confirmed.
Specifically, 1.0 parts by weight, 0.5 parts by weight, and 0.1 parts by weight of ionic liquid, and Z-DOL and Z-TETRAOL are added to 100 parts by weight of Bertrell XF (25 ° C.). After being left for 1 day after being irradiated with ultrasonic waves for 5 minutes, its solubility was visually confirmed and evaluated according to the following evaluation criteria.

In addition, it confirmed visually and judged that it was melt | dissolving when it was transparent. Moreover, it was judged that it was not melt | dissolved (insoluble) when it is opaque or an insoluble part is seen.
The results are shown in Table 2.
〔Evaluation criteria〕
・ 0.5% by mass or more:
It dissolves by addition of 0.5 part by mass.
・ 0.1 mass% or more and less than 0.5 mass%:
The addition of 0.5 part by mass is insoluble, but the addition of 0.1 part by mass dissolves.
-Less than 0.1% by mass:
Any addition of 0.5 parts by mass and 0.1 parts by mass is insoluble.

The solubility of the ionic liquid of Example 1A in the fluorinated solvent was less than 0.1% by mass.
The solubility of the ionic liquid of Example 2A in the fluorine-based solvent was 0.1% by mass or more and less than 0.5% by mass.
The solubility of the ionic liquid of Example 3A in the fluorine-based solvent was 0.5% by mass or more.
The solubility of the ionic liquid of Example 4A in the fluorinated solvent was 0.1% by mass or more and less than 0.5% by mass.
The solubility of the ionic liquid of Example 5A in the fluorine-based solvent was 0.1% by mass or more and less than 0.5% by mass.

The solubility of the ionic liquids of Comparative Examples 1A to 5A in the fluorine-based solvent was less than 0.1% by mass.
The solubility of Z-DOL and Z-TETRAOL in a fluorine-based solvent was 0.5% by mass or more.

As can be seen, it can be seen that the ionic liquids used in the examples have improved solubility in the fluorinated solvent Bartrel XF. The compounds of Examples 2A-5A are sufficient for use in production for hard disk applications.

As can be seen from Comparative Example 1B and Comparative Example 2B, the imidazole-based ionic liquid has low solubility in Vertrel, but it can be seen that Example 2B into which hydroxyl groups have been introduced has improved solubility. That is, it can be seen that introduction of a hydroxyl group as a molecular design method is effective for solubility in vertell.

The ionic liquid having a pyrrolidine skeleton exhibited the highest solubility in Example 3A having bis (nonafluorobutanesulfonyl) imide as an anion.
Even in the case of having the same octadecyl-1,8-diazabicyclo [5.4.0] -7-undecene skeleton, Comparative Examples 3B and 4B have low solubility in Vertrel but are improved in Examples 4B and 5B. ing.

From the examination results of the present inventors, it was found that the solubility in a fluorinated solvent is improved by introducing a hydroxyl group into the ionic liquid. Those having bis (nonafluorobutanesulfonyl) imide as anions generally have higher solubility than nonafluorobutanesulfonic acid.

(Example 6B to Example 10B and Comparative Example 6B to Comparative Example 11B)
<Solubility measurement results in solvent>
Vertrel XF [CF ₃ (CHF) ₂ CF ₂ manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.] as a fluorinated solvent for the ionic liquids synthesized in the examples and comparative examples, and Z-DOL and Z-TETRAOL) CF ₃ ], and a reagent-grade n-hexane and ethanol manufactured by Junsei Chemical Co., Ltd. were used for the solubility test.
An ionic liquid was added to a predetermined mass of Bertrell XF, n-hexane, or ethanol, and the mixture was allowed to stand for 1 day after being irradiated with ultrasonic waves for 5 minutes, and its solubility was visually confirmed.
Specifically, 0.2 parts by mass of an ionic liquid is added to 100 parts by mass of Bertrell XF (25 ° C.), irradiated with ultrasonic waves for 5 minutes, and left for 1 day, and then its solubility is visually checked. Confirmed and evaluated according to the following evaluation criteria. In the case of n-hexane and ethanol, similarly, at 25 ° C., after adding 0.5 parts by mass of ionic liquid to 100 parts by mass, similarly, after irradiating with ultrasonic waves for 5 minutes, The solubility was visually confirmed and evaluated according to the following evaluation criteria.

