JP2019019278A - Lubricant and use thereof - Google Patents

Abstract

To provide the lubricant having excellent sliding durability and having less deterioration in conductivity.SOLUTION: The lubricant used comprises: perfluoropolyether (A) having no functional group; and a fluoropolyether compound (B) that is a compound having a perfluoropolyether structure in a main chain and has at least one functional group at an end thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a lubricant and use thereof, and more particularly to a lubricant for electronic components such as connectors and use thereof.

  Lubricants used for electronic parts such as connectors where sliding members such as memory cards and memory sticks are frequently inserted and removed require excellent lubricity and sliding durability.

  In general, as a lubricant for connectors, fluorine resin fine particles such as polytetrafluoroethylene (hereinafter also referred to as “PTFE”) and perfluoropolyether (hereinafter also referred to as “PFPE”) oil are mixed. A lubricant is used (see, for example, Patent Document 1). Patent Document 1 describes that when fluorine-based resin fine particles and fluorine-based oil are applied, the coefficient of friction can be lowered to a small level by dispersing and adhering the fluorine-based resin fine particles to the fitting portion of the connector. .

  Patent Document 2 proposes a connector lubricant that does not contain solid particles from the viewpoint of electrical conduction. Specifically, Patent Document 2 includes at least a contact member having a main plating layer on the surface of a contact portion in contact with another contact member, and a coating containing a fluorinated oil is provided on the main plating layer. An electronic component provided is disclosed, and it is described that the fluorine-based oil is a perfluoropolyether oil.

JP 2006-173059 (June 29, 2006) International Publication No. 2014/178259 (Released on November 6, 2014)

  However, the conventional connector lubricant has room for further improvement from the viewpoint of realizing a lubricant that is excellent in sliding durability and has little decrease in conductivity. Specifically, when the lubricant described in Patent Document 1 is applied, there is a problem that the conductivity of the connector is lowered. Moreover, the lubricant described in Patent Document 2 is inferior in sliding durability.

  Therefore, an object of one embodiment of the present invention is to provide a lubricant that is excellent in sliding durability and has little decrease in conductivity.

  As a result of intensive studies to solve the above problems, the present inventors have found that a perfluoropolyether (A) having no functional group and a fluoropolyether compound (B) having at least one functional group at its terminal are used. )), It has been found that a lubricant having excellent sliding durability and little decrease in electrical conductivity can be provided, and the present invention has been completed.

That is, this invention consists of the following structures.
[1] A perfluoropolyether (A) having no functional group and a compound having a perfluoropolyether structure in the main chain and having at least one functional group at the terminal And a lubricant characterized by comprising.
[2] The lubricant according to [1], which does not contain a solid content.
[3] The perfluoropolyether structure of the fluoropolyether compound (B) in the main chain is a structure represented by the following formula (1), [1] or [2] Lubricant.
_{- (OCF 2) m (OCF} 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) r - ··· (1)
(In the formula (1), m, n, p, q, and r are each a real number of 0 to 60)
[4] The content of the fluoropolyether compound (B) with respect to the content of the perfluoropolyether (A) is 1% by weight to 45% by weight. The lubricant according to any one of the above.
[5] The functional group is at least one group selected from the group consisting of a hydroxyl group, a phosphazene group, an amino group, a carboxyl group, a phenyl group, a phenoxy group, and a thiol group, [1] The lubricant according to any one of [4].
[6] The lubricant according to any one of [1] to [5], wherein the perfluoropolyether (A) has a structure represented by the following formula (2).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y -CF} 3
... (2)
(In the formula (2), m, n, p, q and r are each a real number of 0 to 200, and x and y are each a real number of 0 to 3)
[7] The lubricant according to any one of [1] to [6], wherein the fluoropolyether compound (B) has a structure represented by the following formula (3).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y (} CF (CF 3)) w CH 2 -R l -Z ··· (3)
(In the formula (3), m, n, p, q and r are each a real number of 0 to 60, x, y and w are each a real number of 0 to 3, and R is a substituted or unsubstituted oxy. An alkylene group, l is a real number from 0 to 4, and when l ≧ 2, R may be the same or different and Z is a functional group)
[8] The lubricant according to any one of [1] to [7], wherein the fluoropolyether compound (B) has a structure represented by the following formula (4).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y (} CF (CF 3)) w CH 2 - (OR 2) l -OH ··· (4)
(In the formula (4), R ² is an n-propylene group substituted with at least one hydroxyl group, m, n, p, q and r are each a real number of 0 to 60, and x, y, w is a real number of 0 to 3 respectively, l is a real number of 0 to 4, and when l ≧ 2, R ² may be the same or different)
[9] The fluoropolyether compound (B) is selected from the group consisting of compounds having structures represented by the following formulas (5) to (8): [1] to [7] The lubricant according to any one of the above.

[10] A connector contact member comprising a lubricant layer, wherein the lubricant layer contains the lubricant according to any one of [1] to [9].

  According to one embodiment of the present invention, particularly when used in an electronic component such as a connector, there is an effect that it is possible to provide a lubricant that is excellent in sliding durability and has little decrease in conductivity.

  According to one embodiment of the present invention, there is an effect that it is possible to provide a connector contact member that is excellent in sliding durability and has little decrease in conductivity.

It is sectional drawing which shows the structure of the connector contact member which concerns on one Embodiment of this invention. It is a front view which shows the structure of the outline of the contact resistance measurement of the lubricant produced in the Example and the comparative example.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to this, and various modifications can be made within the range described, and the present invention also relates to embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is included in the technical scope. Unless otherwise specified in this specification, “A to B” representing a numerical range is intended to be “A or more and B or less”.

[1. lubricant〕
The lubricant according to an embodiment of the present invention includes a perfluoropolyether (A) having no functional group and a compound having a perfluoropolyether structure in the main chain, wherein the terminal has at least one functional group. And a fluoropolyether compound (B).

