JP2017155121A - Debris removal lubrication composition, coating member of debris removal lubrication composition and application method of debris removal lubrication composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a debris removal lubrication composition high in debris removal effect and capable of enhancing lubricity compared to conventional ones, a coating member of the debris removal lubrication composition and an application method of the debris removal lubrication composition.SOLUTION: A debris removal lubrication composition contains a fluoropolyether-containing compound (S). Thereby debris removal effect can be enhanced and lubricity can be enhanced compared to conventional ones. The fluoropolyether-containing compound is preferably contained in a range of 0.01 pts.wt. to 10 pts.wt. based on 100 pts.wt. of the debris removal lubrication composition.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a foreign matter removing lubricant composition, an application member of the foreign matter removing lubricant composition, and a method of using the foreign matter removing lubricant composition.

  Lubricating oil or grease is used for members having sliding parts in door parts, window regulators, seat rails, sunroofs and other automobile parts and various devices.

  By the way, when foreign matters such as dust and sand are mixed in the lubricating oil or grease, there is a problem that the wear of the sliding member is promoted and abnormal noise is generated in some cases.

JP 2008-38047 A

  As a conventional technique, for example, improvement of lubricity by a highly crosslinked resin-added grease composition is known (see Patent Document 1).

  However, since the above-mentioned highly crosslinked resin-added grease composition has no action of removing foreign matters such as dust and sand, it has not been possible to suppress wear and noise.

  Accordingly, the present invention has been made in view of the above problems, and has a high foreign matter removing effect and a foreign matter removing lubricating composition capable of improving the lubricity as compared with the prior art, an application member of the foreign matter removing lubricating composition, and Another object of the present invention is to provide a method of using the foreign matter removing lubricating composition.

  The foreign matter removing lubricating composition of the present invention is characterized by containing a fluoropolyether-containing compound.

  In the present invention, the fluoropolyether-containing compound is preferably contained in the range of 0.01 parts by weight or more and 10 parts by weight or less when the foreign matter removing lubricating composition is 100 parts by weight.

  Moreover, in this invention, it is preferable to contain the said fluoro polyether containing compound represented by the following general formula (1) or (2).

Here, m + n = 3 to 500, m: n = 10 to 90:90 to 10, and one or both of X is a functional group, and when the functional group X is attached to one end, X on the opposite side is fluorine. (F), and the functional groups are carboxylate, alkylamide, carboxylate triethanolamine, dinitrobenzene, alcohol, methyl ester, ethoxylated alcohol, alkylamide, polyamide, alkoxysilane, phosphate, urethane methacrylate, and urethane. A compound comprising at least one of alkylates.

  Moreover, in this invention, it can be set as the structure containing the said lubricating component of the said fluoropolyether containing compound and lubricating oil or grease.

  In the present invention, the lubricating component is selected from at least one of mineral oil, synthetic hydrocarbon oil, diester oil, polyol ester oil, ether oil, glycol oil, silicone oil, and fluorine oil. It is preferable.

  In the present invention, the thickener contained in the grease includes lithium soap, calcium soap, sodium soap, aluminum soap, lithium composite soap, calcium composite soap, aluminum composite soap, urea compound, organic bentonite, polytetrafluoroethylene. , Silica gel, and sodium terephthalate are preferably selected from at least one of them.

  Further, in the present invention, when a foreign matter having at least 7 or 8 types as defined in JIS Z 8901 is added to the foreign matter removing lubricating composition containing the fluoropolyether-containing compound and the lubricating oil. In addition, it is preferable that sedimentation of the foreign matter is observed.

  Further, in the present invention, a foreign substance having at least one or two kinds defined in JIS Z 8901 is added to the foreign substance removing lubricating composition containing the fluoropolyether-containing compound and the lubricating component of the grease. The friction coefficient measured in this manner preferably does not include the fluoropolyether-containing compound and is smaller than the friction coefficient of the lubricating composition to which the foreign matter is added.

  Further, in the present invention, a foreign substance having at least one or two kinds as defined in JIS Z 8901 is added to the foreign substance removing lubricating composition containing the fluoropolyether-containing compound and the lubricating component of the grease. When the initial friction coefficient measured by the above is μ1, and the initial friction coefficient measured without adding the foreign matter is μ0, the rate of change of the friction coefficient represented by {(μ1-μ0) / μ0} × 100 (%) Is preferably less than 40%.