In addition, it confirmed visually and judged that it was melt | dissolving when it was transparent. Moreover, it was judged that it was not melt | dissolved (insoluble) when it is opaque or an insoluble part is seen.
The results are shown in Table 2-2.
〔Evaluation criteria〕
<< Bertrel XF >>
・ 0.2% by mass or more:
It dissolves by addition of 0.2 part by mass.
-Less than 0.2% by mass:
The addition of 0.2 part by mass is insoluble.

<< n-hexane and ethanol >>
・ 0.5% by mass or more:
It dissolves by addition of 0.5 part by mass.
-Less than 0.5% by mass:
The addition of 0.5 part by mass is insoluble.

The solubility of the ionic liquid of Example 6A in the fluorine-based solvent is 0.2% by mass or more, the solubility in n-hexane is 0.5% by mass or more, and the solubility in ethanol is 0.5% by mass or more. there were.
The solubility of the ionic liquid of Example 7A in a fluorine-based solvent is 0.2% by mass or more, the solubility in n-hexane is 0.5% by mass or more, and the solubility in ethanol is 0.5% by mass or more. there were.
The solubility of the ionic liquid of Example 8A in the fluorine-based solvent is 0.2% by mass or more, the solubility in n-hexane is 0.5% by mass or more, and the solubility in ethanol is 0.5% by mass or more. there were.
The solubility of the ionic liquid of Example 9A in a fluorine-based solvent is 0.2% by mass or more, the solubility in n-hexane is 0.5% by mass or more, and the solubility in ethanol is 0.5% by mass or more. there were.
The solubility of the ionic liquid of Example 10A in the fluorine-based solvent is 0.2% by mass or more, the solubility in n-hexane is 0.5% by mass or more, and the solubility in ethanol is 0.5% by mass or more. there were.

Although the solubility of the ionic liquids of Comparative Examples 6A to 9A in ethanol was 0.5% by mass or more, the solubility in a fluorine-based solvent was less than 0.2% by mass, and the solubility in n-hexane The solubility was less than 0.5% by mass. The ionic liquid of Comparative Example 5A had a solubility in a fluorine-based solvent of less than 0.2% by mass, but the solubility in n-hexane and ethanol was 0.5% by mass or more. The solubility of Z-DOL and Z-TETRAOL in a fluorine-based solvent was 0.2% by mass or more, but the solubility in n-hexane and ethanol was less than 0.5% by mass.

As can be seen, the ionic liquid using the sulfonate shown in the comparative example as a raw material has poor solubility in fluorine and hydrocarbon solvents, although it is a sulfonate having the same polarity. It can be seen that the solubility of the example sulfonate ionic liquid is greatly improved. Taking into account that the material widely used as a lubricant is a long-chain fatty acid or an ester thereof, dissolving in hexane means that the effect as an additive can be exhibited from the compatibility. Further, since it dissolves in the fluoric solvent Vertrel XF, it is sufficient for use in production as a micromachine or a hard disk. Comparative Examples 10B and 11B having a perfluoropolyether skeleton have high solubility in a fluorine solvent, but their use is limited because of their low solubility in hydrocarbon solvents or alcohols.

Generally, regarding the solubility, the influence of the molecular structure is very complicated and difficult to predict. However, from the examination results of the present inventors, the imidazole ionic liquid is low in solubility in bartrel or n-hexane in the imidazole ionic liquid having a long alkyl chain, as can be seen from Comparative Example 6B and Comparative Example 7B. However, it can be seen that the solubility was improved in Examples 6B and 7B into which a hydroxyl group was introduced.

Also, as can be seen from Comparative Example 8B and Comparative Example 9B, ammonium-based lubricants have poor solubility with sulfonates or sulfoimide salts, but it is also found that the solubility is improved by the introduction of hydroxyl groups. That is, it can be seen that introduction of a hydroxyl group as a molecular design method is effective for solubility in Vertrel or n-hexane.

From the examination results of the present inventors, it was found that the solubility in a fluorine-based or hydrocarbon-based solvent is improved by introducing a hydroxyl group into the ionic liquid. Those having bis (nonafluorobutanesulfonyl) imide as anions generally have higher solubility than nonafluorobutanesulfonic acid.