  When a lubricant containing particles such as PTFE is applied to the contact base material, since the particles such as PTFE are insulators, there is a concern about a decrease in conductivity on the coated surface. In addition, since electrical components and electronic components dislike contamination from the atmosphere, there is a concern about contamination of the work environment in the case of a lubricant containing PTFE particles. Furthermore, since PTFE particles are precipitated in the lubricant, stirring is required when the lubricant is used, and there is a problem in handling at the time of manufacture.

  In addition, when a lubricant containing only a perfluoropolyether having no functional group is applied to the contact base material, it is difficult to stay on the coated surface because the fluidity of the lubricant is high. Therefore, when the sliding member is reciprocated while being in contact with the lubricant, the sliding member comes into contact with the contact base material. As a result, the durability of the contact base material is poor.

  On the other hand, in one embodiment of the present invention, sliding is achieved by using a perfluoropolyether (A) having no functional group and a fluoropolyether compound (B) having at least one functional group at the terminal. It is possible to provide a lubricant that is excellent in durability and has little decrease in conductivity. Details will be described below with reference to FIG.

  When the lubricant according to one embodiment of the present invention is applied to the contact base material, the lubricant forms the lubricant layer 4 on the contact base material 5. The fluoropolyether compound (B) having at least one functional group at the terminal contained in the lubricant adheres to the contact base material 5 due to the interaction between the contact base material 5 and the functional group, and the fixing layer 3. It is thought to form mainly. The perfluoropolyether (A) having no functional group contained in the lubricant is considered to mainly form the fluidized bed 2 having lubricity on the fixed layer 3. Since the perfluoropolyether (A) does not have a functional group, it hardly adheres to the sliding member 1 when the sliding member 1 is reciprocated while being in contact with the fluidized bed 2. Therefore, when the perfluoropolyether (A) forms the fluidized bed 2 on the contact base material 5, wear of the lubricant can be suppressed. As a result, the durability of the contact base material 5 is excellent. Further, the fixing layer 3 is attached to the contact base material 5. Therefore, the fluoropolyether compound (B) forms the fixing layer 3 on the contact base material 5. When the fixing layer 3 reduces the contact between the sliding member 1 and the contact base material 5, the sliding durability of the lubricant can be improved.

  In this specification, the expression “excellent sliding durability” means that the lubricant is applied to the exposed surface of the contact base material, and the sliding member is reciprocated while contacting the contact base material coated with the lubricant. In this case, it is intended that the lubricant is not easily worn and the durability of the contact base material is excellent. The sliding durability can be evaluated by, for example, a sliding test using a tribo tester (manufactured by Kyoshin Denki Seisakusho), as described later in Examples.

  In the present specification, the expression “there is little decrease in conductivity” intends that the contact resistance between the contact base material coated with the lubricant and the sliding member is small. The conductivity can be evaluated, for example, by determining the contact resistance using a vibration friction wear tester (manufactured by Optimol), as will be described later in Examples. Since an increase in contact resistance causes a decrease in the transmission speed of an electric signal, a low resistance is required.

  Moreover, it is preferable that the lubricant which concerns on one Embodiment of this invention does not contain solid content. Examples of the solid content include fluorine-based fine particles such as PTFE and PVF (polyvinyl fluoride).

  The fact that the lubricant “does not contain solids” specifically intends the following cases. If the amount of precipitate obtained when the lubricant is centrifuged at 2000 rpm for 2 hours is 0% to 0.01% by weight with respect to the weight of the lubricant, Is not considered. Alternatively, if the amount of the residue obtained when the lubricant is filtered is 0% by weight to 0.01% by weight with respect to the weight of the lubricant, the lubricant is regarded as “not including solids”.

  In addition, for example, by using SEM-EDX (scanning electron microscope / energy dispersive X-ray spectroscopy), elemental analysis of the precipitate or the residue may specifically specify the composition of the solid content. it can.

[1-1. Perfluoropolyether (A)]
Perfluoropolyether (A) does not have a functional group. Therefore, the perfluoropolyether (A) is considered to mainly form a fluidized bed having lubricity without interacting with the contact base material. In addition, since it is difficult to interact with the sliding member, even when the sliding member is reciprocated while being in contact with the fluidized bed, it is considered that the lubricant is not easily worn and the durability of the contact base material is excellent. . Hereinafter, a perfluoropolyether having no functional group is also referred to as “nonfunctional perfluoropolyether”.

Examples of the perfluoropolyether (A) include compounds having a structure represented by the following formula (2).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y -CF} 3
... (2)
(In the formula (2), m, n, p, q, and r are real numbers of 0 to 200, and x and y are real numbers of 0 to 3, respectively).

  In the formula (2), m, n, p, q, and r are each a real number of 0 to 200, preferably a real number of 3 to 200, and more preferably a real number of 60 to 120.

The number average molecular weight of the perfluoropolyether (A) is 1000 to 30000, preferably 1250 to 25000, and more preferably 1500 to 20000. Here, the number average molecular weight can be measured, for example, by ¹⁹ F-NMR using JNM-ECX400 (manufactured by JEOL Ltd.).

  As the perfluoropolyether (A), a conventionally known commercially available compound can be used.

Examples of the commercially available compound include Fomblin (registered trademark) Y (manufactured by Solvay) having a structure represented by the following formula (9):
_{CF 3 - (OCF (CF 3} ) CF 2) r (OCF 2) m -O-CF 3
... (9)
(In the formula (9), r and m are each a real number of 0 to 200),
Demnum (registered trademark) having a structure represented by the following formula (10) (manufactured by Daikin Kogyo Co., Ltd., Japan):
_{CF 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) p -O-CF 2 CF 3 ··· (10)
(In the formula (10), p is a real number from 0 to 200),
And Krytox (registered trademark) having a structure represented by the following formula (11) (DuPont Specialty Chemicals, DeepWater, NJ):
CF ₃ CF ₂ CF ₂ — (OCF (CF ₃ ) CF ₂ ) _r —O—CF ₂ CF ₃ (11)
(In the formula (11), r is a real number from 0 to 200),
Is mentioned.