  Moreover, in this invention, the said foreign material removal lubricating composition as described above is placed in an environment containing dust.

  In the present invention, it is preferable that the dust has a volume ratio of 50% or less of the foreign matter removing lubricant composition.

In the present invention, the dust preferably contains SiO ₂ as a main component.

  Moreover, the application member of the foreign matter removing lubricating composition in the present invention is characterized in that the member applied with the foreign matter removing lubricating composition described above is placed in an environment containing dust.

  Further, the method for using the foreign matter removing lubricating composition in the present invention is characterized in that the member coated with the foreign matter removing lubricating composition described above is used in an environment containing dust.

  By containing the fluoropolyether-containing compound, the foreign matter removing lubricating composition of the present invention can enhance the foreign matter removing effect and improve the lubricity as compared with the conventional one.

It is a schematic diagram which shows the behavior of the fluoropolyether containing compound in grease. It is a schematic diagram which shows the behavior of the fluoropolyether containing compound in the grease mixed with foreign substances. It is a photograph which shows the mixed state of the foreign material of each sample of the comparative example 1 and Example 1. FIG. FIG. 4 is a schematic diagram of FIG. 3. It is a schematic diagram for demonstrating a reciprocating sliding test method. It is a graph which shows the relationship between the frequency | count of a reciprocating sliding in the state which does not contain a foreign material with respect to the sliding speed of Example 11 and the comparative example 4, and a friction coefficient. It is a graph which shows the relationship between the frequency | count of reciprocating sliding in the state containing the foreign material with respect to the sliding speed of Example 11 and Comparative Example 4, and a friction coefficient.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The present inventors blend various additives in lubricating oil or grease for automobile parts such as door lock mechanisms, window regulators, seat rails, sunroofs, and members with sliding parts in various devices. Then, the lubricity when containing foreign matters such as dust and sand was tested.

  As a result, solid lubricants generally prevent solid physical contact (abrasion), and reduce friction and impact relaxation with solids by rolling and intermolecular sliding. However, the generation of wear and noise cannot be suppressed, and the lubricity when foreign matter is mixed cannot be improved dramatically. In addition, the cleaning dispersant that acts to remove sludge also exhibits the effect of dispersing foreign matter, but cannot suppress the occurrence of wear and abnormal noise, and dramatically improves the lubricity when foreign matter is mixed. It did not reach.

  Therefore, as a result of sincere research on the foreign matter-removing lubricating composition, the present inventors can effectively improve the lubricity by using a lubricating composition containing a fluoropolyether-containing compound as compared with the conventional one. I found.

  The foreign substance removing lubricating composition in the present embodiment is characterized by containing a fluoropolyether-containing compound. Fluoropolyether-containing compounds are included as the basic skeleton. The basic skeleton means a repeating unit, and includes one in which a part of the fluoropolyether-containing compound is substituted with another substituent. “Fluoro” refers to a state in which at least a part of hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms, and “perfluoro” in which all are substituted with fluorine is also included.

  The foreign matter removal mechanism when using the foreign matter removing lubricating composition containing the fluoropolyether-containing compound is presumed as follows.

  FIG. 1 is a schematic diagram showing the behavior of a fluoropolyether-containing compound in grease. As shown in FIG. 1, since the fluoropolyether-containing compound S contained in the grease G as the foreign matter removing lubricating composition has the highest electronegativity of the fluorine atom F, it is charged to δ−, and the functional group R is , Δ + are charged.

  Since the fluorine atom F has a smaller affinity for grease (lubricating oil) than the functional group R, the fluorine atom F is likely to be arranged outward from the grease surface as shown in FIG. Although not shown, the fluorine atoms F are also arranged on the member side including the application surface 1 on which the grease G is applied. In order to keep the surface energy as small as possible inside the grease, the grease is arranged in a micelle structure with the fluorine atoms F on the inside and the functional groups R on the outside.