(Example 1C)
<Thermal stability measurement result>
The 5%, 10% and 20% weight loss temperatures of nonafluorobutanesulfonic acid 1-3′hydroxylpropyl-3-octadecylimidazolium are 307.7 ° C., 357.2 ° C. and 388.2 ° C., respectively. Compared with a commercially available perfluoropolyether Z-DOL (Comparative Example 10C), which is generally known as a lubricant for magnetic recording media, shown as a comparative example, 140 ° C. or higher, and Z-TETRAOL (Comparative Example 11C) ) And 60 ° C. or higher.

(Example 2C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide 1-3′hydroxylpropyl-3-octadecylimidazolium are 327.7 ° C., 361.7 ° C., and 389.3 ° C., respectively. there were. It can be seen that the thermal stability is improved by 150 ° C. and 90 ° C. or more, respectively, as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Example 3C)
<Thermal stability measurement result>
The 5%, 10% and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxylpropyl-N-octadecylpyrrolidinium were 349.8 ° C., 370.8 ° C. and 387.6 respectively. ° C. Even when compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C), it can be seen that the thermal stability is improved by 160 ° C. and 100 ° C. or more, respectively.

(Example 4C)
<Thermal stability measurement result>
Nonafluorobutanesulfonic acid-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium 5%, 10%, 20% It was 0.0 degreeC, 356.5 degreeC, and 390.1 degreeC. It can be seen that the thermal stability is improved by 160 ° C. and 85 ° C. or more, respectively, as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Example 5C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide-6-octadecyl-8-3′-hydroxylpropyl-1,8-diazabicyclo [5.4.0] -7-undecenium are The temperature was 326.2 ° C., 360.8 ° C., and 387.7 ° C., respectively. It can be seen that the thermal stability is improved by 160 ° C. and 85 ° C. or more, respectively, as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Example 6C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of 1-dodecyl-2-undecyl-3-'hydroxypropylimidazolium nonafluorobutanesulfonate were 335.4 ° C, 368.6 ° C, 396.2 ° C, respectively. Compared to a commercially available perfluoropolyether Z-DOL (Comparative Example 10C), which is generally known as a lubricant for magnetic recording media, shown as a comparative example, is 170 ° C. or higher, and Z-TETRAOL Even if it compares with (Comparative Example 11C), it turns out that it is 90 degreeC or more higher.

(Example 7C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imido-1-dodecyl-2-undecyl-3-'hydroxylpropyloctadecylimidazolium were 350.9 ° C and 373.7 ° C, respectively. It was 394.8 degreeC. Even when compared with the commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C), it can be seen that the thermal stability is improved by 170 ° C. and 110 ° C. or more, respectively.

(Example 8C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide-1- 3'hydroxypropyl-2-heptadecyl-3-octadecylimidazolium are 327.8 ° C, 364.3 ° C, respectively. The temperature was 398.8 ° C. It can be seen that the thermal stability is improved by 160 ° C. and 85 ° C. or more, respectively, as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Example 9C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxypropyl-N, N-dimethyltetradecylammonium were 340.0 ° C., 359.0 ° C., 375 respectively. 0 ° C. It can be seen that the thermal stability is improved at 145 ° C. and 90 ° C. or more, respectively, as compared with the commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Example 10C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide-N-3′hydroxypropyl-N, N-dimethyloctadecylammonium were 336.5 ° C., 359.4 ° C., and 376. It was 6 ° C. It can be seen that the thermal stability is improved by 150 ° C. and 90 ° C. or more, respectively, as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 1C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of nonafluorobutanesulfonic acid-1-octadecylimidazolium were 349.3 ° C., 375.0 ° C., and 397.5 ° C., respectively. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 2C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of hexafluorocyclopropane-1,3-bis (sulfonyl) imido-1-butyl-3-n-octadecylimidazolium are 347.2 ° C. and 367.0 ° C., respectively. 387.8 ° C. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 3C)
<Thermal stability measurement result>
The 5%, 10% and 20% weight loss temperatures of 6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium heptadecafluorooctane sulfonate are 361.9 ° C. and 382.7 respectively. And 403.5 ° C. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 4C)
<Thermal stability measurement result>
Hexafluorocyclopropane-1,3-bis (sulfonyl) imide-6-octadecyl-1,8-diazabicyclo [5.4.0] -7-undecenium 5%, 10%, 20% It was 346.3 degreeC, 384.1 degreeC, and 414.0 degreeC. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 5C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of octadecylammonium pentadecafluorooctanoate were 206.9 ° C., 215.8 ° C., and 223.4 ° C., respectively. Although it is an ionic liquid, since the pKa of the acid is larger than 10, the binding force between ions is weak, resulting in lack of thermal stability. In the case of this comparative example, although it is an ionic liquid, the thermal stability is greatly improved as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 7C). Not.