The perfluoropolyether (A) more preferably has a structure represented by the following formula (12) in the main chain.
_{- (OCF 2) m (OCF} 2 CF 2) n - ··· (12)
In said Formula (12), m + n is a real number of 10-300, and the real number of 150-200 is more preferable.

  In said Formula (12), n / m is a real number of 0.5-2, and a real number of 0.8-1.2 is more preferable.

  In the formula (12), m and n are not particularly limited as long as m + n is a real number of 10 to 300 and n / m is a real number of 0.5 to 2, but n is 3 to 200. A real number is preferable, and a real number of 60 to 120 is more preferable. Further, m is preferably a real number of 60 to 120.

The fluoropolyether (A) more preferably has a structure represented by the following formula (13).
_{CF 3 - (OCF 2) m} (OCF 2 CF 2) n -OCF 3 ··· (13)
In the formula (13), m + n is a real number of 10 to 300, a real number of 50 to 250 is preferable, and a real number of 150 to 200 is more preferable.

  In said Formula (13), n / m is a real number of 0.5-2, and the real number of 0.8-1.2 is preferable.

  In the formula (13), m and n are not particularly limited as long as m + n is a real number of 10 to 300 and n / m is a real number of 0.5 to 2, but n is 3 to 200. A real number is preferable, and a real number of 60 to 120 is more preferable. Moreover, m is preferably a real number of 3 to 200, and more preferably a real number of 60 to 120.

  Examples of the compound having the structure represented by the formula (13) include Fomblin (registered trademark) M and Z (manufactured by Solvay, m + n is a real number of 40 to 180, and n / m is 0.5 to 2 Is a real number).

  The content of the perfluoropolyether (A) with respect to the total amount of the lubricant is preferably 55% by weight to 99.5% by weight, and more preferably 60% by weight to 99% by weight.

[1-2. Fluoropolyether compound (B)]
The fluoropolyether compound (B) is a compound having a perfluoropolyether structure in the main chain, and has at least one functional group at the terminal. Therefore, it is considered that the fluoropolyether compound (B) adheres to the contact base material due to the interaction between the contact base material and the functional group, and mainly forms a fixing layer.

As an example of the perfluoropolyether structure,
_{- (OCF 2) m (OCF} 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) r - ··· (1)
(In the formula (1), m, n, p, q, and r are each a real number of 0 to 60)
Is mentioned.

The perfluoropolyether structure is more preferably, for example, a structure represented by the following formula (14).
_{- (OCF 2 CF 2 CF 2} ) p - ··· (14)
In said Formula (14), p is a real number of 1-60, Preferably, it is a real number of 3-50, More preferably, it is a real number of 6-21.

The number average molecular weight of the said fluoro polyether compound (B) is 500-10000, Preferably, it is 1000-7500, More preferably, it is 2000-5000, More preferably, it is 2000-4000. Here, the number average molecular weight can be measured, for example, by ¹⁹ F-NMR using JNM-ECX400 (manufactured by JEOL Ltd.).

  Examples of the functional group include at least one group selected from the group consisting of a hydroxyl group, a phosphazene group, an amino group, a carboxyl group, a phenyl group, a phenoxy group, and a thiol group.

  In the present specification, the phosphazene group means a functional group having a structure of the following formula (15) as a central skeleton.

  When the functional group is a phosphazene group, the lubricant can adhere to the contact base material by the interaction of the nitrogen atom in the phosphazene group with the contact base material.

  The fluoropolyether compound (B) may have at least one functional group at the terminal. Accordingly, the fluoropolyether compound (B) may have a functional group only at one end, or may have a functional group at both ends.

  The fluoropolyether compound (B) includes a compound having a functional group in the main chain other than the terminal in addition to one terminal or both terminals.

  When the functional group is a hydroxyl group, the fluoropolyether compound (B) has two or more hydroxyl groups from the viewpoint that the fluoropolyether compound (B) can adhere to the contact base material. It is preferable.

The fluoropolyether compound (B) preferably has a structure represented by the following formula (3).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y (} CF (CF 3)) w CH 2 -R l -Z ··· (3)
(In the formula (3), m, n, p, q and r are each a real number of 0 to 60, x, y and w are each a real number of 0 to 3, and R is a substituted or unsubstituted oxy. An alkylene group, l is a real number from 0 to 4, and when l ≧ 2, R may be the same or different and Z is a functional group).

  In the above formula (3), m, n, p, q, and r are each a real number of 0 to 60, preferably a real number of 3 to 50, and more preferably a real number of 6 to 21.

More preferably, the fluoropolyether compound (B) has a structure represented by the following formula (4).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y (} CF (CF 3)) w CH 2 - (OR 2) l -OH ··· (4)
(In the formula (4), R ² is an n-propylene group substituted with at least one hydroxyl group, m, n, p, q and r are each a real number of 0 to 60, and x, y, w is a real number of 0 to 3 respectively, l is a real number of 0 to 4, and when l ≧ 2, R ² may be the same or different.

More preferably, the fluoropolyether compound (B) includes, for example, a compound having a structure represented by the following formula (16).
_{CF 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) p - (OR 1) y -X ··· (16)
In said Formula (16), p is a real number of 0-60, Preferably, it is a real number of 3-50, More preferably, it is a real number of 6-21.

In said formula (16), R < ¹ > is a substituted or unsubstituted n-propylene group. When R ¹ is a substituted n-propylene group, a hydrogen atom may be substituted with a fluorine atom, a hydroxyl group, or the like, and a carbon atom may be substituted with an oxygen atom, a sulfur atom, or the like.