FIG. 2 is a schematic diagram showing the behavior of the fluoropolyether-containing compound in the grease mixed with foreign matter. FIG. 2 shows a state in which the foreign matter C is mixed into the grease G. The foreign matter C has, for example, SiO ₂ as a main component, and the surface of the foreign matter C is polarized δ−. For this reason, as shown in FIG. 2, the functional group (δ +) R is adsorbed on the foreign matter C so as to be electrically neutralized. Therefore, the fluorine atoms F are arranged outside the foreign substance C (on the side opposite to the adsorption side). The foreign matter C in which fluorine atoms F are arranged on the outside has a low affinity with the grease G. As a result, the foreign matter C is in a state of floating in the grease G, and an action of moving toward the surface of the grease G occurs (indicated by an arrow in FIG. 2). As a result, the foreign matter C is easily removed to the outside of the grease G. The foreign matter C removed from the grease G is in a state in which the outer peripheral surface is covered with the fluorine atoms F having low affinity with the grease G, and therefore, it is difficult for the foreign matter C to be mixed into the grease G (marked with a cross in FIG. 2). reference).

  The foreign matter removing action described above is particularly effective when, for example, there is a sliding relationship such as a rail and a slider in which members move greatly. That is, even in the case of semi-solid grease, foreign matter (see FIG. 2) that is fluidized by sliding and covered with fluorine atoms quickly moves to the surface of the grease and is easily discharged to the outside. Moreover, since the fluoropolyether-containing compound itself forms a film on the surface in contact with the sliding surface, it is possible to more effectively impart lubricity to the foreign matter removing lubricating composition.

  In the present embodiment, the fluoropolyether-containing compound is preferably contained in the range of 0.01 parts by weight or more and 10 parts by weight or less when the foreign matter removing lubricating composition is 100 parts by weight. When the content of the fluoropolyether-containing compound is less than 0.01 parts by weight, the effect of removing foreign matter is reduced and the effect of improving lubricity is insufficient. In addition, if the content of the fluoropolyether-containing compound exceeds 10 parts by weight, the content of the fluoropolyether-containing compound in the foreign matter-removing lubricating composition is too much, and the original lubricating performance of the lubricating composition is reduced. Resulting in. Moreover, even if it contains more fluoropolyether containing compounds than this, the further improvement of the target effect according to content is not acquired, and since price also becomes expensive, it is not practical. The fluoropolyether-containing compound is more preferably contained in the range of 0.05 parts by weight or more and 10 parts by weight or less.

(Fluoropolyether-containing compound)
In the present embodiment, for example, the following fluoropolyether-containing compounds can be presented.

  That is, in this Embodiment, the fluoro polyether containing compound represented by the following general formula (1) or (2) can be contained.

Here, m + n = 3 to 500, m: n = 10 to 90:90 to 10, and one or both of X is a functional group, and when the functional group X is attached to one end, X on the opposite side is fluorine. (F), and the functional groups are carboxylate, alkylamide, carboxylate triethanolamine, dinitrobenzene, alcohol, methyl ester, ethoxylated alcohol, alkylamide, polyamide, alkoxysilane, phosphate, urethane methacrylate, and urethane. A compound comprising at least one of alkylates.

  When both X are functional groups, the functional groups X may be the same or different, but are usually the same. The above-mentioned fluoropolyether-containing compounds can be used alone or in combination of two or more. At this time, the mixing ratio and the amount used are not limited and can be appropriately adjusted according to the coating suitability.

  The viscosity (20 ° C.) of the fluoropolyether-containing compound is about 50 cSt to 30000 cSt.

(Lubricant type, grease type)
The foreign matter removing lubricating composition of the present embodiment is characterized by containing a fluoropolyether-containing compound and a lubricating component of lubricating oil or grease. That is, the lubricating oil type includes a fluoropolyether-containing compound and a lubricating oil as a lubricating component. The grease type includes a fluoropolyether-containing compound and a base oil and a thickener as lubricating components.

  The content of the fluoropolyether-containing compound and the amount of the lubricating component should be appropriately adjusted within the range of the content of 0.01 to 10 parts by weight of the fluoropolyether-containing compound, depending on the intended use. Can do.

  The lubricating component is preferably selected from at least one of mineral oil, synthetic hydrocarbon oil, diester oil, polyol ester oil, ether oil, glycol oil, silicone oil, and fluorine oil. These lubricating components can be used alone or in combination of two or more, and the amount used is not particularly limited, and the amount can be selected according to the coating suitability. As the lubricating component, poly α olefins and ethylene α olefin oligomers are particularly preferable from the viewpoint that they can be used in a wide temperature range, compatibility with rubbers and resins, and compatibility with additives.