(Comparative Example 6C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of nonafluorobutanesulfonic acid-1-octadecyl-2-heptadecylimidazolium were 338.2 ° C., 365.9 ° C., and 390.1 ° C., respectively. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 7C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of hexafluorocyclopropane-1,3-bis (sulfonyl) imide-1-octadecyl-2-heptadecylimidazolium are 303.7 ° C., 366.4 ° C., respectively. It was 405.0 ° C. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 8C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of bis (nonafluorobutanesulfonyl) imide-octadecylammonium were 311.8 ° C., 329.8 ° C., and 348.0 ° C., respectively. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 9C)
<Thermal stability measurement result>
The 5%, 10%, and 20% weight loss temperatures of nonafluorobutanesulfonic acid-N, N, N-trimethyloctadecylammonium were 340.5 ° C., 356.2 ° C., and 371.9 ° C., respectively. Since it is an ionic liquid, its thermal stability is high as compared with commercially available perfluoropolyether Z-DOL (Comparative Example 10C) and Z-TETRAOL (Comparative Example 11C).

(Comparative Example 10C)
<Thermal stability measurement result>
As a comparative example 10C, a commercially available perfluoropolyether Z-DOL having a hydroxyl group at the terminal and having a molecular weight of about 2000 was measured. As a result, the 5%, 10%, and 20% weight loss temperatures were 165.0 ° C., 197.0 ° C., 226.0 ° C. The weight loss is attributed to evaporation.

(Comparative Example 11C)
<Thermal stability measurement result>
Perfluoropolyether (Z-TETRAOL) having a molecular weight of about 2000 and having a plurality of hydroxyl groups at the terminals, which is a commercially available product and is generally used as a lubricant for magnetic recording media, was used as the lubricant of Comparative Example 11C. The 5%, 10%, and 20% weight loss temperatures of Z-TETRAOL are 240.0 ° C., 261.0 ° C., and 282.0 ° C., respectively. Like Z-DOL, the weight loss is caused by evaporation.

The results of Examples 1C to 10C and Comparative Examples 1C to 11C are summarized in Table 3 together with the melting points.

Thus, it can be seen that the ionic liquid lubricant is overwhelmingly superior in thermal stability as compared with the commercially available perfluoropolyethers of Comparative Examples 10C and 11C, except for Comparative Example 5C.
Although it is a comparison in the ionic liquid about thermal stability, it compares in Example 1C and 2C and Comparative Example 2C and 3C about an imidazole type | system | group ionic liquid. In Examples into which hydroxyl groups were introduced, the weight loss temperatures of 5% and 10% were lower than those of the Comparative Examples, but the weight loss temperatures of 20% were almost the same, and it is considered that they had sufficient thermal stability.
The pyrrolidine ionic liquid into which the hydroxyl group is introduced also exhibits almost the same thermal stability as the imidazole ionic liquid.
Examples having an octadecyl-1,8-diazabicyclo [5.4.0] -7-undecene structure can be compared from Examples 3C and 4C and Comparative Examples 3C and 4C. In this case as well, the weight reduction temperature is higher in the comparative example of about 20 ° C to 430 ° C. However, an ionic liquid having an octadecyl-1,8-diazabicyclo [5.4.0] -7-undecene structure has a considerably high weight loss temperature, and the 20% weight loss temperature is close to 390 ° C., so that it has sufficient thermal stability. It is considered to have
Further, in Examples 6C to 10C, the weight reduction temperature does not change much compared with Comparative Examples 6C to 9C, and is almost the same, and is considered to have sufficient thermal stability.

As for the melting point, there is a great reduction effect by introducing a hydroxyl group. That is, the ionic liquid shown in the comparative example is a solid at 25 ° C. because it has a long-chain alkyl group. However, all ionic liquids having a hydroxyl group introduced and having bis (nonafluorobutanesulfonyl) imide as a conjugate base are liquid at room temperature. In the case of imidazole having the sulfonic acid of Example 1A as a conjugate base, the melting point is lower than that of the comparative example. The low melting point of the lubricant is advantageous in that the application can be greatly expanded in addition to the hard disk. For example, it can be expected that high-efficiency production with a liquid-type lubricant is realized in high-temperature extrusion / high-temperature forging (Non-Patent Document: Tribology Society 2014 Spring, Proceedings).