In said Formula (16), y is a real number of 1-4, Preferably, it is a real number of 1-3, More preferably, it is a real number of 1-2. Since R ¹ are independent of each other, when y ≧ 2, R ¹ may be the same or different.

  In the formula (16), X is a functional group, and examples of the functional group include a hydroxyl group, an amino group, a phosphazene group, a carboxyl group, a phenyl group, a phenoxy group, or a thiol group.

As said fluoro polyether compound (B) which has a structure represented by the said Formula (4), the compound which has a structure represented by following formula (17) is mentioned, for example.
_{CF 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) p -OCF 2 CF 2 CH 2 - (OR 2) l -OH
... (17)
In said Formula (17), p is a real number of 0-60, Preferably, it is a real number of 3-50, More preferably, it is a real number of 6-21.

In the formula (17), R ² is an n-propylene group substituted with at least one hydroxyl group.

In said Formula (17), l is a real number of 0-5, Preferably, it is a real number of 1-3, More preferably, it is a real number of 1-2. Since R ² is independent of each other, R ² may be the same or different when l ≧ 2.

  As a more specific example of the compound which concerns on one Embodiment of this invention, the said fluoro polyether compound (B) can mention the compound which has a structure represented by following formula (5)-(8). .

  The content of the fluoropolyether compound (B) with respect to the total amount of the lubricant is preferably 0.005% to 45% by weight, preferably 0.01% to 15% by weight, and 0.02% by weight. 10 to 10% by weight is more preferable.

  The content of the fluoropolyether compound (B) with respect to the content of the perfluoropolyether (A) is 1% to 45% by weight, preferably 1% to 15% by weight, and preferably 1% to 10%. Weight percent is more preferred.

  As the fluoropolyether compound (B), a conventionally known commercially available compound can be used.

[1-3. Other ingredients
The lubricant may contain other components other than the perfluoropolyether (A) and the fluoropolyether compound (B) as long as the performance is not impaired.

  Moreover, the lubricant according to an embodiment of the present invention may further contain a solvent.

  Examples of the solvent include acetone, methanol, and a fluorine-based solvent. From the viewpoint of good solubility of the perfluoropolyether (A) and the fluoropolyether compound (B), the solvent is preferably a fluorinated solvent. Examples of commercially available fluorinated solvents include PF-5060, PF-5080, HFE-7100, HFE-7200 (manufactured by 3M), Vertrel-XF (Mitsui / DuPont Fluorochemical), Asahi Clin AK-225 (Asahi Glass) Can be used as appropriate.

  The content of the solvent is preferably 50% by weight to 99.5% by weight and more preferably 80% by weight to 99% by weight with respect to the total amount of the lubricant.

  Further, the content of the solvent is preferably from 50% by weight to 99.5% by weight, preferably from 80% by weight to the total content of the perfluoropolyether (A) and the fluoropolyether compound (B). 99 weight% is more preferable and 90 weight%-99 weight% is further more preferable. If the content of the solvent is 50 wt% to 99.5 wt% with respect to the total content of the perfluoropolyether (A) and the fluoropolyether compound (B), the viscosity of the lubricant is This is preferable because it can be made sufficiently small and the thickness of the lubricating layer can be easily adjusted.

[2. Connector contact member
The connector contact member according to an embodiment of the present invention may include a lubricating layer, and the lubricating layer may include the lubricant.

  In this specification, the “connector” means a component provided so that an electronic component and a cable can be attached to and detached from other components. More specifically, examples of the “connector” include a connector for a portable storage medium such as a memory card and a memory stick, a connector for an earphone, and a connector for an AC adapter. Examples of the memory card include SD cards such as SD memory cards, miniSD (registered trademark) cards, transflash (T-Flash), and microSD (registered trademark) cards; SIM cards. An example of the memory stick is a USB memory.

  FIG. 1 is a cross-sectional view showing a configuration of a connector contact member according to an embodiment of the present invention. The connector contact member 6 includes a lubricating layer 4 containing a lubricant according to an embodiment of the present invention on the contact surface between the contact base material 5 and the sliding member 1. The lubricant contains a non-functional perfluoropolyether (A) and a fluoropolyether compound (B) having at least one functional group at the terminal. Therefore, it is considered that the fluoropolyether compound (B) adheres to the contact base material 5 by the interaction between the contact base material 5 and the functional group and mainly forms the fixing layer 3. The perfluoropolyether (A) is considered to mainly form the fluidized bed 2 having lubricity on the fixed layer 3.

  The connector contact member according to an embodiment of the present invention preferably includes the lubricating layer on the surface of the female terminal of the connector.

  The contact base material 5 is generally called a terminal. In the contact base material, gold or a gold alloy may be applied to the outermost surface of a contact member such as copper, copper alloy, or iron alloy by a plating method or vapor deposition.

  The sliding member 1 corresponds to a male terminal such as a memory card.

  In the contact base material 5, the method of forming the lubricant layer 4 on the contact surface with the sliding member 1 is not particularly limited. For example, the contact base material 5 is immersed in a lubricant and a lubricant is applied. Can be mentioned. In the contact base material 5, the lubricant may be immersed in the contact surface with the sliding member 1, and then ultraviolet irradiation or heat treatment may be performed.

  By performing ultraviolet irradiation or heat irradiation, a stronger bond can be formed between the lubricating layer 4 and the contact base material 5. In the case of performing ultraviolet irradiation, it is preferable to use ultraviolet light having a wavelength of 185 nm or 254 nm as a main wavelength because it does not affect the deep portions of the lubricating layer 4 and the contact base material 5. The temperature when the heat treatment is performed may be appropriately determined according to the size of the contact base material, but is preferably 60 to 170 ° C, more preferably 60 to 120 ° C, and further preferably 60 to 80 ° C. . What is necessary is just to determine the length of heat processing suitably according to the temperature in the case of performing the said heat processing.