  The thickener contained in the grease of the present embodiment is lithium soap, calcium soap, sodium soap, aluminum soap, lithium composite soap, calcium composite soap, aluminum composite soap, urea compound, organic bentonite, polytetrafluoroethylene, It is preferably selected from at least one of silica gel and sodium terephthalate. The thickener is preferably lithium stearate and / or lithium 12-hydroxystearate from the viewpoint of shear stability. Lithium soap is a saponification reaction product of a fatty acid or a derivative thereof and lithium hydroxide. The fatty acid used is at least one selected from the group consisting of saturated or unsaturated fatty acids having 2 to 22 carbon atoms and derivatives thereof. Further, “soap” obtained by reacting the above fatty acid or derivative thereof with lithium hydroxide is commercially available, and this can also be used.

  Moreover, antioxidant, rust preventive agent, metal corrosion inhibitor, oiliness agent, antiwear agent, extreme pressure agent, solid lubricant, etc. can be added as needed. The content of these additives is within the range of about 0.01 to 30 parts by weight. The antioxidant can be selected from hindered phenol, alkylated diphenylamine, phenyl-α-naphthylamine and the like. The rust preventive agent can be selected from carboxylic acids such as stearic acid, dicarboxylic acids, metal soaps, carboxylic acid amine salts, metal salts of heavy sulfonic acids, or carboxylic acid partial esters of polyhydric alcohols. The metal corrosion inhibitor can be selected from benzotriazole or benzimidazole. The oily agent may be selected from amines such as laurylamine, higher alcohols such as myristyl alcohol, higher fatty acids such as palmitic acid, fatty acid esters such as methyl stearate, or amides such as oleylamide. it can. The antiwear agent can be selected from zinc, sulfur, phosphorus, amine, ester, and the like. The extreme pressure agent should be selected from zinc dialkyldithiophosphate, molybdenum dialkyldithiophosphate, sulfurized olefin, sulfurized oil, methyltrichlorostearate, chlorinated naphthalene, benzylated iodinated, fluoroalkylpolysiloxane, lead naphthenate, etc. Can do. The solid lubricant can be selected from graphite, graphite fluoride, polytetrafluoroethylene, melamine cyanurate, molybdenum disulfide, antimony sulfide, and the like.

(Foreign matter removal effect)
In the present embodiment, the foreign matter is not particularly limited. For example, the foreign matter is mainly composed of SiO ₂ (silicon dioxide). SiO ₂ has a crystal structure in which Si ₄ ⁺ is in the center and SiO ₄ tetrahedrons surrounded by _four O ₂ are connected to each other. The electronegativity of Si is 1.8, the electronegativity of O is 3.5, and both have a difference in electronegativity of 1.7. For this reason, SiO ₂ is polarized negatively (δ−).

In the present embodiment, as described in detail in an experiment described later, at least JIS Z 8901 is defined for a foreign matter removing lubricating composition (lubricating oil type) containing a fluoropolyether-containing compound and a lubricating oil. Foreign substances with 7 or 8 species were added. Both 7 types and 8 types defined in JIS Z 8901 contain SiO ₂ as a main component. Even if foreign matter is mixed in, the sedimentation of the foreign matter was observed in the lubricating oil of the present embodiment. That is, in the foreign matter removing lubricating composition of the present embodiment, foreign matter was not taken into the lubricating composition, and the foreign matter removing effect was confirmed.

Further, as will be described in detail in an experiment to be described later, at least one or two or more of those defined in JIS Z 8901 are used for a foreign matter removing lubricating composition (grease) containing a fluoropolyether-containing compound and a lubricating component of grease. The foreign material with seeds was added and the coefficient of friction was measured. As a result, it was found that the grease of the present embodiment does not contain a fluoropolyether-containing compound and is smaller than the friction coefficient of the conventional lubricating composition to which foreign matters are added. Both 1 type and 2 types defined in JIS Z 8901 contain SiO ₂ as a main component.