(Examples 1D to 10D and Comparative Examples 1D to 4D and Comparative Examples 6D to 9D)
<Disk durability test>
Lubricants containing the respective ionic liquids of Examples 1A to 10A, Comparative Examples 1A to 4A, and Comparative Examples 6A to 9A were applied to produce magnetic disks. As shown in Table 4, the CSS measurement of the magnetic disk exceeded 50,000 times, and the CSS measurement after the heating test exceeded 50,000 times, indicating excellent durability.

(Comparative Example 5D)
<Disk durability test>
The magnetic disk described above was produced using a lubricant containing octadecylammonium pentadecafluorooctanoate. As shown in Table 4, although the CSS measurement of the magnetic disk exceeded 50,000 times, the CSS measurement after the heating test was 891 times, and the durability deteriorated by the heating test. As shown in Comparative Example 5C, octadecylammonium pentadecafluorooctanoate is an ionic liquid. However, since the pKa of the acid is larger than 10, the bond strength between ions is weak and the thermal stability is lowered. It is thought that the characteristics of

(Comparative Example 10D)
<Disk durability test>
The magnetic disk described above was produced using a lubricant containing Z-DOL. As shown in Table 4, although the CSS measurement of the magnetic disk exceeded 50,000 times, the CSS measurement after the heating test was 12,000 times, and the durability deteriorated due to the heating test.

(Comparative Example 11D)
<Disk durability test>
The magnetic disk described above was manufactured using a lubricant containing Z-TETRAOL. As shown in Table 4, although the CSS measurement of the magnetic disk exceeded 50,000 times, the CSS measurement after the heating test was 36,000 times, and the durability deteriorated by the heating test.

Table 4 summarizes the results of Example 1D to Example 10D and Comparative Example 1D to Comparative Example 11D.

(Example 1E to Example 10E, Comparative Example 1E to Comparative Example 11E)
After the magnetic tapes described above were prepared using the ionic liquids of Examples 1A to 10A, the ionic liquids of Comparative Examples 1A to 9A, Z-DOL, and Z-Tetraol, the following measurements were performed. It was.
・ Friction coefficient of magnetic tape after 100 times of shuttle operation Temperature -5 ℃ or 40 ℃, relative humidity 90% ・ Still endurance test -5 ℃ or 40 ℃ relative Under 30% humidity environment ・ Shuttle endurance test -5 ° C environment or 40 ° C temperature, 90% relative humidity environment ・ Coefficient of friction of magnetic tape after 100 shuttle runs after heating test Environment or temperature 40 ° C, relative humidity 90% • Still durability test after heating test Temperature −5 ° C environment or temperature 40 ° C, relative humidity 30% environment • Shuttle durability test after heating test Temperature Under an environment of -5 ° C or under a temperature of 40 ° C and relative humidity of 90%

The results of Examples 1E to 10E and Comparative Examples 1E to 11E are summarized in Table 5-1 and Table 5-2.

In the table, “> 60” in the still durability means that it is longer than 60 minutes.
In the table, “> 200” of shuttle durability indicates that it exceeds 200 times.

The following could be confirmed.
It was found that the magnetic tape coated with the lubricant containing the ionic liquids of Examples 1A to 10A had excellent friction characteristics, still durability, and shuttle durability.
It was found that the magnetic tape coated with the lubricant containing the ionic liquids of Comparative Examples 1A to 4A and Comparative Examples 6A to 9A had excellent friction characteristics, still durability, and shuttle durability. Since this comparative lubricant was an ionic liquid, it exhibited excellent magnetic tape durability even after the heating test.
The magnetic tape coated with the lubricant containing the ionic liquid of Comparative Example 5A was found to have excellent friction characteristics, still durability, and shuttle durability. This comparative example lubricant greatly deteriorated in durability of the magnetic tape after the heating test.
It was found that the magnetic tape coated with Z-DOL was greatly deteriorated in still durability and shuttle durability.
It was found that the magnetic tape coated with Z-Tetraol has a large deterioration in still durability and shuttle durability.