  In the connector contact member according to an embodiment of the present invention, the fluidized layer includes perfluoropolyether (A) having no functional group, and the fixing layer has at least one functional group at the end. What is necessary is just to contain the fluoro polyether compound (B). Therefore, after applying the lubricant containing the fluoropolyether compound (B) having at least one functional group at the terminal to the exposed surface of the contact base material 5 to form the fixed layer 3, the exposed surface of the fixed layer 3 Alternatively, the fluidized bed 2 may be formed by applying a lubricant containing non-functional perfluoropolyether (A).

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Sliding durability test]
A phosphor bronze substrate (manufactured by TP Giken Co., Ltd.) was used as the substrate, and the substrate was first pretreated. Specifically, the substrate polished with sandpaper (# 2000) was ultrasonically cleaned in ethanol, and then the ethanol was removed with methanol. Thereafter, the substrate was dried in an oven at 110 ° C. for 2 hours.

  The prepared base material is put in the prepared lubricant at a speed of 6 mm / sec and immersed for 10 seconds, and then the base material is pulled up at a speed of 6 mm / sec, thereby adding the lubricant to the base material. It was applied to. The base material coated with the lubricant was heated at 80 ° C. for 1 hour, and a sliding test was performed using a tribo tester (manufactured by Kyoshin Seisakusho Co., Ltd.). The test conditions were as follows.

  Using the tribotester, a test sphere (material: SUJ2, diameter: 3/16 inch) was brought into contact with the substrate under a load of 200 g (2N). The substrate was reciprocated while contacting the test ball at a reciprocating frequency of 2 Hz and a sliding distance of 5 mm, thereby continuously measuring the friction coefficient generated on the contact surface between the test ball and the base material. The measurement was performed at room temperature. The time from the start of sliding until the friction coefficient suddenly increased (in the table, described as “time until the friction coefficient increases”) was measured, and the sliding durability of each lubricant was evaluated based on the length of the time. .

(Contact resistance measurement)
FIG. 2 is a conceptual diagram showing a schematic configuration of contact resistance measurement.

  A phosphor bronze substrate (manufactured by TP Giken Co., Ltd.) was used as the base material 15, and the base material was first pretreated. Specifically, the substrate polished with sandpaper (# 2000) was ultrasonically cleaned in ethanol, and then the ethanol was removed with methanol. Thereafter, the substrate was dried in an oven at 110 ° C. for 2 hours.

  The copper tape 16 and the base material 15 (thickness: 1 mm) subjected to the pretreatment were laminated. The resistance value between the test ball 13 (material: SUJ5, diameter 10 mm) and the base material 15 is measured using the vibration friction wear tester 12 (manufactured by Optimol, SRV5) while applying a constant load. And measured. In Tables 5 and 6, the measured value at this time is described as “resistance value before application of Example 2”. Thereafter, the base material 15 subjected to the pretreatment is immersed in the lubricant 14 having a concentration of 2% by weight to apply the lubricant 14 to the base material 15, and then the base material 15 to which the lubricant 14 is applied. The resistance value between the test balls 13 was measured. In Tables 5 and 6, the measured value at this time is described as “resistance value after application of Example 2”.

[Production of fluoropolyether compound]
(Production of Compound B1)
The compound B1 (number average molecular weight 2190, n is a real number of 6 to 21) represented by the following formula (5) was produced as follows.

2.5 kg of Demnun SA-1 (manufactured by Daikin Industries) was purified by silica gel column chromatography to obtain 1.6 kg of compound B1. ^When analyzed by ¹ H-NMR and ¹⁹ F-NMR spectrum measurement, the number average molecular weight of Compound B1 was 2190. The result of ¹⁹ F-NMR spectrum measurement is shown below.

¹⁹ F-NMR (neat, reference material: -OCF in the product ₂ C F ₂ CF ₂ O- to a -129.7ppm.)
_{δ = -129.7ppm [23F, -OCF 2} C F 2 CF 2 O-]
δ = −83.7 ppm [45F, —OC F ₂ CF ₂ C F ₂ O—]
δ = −86.5 ppm [2F, —OC F ₂ CF ₂ CH ₂ OH]
δ = −127.5 ppm [2F, —OCF ₂ C F ₂ CH ₂ OH]
δ = −82.4 ppm [3F, —OCF ₂ CF ₂ C F ₃ ]
_{δ = -130.7ppm [2F, -OCF 2} C F 2 CF 3]
δ = −84.7 ppm [2F, —OC F ₂ CF ₂ CF ₃ ]
¹ H-NMR (no solvent, reference material: D ₂ O)
_{δ = 2.5~4.5ppm [3H, CF 3} CF 2 CF 2 O (CF 2 CF 2 CF 2 O) n CF 2 CF 2 C H 2 O H].

(Production of Compound B2)
The compound B2 (number average molecular weight 2163, n is a real number of 6 to 21) represented by the following formula (6) was produced as follows.

Perfluoropolyether represented by 68.6 g of t-butyl alcohol, HO—CH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CF ₃ (number average molecular weight) under an argon atmosphere 2100) A mixture of 160 g, 2.1 g potassium t-butoxide, and 9.3 g glycidol was stirred at 70 ° C. for 22 hours. Thereafter, the mixture was washed with water, dehydrated, and purified by molecular distillation. As a result, 176 g of a mixture of the raw material perfluoropolyether and perfluoropolyether having two hydroxyl groups at its ends was obtained by reaction with glycidol. The mixture was washed with water, dehydrated, unreacted raw materials were removed by distillation, and then purified by distillation again to obtain 106 g of compound B2 (number average molecular weight 2163) as a fraction. The results of ¹ H-NMR and ¹⁹ F-NMR spectrum measurements are shown below.