  In addition, as will be described in detail in the experiment described later, at least one or two or more of those defined in JIS Z 8901 are used for a foreign matter removing lubricating composition (grease) containing a fluoropolyether-containing compound and a lubricating component of grease. The initial friction coefficient μ1 was measured by adding a foreign substance with seeds. Further, the initial friction coefficient μ0 in a state where no foreign matter was added was also measured. Then, when the change rate (%) of the coefficient of friction represented by {(μ1-μ0) / μ0} × 100 was obtained, the change rate of the initial friction coefficient was less than 40% in the grease of the present embodiment. I understood that I can do it. Here, the “initial time” refers to a sliding condition in which the number of reciprocating sliding operations is 5 to 50 times. In the present embodiment, the rate of change is more preferably less than 30%, and even more preferably less than 20%.

  By using the foreign matter removing lubricating composition of the present embodiment, when the foreign matter removing lubricating composition is applied to the lubricated surface and the sliding member is slid, the friction coefficient is stably reduced due to the foreign matter removing effect. Can be kept. For this reason, by using the foreign matter removing lubricating composition of the present embodiment, it is possible to stably obtain high lubricity as compared with the conventional case.

  In addition, as shown in the experiment to be described later, the foreign matter described above is used by using a foreign matter obtained by mixing at least two types of one, two, seven, and eight types defined in JIS Z 8901 at a predetermined ratio. Observation of sedimentation and experiment of friction coefficient. The mixing ratio at this time is not particularly limited. For example, as shown in an experiment to be described later, one, two, seven and eight kinds defined in JIS Z 8901 can be mixed at a ratio of 1: 1: 1: 1.

  The foreign matter removing lubricating composition of the present embodiment can maintain highly stable lubricity due to the foreign matter removing effect even when placed in an environment containing dust. “In an environment containing dust” is, for example, an environment in which dust is contained at a volume ratio of 50% or less of the foreign matter removing lubricant composition. That is, with the foreign matter removing lubricant composition of the present embodiment, the foreign matter removing effect can be appropriately exhibited even if dust is contained up to about 50% in the volume ratio of the foreign matter removing lubricant composition. In the present embodiment, in an environment where dust is contained in an amount of about 0.01% or more by volume ratio of the foreign matter removing lubricant composition, the foreign matter removal such as the friction coefficient is clearly lower than that of the conventional lubricating composition. The effect is noticeable.

  In addition, the foreign matter removing lubricating composition of the present embodiment includes a lubricant, or a member having a sliding part in a door lock mechanism, a window regulator, a seat rail, a sunroof, and various other devices. Used as grease. Even if such a member having an automobile part and a sliding part is placed in an environment containing dust as described above, the foreign matter removing effect can be appropriately exhibited by using the foreign matter removing lubricating composition of the present embodiment. Thus, it is possible to stably obtain high lubricity as compared with the conventional case.

  Hereinafter, the present invention will be described in detail with reference to examples carried out in order to clarify the effects of the present invention. In addition, this invention is not limited at all by the following examples.

[Lubricant type]
Examples 1 to 10 and Comparative Examples 1 to 3 as lubricant types were prepared with the formulations shown in Table 1, Table 2, and Table 3 below. The raw materials used are as follows.

Example 1
Fluoropolyether-containing compound A (Product name: Fomblin (registered trademark, the same shall apply hereinafter) DA305): 1.0 part by weight Lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight Antioxidant Hindered phenol antioxidant (see the following general formula (3)): 0.2 parts by weight

Dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

(Example 2)
Fluoropolyether-containing compound B (product name: Fomblin DA306VAC): 1.0 part by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight antioxidant hindered phenol Antioxidant: 0.2 part by weight dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

(Example 3)
Fluoropolyether-containing compound B (Product name: Fomblin DA306VAC): 0.01 parts by weight Lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 98.8 parts by weight Antioxidant Hindered phenol Antioxidant: 0.2 part by weight dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

Example 4
Fluoropolyether-containing compound B (product name: Fomblin DA306VAC): 5.0 parts by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 64.8 parts by weight antioxidant hindered phenol Antioxidant: 0.2 parts by weight Dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 30.0 parts by weight

(Example 5)
Fluoropolyether-containing compound C (product name: Fomblin DA308): 1.0 part by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight antioxidant hindered phenol Antioxidant: 0.2 parts by weight Dust (JIS Z 8901 2 types, 8 types mixed at 1: 1): 1.0 parts by weight