From Table 5-1 and Table 5-2, an ionic liquid having a conjugated base and a conjugated acid is contained, and the conjugated acid is a group containing a linear hydrocarbon group having 6 or more carbon atoms and a hydroxyl group. By using an ionic liquid lubricant having a pKa in acetonitrile of the base acid of the conjugate base of 10 or less, excellent heat resistance and durability in magnetic tape and magnetic disk are obtained. I found out that Furthermore, not only is the heat resistance and durability of the magnetic recording medium excellent, but some of them also dissolve in the vertebral solvent bartrel, so when considering the application of hard disks in particular, the manufacturing process can be improved. But there is no problem.
As is clear from the above description, it contains an ionic liquid having a conjugate base and a conjugate acid, and the conjugate acid includes a linear hydrocarbon group having 6 or more carbon atoms and a group containing a hydroxyl group. The ionic liquid lubricant having pKa in acetonitrile of 10 or less of the acid that is the base of the conjugate base has a high decomposition temperature, 5%, 10%, and 20% weight loss temperature, and is thermally stable. Excellent. In addition, excellent lubricity can be maintained even under high temperature conditions as compared with conventional perfluoropolyethers, and lubricity can be maintained over a long period of time. Therefore, the magnetic recording medium using the lubricant containing the ionic liquid can obtain very excellent running performance, wear resistance, and durability.

DESCRIPTION OF SYMBOLS 11 Substrate 12 Underlayer 13 Magnetic layer 14 Carbon protective layer 15 Lubricant layer 21 Substrate 22 Magnetic layer 23 Carbon protective layer 24 Lubricant layer 25 Backcoat layer

Claims (7)

1. Containing an ionic liquid having a conjugate base and a conjugate acid,
   The conjugate acid has a group containing a hydroxyl group and a group containing a linear hydrocarbon group having 6 or more carbon atoms;
   Lubricant characterized in that the pKa in acetonitrile of the acid which is the base of the conjugate base is 10 or less.
2. The lubricant according to claim 1, wherein the conjugate acid is represented by any one of the following general formula (A), the following general formula (B), the following general formula (C), and the following general formula (D).
   

   

   However, the general formula (A), R _1, and R ₂ represents independently a hydrogen atom, and one of the group carbon atoms containing 6 or more straight chain hydrocarbon radical, n Represents an integer of 1 or more. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
   However, in said general formula (B), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
   However, in said general formula (C), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
   However, the general formula (D), R represents a group containing a straight chain hydrocarbon group having 6 or more carbon atoms, R _1, and R ₂ are each independently a hydrogen atom, and hydrocarbon Represents one of hydrogen groups, and n represents an integer of 1 or more.
3. The lubricant according to any one of claims 1 to 2, wherein the conjugate base is represented by any one of the following general formula (X) and the following general formula (Y).
   

   

   However, in said general formula (X), l represents an integer of 1-12.
   However, in said general formula (Y), l represents the integer of 1-12.
4. A magnetic recording medium comprising: a nonmagnetic support; a magnetic layer on the nonmagnetic support; and the lubricant according to any one of claims 1 to 3 on the magnetic layer.
5. Having a conjugate base and a conjugate acid,
   The conjugate acid has a group containing a hydroxyl group and a group containing a linear hydrocarbon group having 6 or more carbon atoms;
   An ionic liquid, wherein an acid serving as a base of the conjugate base has a pKa in acetonitrile of 10 or less.
6. The ionic liquid according to claim 5, wherein the conjugate acid is represented by any one of the following general formula (A), the following general formula (B), the following general formula (C), and the following general formula (D).
   

   

   However, the general formula (A), R _1, and R ₂ represents independently a hydrogen atom, and one of the group carbon atoms containing 6 or more straight chain hydrocarbon radical, n Represents an integer of 1 or more. However, at least one of R ₁ and R ₂ is a group containing a linear hydrocarbon group having 6 or more carbon atoms.
   However, in said general formula (B), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
   However, in said general formula (C), R represents group containing a C6 or more linear hydrocarbon group, and n represents an integer greater than or equal to 1.
   However, the general formula (D), R represents a group containing a straight chain hydrocarbon group having 6 or more carbon atoms, R _1, and R ₂ are each independently a hydrogen atom, and hydrocarbon Represents one of hydrogen groups, and n represents an integer of 1 or more.
7. The ionic liquid according to any one of claims 5 to 6, wherein the conjugate base is represented by any one of the following general formula (X) and the following general formula (Y).
   
   

   

   However, in said general formula (X), l represents an integer of 1-12.
   However, in said general formula (Y), l represents the integer of 1-12.

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