¹⁹ F-NMR (neat, reference material: -OCF in the product ₂ C F ₂ CF ₂ O- to a -129.7ppm.)
_{δ = -129.7ppm [23F, -OCF 2} C F 2 CF 2 O-]
δ = −83.7 ppm [46F, —OC F ₂ CF ₂ C F ₂ O—]
δ = −86.5 ppm [2F, —OC F ₂ CF ₂ CH ₂ OH]
δ = −127.5 ppm [2F, —OCF ₂ C F ₂ CH ₂ OH]
δ = −82.4 ppm [3F, —OCF ₂ CF ₂ C F ₃ ]
_{δ = -130.7ppm [2F, -OCF 2} C F 2 CF 3]
δ = −84.7 ppm [2F, —OC F ₂ CF ₂ CF ₃ ]
¹ H-NMR (no solvent, reference material: D ₂ O)
_{δ = 2.5~4.5ppm [9H, CF 3} CF 2 CF 2 O (CF 2 CF 2 CF 2 O) n CF 2 CF 2 C H 2 OC H 2 C H (O H) C H 2 O H ].

(Production of Compound B3)
Compound B3 (number average molecular weight 2805, n is a real number of 6 to 21) represented by the following formula (7) was produced as follows.

Perfluoropolyether represented by 68.6 g of t-butyl alcohol, HO—CH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CF ₃ (number average molecular weight) under an argon atmosphere 2100) A mixture of 160 g, 2.1 g potassium t-butoxide, and 9.3 g glycidol was stirred at 70 ° C. for 22 hours. Thereafter, the mixture was washed with water, dehydrated, and purified by molecular distillation. As a result, 176 g of a mixture of the raw material perfluoropolyether and perfluoropolyether having two hydroxyl groups at its ends was obtained by reaction with glycidol. The mixture was washed with water, dehydrated, unreacted raw materials were removed by distillation, and then purified by distillation again to obtain 40 g of compound B3 (number average molecular weight 2100) as the residue.

¹⁹ F-NMR (solvent: None, reference material: -OCF in the product ₂ C F ₂ CF ₂ O- to a -129.7ppm.)
_{δ = -129.7ppm [28F, -OCF 2} C F 2 CF 2 O-]
δ = −83.7 ppm [56F, —OC F ₂ CF ₂ C F ₂ O—]
δ = −86.5 ppm [2F, —OC F ₂ CF ₂ CH ₂ OH]
δ = −127.5 ppm [2F, —OCF ₂ C F ₂ CH ₂ OH]
δ = −82.4 ppm [3F, —OCF ₂ CF ₂ C F ₃ ]
_{δ = -130.7ppm [2F, -OCF 2} C F 2 CF 3]
δ = −84.7 ppm [2F, —OC F ₂ CF ₂ CF ₃ ]
¹ H-NMR (without solvent, reference substance D ₂ O)
_{δ = 2.5~4.5ppm [15H, CF 3} CF 2 CF 2 O (CF 2 CF 2 CF 2 O) n CF 2 CF 2 C H 2 OC H 2 C H (O H) C H 2 OC H _{2 C H (O H) C} H 2 O H].

(Production of Compound B4)
Compound B4 (number average molecular weight 2805, n is a real number of 6 to 21) represented by the following formula (8) was produced as follows.

Perfluoropolyether represented by 68.6 g of t-butyl alcohol, HO—CH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CF ₃ (number average molecular weight) under an argon atmosphere 2100) A mixture of 160 g, 2.1 g sodium and 74.2 g S5ARPN (manufactured by Iki Chemical) was stirred at 70 ° C. for 22 hours. Thereafter, the mixture was washed with water, dehydrated, and purified by molecular distillation to obtain 152 g of Compound B4 (number average molecular weight 2805). The results of ¹ H-NMR and ¹⁹ F-NMR spectrum measurements are shown below.

¹⁹ F-NMR (neat, reference material: -OCF in the product ₂ C F ₂ CF ₂ O- to a -129.7ppm.)
_{δ = -129.7ppm [19F, -OCF 2} C F 2 CF 2 O-]
δ = −83.7 ppm [37F, —OC F ₂ CF ₂ C F ₂ O—]
δ = −86.5 ppm [2F, —OC F ₂ CF ₂ CH ₂ OH]
δ = −127.5 ppm [2F, —OCF ₂ C F ₂ CH ₂ OH]
δ = −82.4 ppm [3F, —OCF ₂ CF ₂ C F ₃ ]
_{δ = -130.7ppm [2F, -OCF 2} C F 2 CF 3]
δ = −84.7 ppm [2F, —OC F ₂ CF ₂ CF ₃ ]
δ = −84.7 ppm [15F, —OC ₆ H ₄ C F ₃ ]
¹ H-NMR (no solvent, reference material: D ₂ O)
_{δ = 2.5~4.5ppm [9H, CF 3} CF 2 CF 2 O (CF 2 CF 2 CF 2 O) n CF 2 CF 2 C H 2 OC H 2 C H (O H) C H 2 O H ]
_{δ = 6~8ppm [20H, -OC 6} H 4 CF 3].

[Production of lubricant 1]
Example 1
Vertrel-XF (manufactured by Mitsui DuPont Fluorochemical), Fomblin (registered trademark) M30 (manufactured by Solvay, average molecular weight 16000, hereinafter also referred to as “M30”), 1% by weight of compound B1 with respect to M30 And the lubricant of Example 1 was produced. The lubricant was prepared so that the total content of M30 and Compound B1 with respect to the total amount of the lubricant was 1.0% by weight.

(Example 2)
The lubricant of Example 2 was produced in the same manner as in Example 1 except that Compound B2 was used instead of Compound B1.

(Example 3)
A lubricant of Example 3 was produced in the same manner as in Example 1 except that Compound B3 was used instead of Compound B1.

Example 4
The lubricant of Example 4 except that Compound B4 represented by the following formula (8) (number average molecular weight 3089, n is a real number of 6 to 21) was used instead of Compound B1. Was made.

(Comparative Example 1)
The lubricant of Comparative Example 1 was prepared by dissolving only M30 in Vertrel-XF (Mitsui / Dupont Fluorochemical) so that the content of M30 was 1% by weight with respect to the total amount of the lubricant.

(Comparative Example 2)
A lubricant of Comparative Example 2 was prepared by adding M30 and 10 wt% PTFE (Asahi Glass) to Vertrel-XF (Mitsui / DuPont Fluorochemical).
The lubricant was adjusted so that the total content of M30 and PTFE with respect to the total amount of the lubricant was 1% by weight.

(Comparative Example 3)
A lubricant of Comparative Example 3 was prepared by dissolving only Compound B1 in Vertrel-XF (Mitsui / Dupont Fluorochemical) so that the content of Compound B1 was 1% by weight with respect to the total amount of the lubricant. .

(Comparative Example 4)
A lubricant of Comparative Example 4 was produced in the same manner as Comparative Example 3 except that Compound B2 was used instead of Compound B1.

(Comparative Example 5)
A lubricant of Comparative Example 5 was produced in the same manner as Comparative Example 3 except that Compound B3 was used instead of Compound B1.

(Comparative Example 6)
A lubricant of Comparative Example 6 was produced in the same manner as Comparative Example 3 except that Compound B4 was used instead of Compound B1.

[Result 1 of sliding durability test]
A sliding durability test was conducted using the lubricants produced in Examples 1 to 4 and the lubricants produced in Comparative Examples 1 to 6. The results are shown in Table 1.

  From Table 1, it can be seen that the lubricants produced in Examples 1 to 4 have a longer time to increase the friction coefficient than the lubricants produced in Comparative Examples 1 and 3 to 6. Therefore, a lubricant containing a non-functional fluoropolyether and a fluoropolyether compound having a functional group at a terminal is less slid than a lubricant containing only a fluoropolyether compound having a functional group at a terminal. It turns out that it is excellent in dynamic durability.

[Production of lubricant 2]
(Example 5)
The lubricant of Example 5 was produced in the same manner as in Example 1 except that the total content of M30 and Compound B1 with respect to the total amount of the lubricant was adjusted to 1.8% by weight.

(Example 6)
A lubricant of Example 6 was produced in the same manner as Example 5 except that Compound B2 was used instead of Compound B1.

(Example 7)
A lubricant of Example 7 was produced in the same manner as Example 5 except that Compound B3 was used instead of Compound B1.

(Example 8)
A lubricant of Example 8 was produced in the same manner as Example 5 except that Compound B4 was used instead of Compound B1.

(Comparative Example 7)
A lubricant of Comparative Example 7 was prepared in the same manner as in Example 1 except that only 1.8% by weight of M30 was added to Vertrel-XF (Mitsui / Dupont Fluorochemical).

(Comparative Example 8)
Comparative Example as in Example 1 except that 1.8% by weight of M30 and 10% by weight of PTFE (made by Asahi Glass) were added to Vertrel-XF (Mitsui / Dupont Fluorochemical). 2 lubricants were prepared.

(Comparative Example 9)
A lubricant of Comparative Example 9 was produced in the same manner as in Example 1 except that only 2% by weight of Compound B1 was added to Vertrel-XF (Mitsui / Dupont Fluorochemical).

(Comparative Example 10)
A lubricant of Comparative Example 10 was produced in the same manner as Comparative Example 9 except that Compound B2 was used instead of Compound B1.

(Comparative Example 11)
A lubricant of Comparative Example 11 was produced in the same manner as Comparative Example 9 except that Compound B3 was used instead of Compound B1.

(Comparative Example 12)
A lubricant of Comparative Example 12 was produced in the same manner as Comparative Example 9 except that Compound B4 was used instead of Compound B1.

[Result 2 of sliding durability test]
Table 2 shows the results of the sliding durability test of the lubricants produced in Examples 5 to 8 and Comparative Examples 7 to 12.

  From Table 2, it can be seen that the lubricants produced in Examples 5 to 8 have a longer time to increase the friction coefficient than the lubricants produced in Comparative Examples 9 to 12. From this, a lubricant containing a non-functional perfluoropolyether and a fluoropolyether compound having a functional group at the terminal is compared with a lubricant containing only a fluoropolyether compound having a functional group at the terminal, It can be seen that the sliding durability is excellent. In addition, it can be seen that the lubricants produced in Examples 5 to 8 have a long time to increase in the friction coefficient even when compared with the lubricants produced in Comparative Examples 7 and 8. Therefore, a lubricant containing a non-functional perfluoropolyether and a fluoropolyether compound having a functional group at a terminal includes a lubricant containing only a non-functional perfluoropolyether and a non-functional perfluoropolyether. Even when compared with a lubricant containing a powder of ether and PTFE, it can be seen that the sliding durability is excellent.

[Production of Lubricant 3]
(Examples 9-12, Comparative Examples 13-18)
For the lubricants produced in Examples 1 to 4 and Comparative Examples 1 to 6, instead of a phosphor bronze substrate (manufactured by TP Giken), a test material test piece (material: SUS301) (manufactured by TP Giken) was used as the base material. The sliding durability test was performed.

[Result of sliding durability test 3]
Table 3 shows the results of the sliding durability test of the lubricants produced in Examples 9-12 and Comparative Examples 13-18.

  From Table 3, it can be seen that the lubricants produced in Examples 9-12 have a longer time to increase the friction coefficient than the lubricants produced in Comparative Examples 15-18. From this, a lubricant containing a non-functional perfluoropolyether and a fluoropolyether compound having a functional group at the terminal is compared with a lubricant containing only a fluoropolyether compound having a functional group at the terminal, It can be seen that the sliding durability is excellent. Further, it can be seen that the lubricants produced in Examples 9 to 12 have a longer time to increase the friction coefficient than the lubricant produced in Comparative Example 13. From this, the lubricant containing the non-functional perfluoropolyether and the fluoropolyether compound having a functional group at the terminal, compared with the lubricant containing only the non-functional perfluoropolyether, It can be seen that the sliding durability is excellent.

[Production of lubricant 4]
(Example 13)
The lubricant of Example 13 was prepared by adding M30 and 5% by weight of Compound B2 to Vertrel-XF (Mitsui / Dupont Fluorochemical). The lubricant was adjusted so that the total content of M30 and compound B2 with respect to the total amount of the lubricant was 1% by weight.

(Example 14)
A lubricant of Example 14 was produced in the same manner as Example 13 except that 10% by weight of Compound B2 was added.

(Example 15)
A lubricant of Example 15 was produced in the same manner as Example 13 except that 30% by weight of Compound B2 was added.

(Comparative Example 19)
A lubricant of Comparative Example 19 was produced in the same manner as in Example 13 except that 50% by weight of Compound B2 was added.

[Result 4 of sliding durability test]
Table 4 shows the results of the sliding durability test of the lubricants produced in Examples 13 to 15 and Comparative Example 19.

  From Table 4, it can be seen that the lubricants produced in Examples 13 to 15 have a longer time to increase the friction coefficient than the lubricants produced in Comparative Examples 1 and 4. Therefore, the lubricant containing the non-functional perfluoropolyether and the fluoropolyether compound having a functional group at the terminal is a fluoropolyether compound having a functional group at the terminal or the nonfunctional perfluoropolyether. It turns out that it is excellent in sliding durability compared with the lubricant containing only any one.

[Results of contact resistance measurement]
Tables 5 and 6 show the results of contact resistance measurement of the lubricants produced in Example 2 and Comparative Example 2.

  From Table 5, in the low load region (load is 0.1 N), the resistance value after applying the lubricant produced in Example 2 to the substrate is based on the lubricant produced in Comparative Example 2. It turns out that it becomes small compared with the resistance value after apply | coating to a material. From this, compared with the case where a lubricant containing PTFE powder is applied to a base material, when applying a lubricant containing no PTFE powder to the base material, there is little decrease in conductivity. Recognize.

  From the above results, the lubricant containing the non-functional perfluoropolyether and the fluoropolyether compound having a functional group at the terminal is the lubricant containing only the non-functional perfluoropolyether and the non-functional perfluoropolyether. It can be seen that compared to a lubricant containing polyether and PTFE powder, the sliding durability is excellent and the decrease in conductivity is small.

  The present invention can be used as a lubricant applied to a connector contact base material.

DESCRIPTION OF SYMBOLS 1 Sliding member 2 Fluidized bed 3 Adhesive layer 4 Lubrication layer 5 Contact base material 6 Connector contact member 11 Measuring instrument 12 Vibrating friction and wear tester 13 Test ball 14 Lubricant 15 Base material 16 Copper tape

Claims (10)

A perfluoropolyether (A) having no functional group;
A lubricant having a perfluoropolyether structure in the main chain and a fluoropolyether compound (B) having at least one functional group at a terminal.   The lubricant according to claim 1, wherein the lubricant does not contain a solid content. The lubricant according to claim 1 or 2, wherein the perfluoropolyether structure of the fluoropolyether compound (B) in the main chain is a structure represented by the following formula (1). .
_{- (OCF 2) m (OCF} 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) r - ··· (1)
(In the above formula (1), m, n, p, q, r are each a real number of 0-60)   The content of the fluoropolyether compound (B) with respect to the content of the perfluoropolyether (A) is 1% by weight to 45% by weight, according to any one of claims 1 to 3, The lubricant as described.   The functional group is at least one group selected from the group consisting of a hydroxyl group, a phosphazene group, an amino group, a carboxyl group, a phenyl group, a phenoxy group, and a thiol group. The lubricant of any one of -4. The lubricant according to any one of claims 1 to 5, wherein the perfluoropolyether (A) has a structure represented by the following formula (2).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y -CF} 3
... (2)
(In the formula (2), m, n, p, q and r are each a real number of 0 to 200, and x and y are each a real number of 0 to 3) The lubricant according to any one of claims 1 to 6, wherein the fluoropolyether compound (B) has a structure represented by the following formula (3).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y (} CF (CF 3)) w CH 2 -R l -Z ··· (3)
(In the formula (3), m, n, p, q and r are each a real number of 0 to 60, x, y and w are each a real number of 0 to 3, and R is a substituted or unsubstituted oxy. An alkylene group, l is a real number from 0 to 4, and when l ≧ 2, R may be the same or different and Z is a functional group) The lubricant according to any one of claims 1 to 7, wherein the fluoropolyether compound (B) has a structure represented by the following formula (4).
_{CF 3 - (CF 2) x} - (OCF 2) m (OCF 2 CF 2) n (OCF 2 CF 2 CF 2) p (OCF 2 CF 2 CF 2 CF 2) q (OCF (CF 3) CF 2) _{r -O (CF 2) y (} CF (CF 3)) w CH 2 - (OR 2) l -OH ··· (4)
(In the formula (4), R ² is an n-propylene group substituted with at least one hydroxyl group, m, n, p, q and r are each a real number of 0 to 60, and x, y, w is a real number of 0 to 3 respectively, l is a real number of 0 to 4, and when l ≧ 2, R ² may be the same or different) The said fluoro polyether compound (B) is selected from the group which consists of a compound which has a structure represented by following formula (5)-(8), The any one of Claims 1-7 characterized by the above-mentioned. Lubricant.

A connector contact member comprising a lubricating layer,
A connector contact member, wherein the lubricant layer contains the lubricant according to claim 1.

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