(Example 6)
Fluoropolyether-containing compound D (product name: Fomblin DA410): 1.0 part by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight antioxidant hindered phenol Antioxidant: 0.2 parts by weight Dust (JIS Z 8901 2 types, 7 types mixed 1: 1): 1.0 parts by weight

(Example 7)
Fluoropolyether-containing compound E (Product name: Fluorolink (registered trademark, the same shall apply hereinafter) E10H): 1.0 part by weight Lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight Antioxidant Hindered phenolic antioxidant: 0.2 parts by weight Dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 parts by weight

(Example 8)
Fluoropolyether-containing compound F (product name: Fluorolink S10): 1.0 part by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight antioxidant hindered phenol Antioxidant: 0.2 part by weight dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

Example 9
Fluoropolyether-containing compound A (Product name: Fomblin DA305): 0.005 parts by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 98.8 parts by weight antioxidant hindered phenol type Antioxidant: 0.2 part by weight dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

(Example 10)
Fluoropolyether-containing compound B (Product name: Fomblin DA306VAC): 0.005 parts by weight Lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 98.8 parts by weight Antioxidant hindered phenol Antioxidant: 0.2 part by weight dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

(Comparative Example 1)
Lubricating oil Poly α-olefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 98.8 parts by weight Antioxidant Hindered phenolic antioxidant: 0.2 parts by weight Dust (JIS Z 8901 1 type, 2 types 7 types and 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

(Comparative Example 2)
Detergent Dispersant A Overbased metal Ca sulfonate (viscosity (100 ° C.) 52 cSt): 1 part by weight lubricating oil Poly α-olefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight antioxidant hinder Dophenol antioxidants: 0.2 parts by weight Dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 parts by weight

(Comparative Example 3)
Detergent Dispersant B Succinimide (viscosity (100 ° C.) 570 cSt): 1 part by weight lubricating oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 97.8 parts by weight antioxidant hindered phenol Antioxidant: 0.2 part by weight dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types mixed at 1: 1: 1: 1): 1.0 part by weight

  In the circles shown in Tables 1 to 3, separation and sedimentation of dust was observed at the bottom of the screw bottle. On the other hand, Δ indicates that although the dust settled and settled at the bottom of the screw bottle, the amount of dust settled was smaller than that of the example in which the same amount of dust was added. X: no separation and settling of dust was observed at the bottom of the screw bottle.

  FIG. 3 is a photograph showing a mixed state of foreign matters in each sample of Comparative Example 1 and Example 1. FIG. 4 is a schematic diagram of FIG. The left photograph and schematic diagram shown in FIGS. 3 and 4 are Comparative Example 1, and the right photograph and schematic diagram are Example 1. FIG. As shown in FIGS. 3 and 4, in Comparative Example 1, it was observed that the entire solution became cloudy and no foreign matter was removed. The reason for becoming cloudy in this way is to maintain a state in which seven or eight kinds of JIS Z 8901 having a small particle diameter are mixed in the lubricating oil. On the other hand, as shown in FIGS. 3 and 4, in Example 1, it was confirmed that the whole solution was in a translucent state, and foreign matters were excluded from the lubricating oil and settled to the bottom. In Example 9 and Example 10 in which “separation and settling of dust” shown in Table 2 was evaluated as Δ, the amount of foreign matter settled was smaller than that in the example evaluated as ○.

[Grease type]
Examples 11 to 13 and Comparative Example 4 were prepared as grease types with the formulation shown in Table 4 below. The raw materials used are as follows.

(Example 11)
Fluoropolyether-containing compound A (Product name: Fomblin DA305): 1.0 part by weight base oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 77.8 parts by weight Thickener Lithium soap (12 -Lithium hydroxystearate): 7.0 parts by weight Antioxidant Hindered phenol antioxidant: 0.2 parts by weight Solid lubricant A Polytetrafluoroethylene (average particle size 6.5 μm): 5.0 parts by weight Solid lubricant B Melamine cyanurate (average particle size 3.1 μm): 5.0 parts by weight Solid lubricant C Ultra high molecular weight polyethylene (average particle size 30 μm): 5.0 parts by weight Dust (JIS Z 8901 1 type, 2 Seeds, 7 kinds, 8 kinds mixed at 1: 1: 1: 1): 2.0 parts by weight

(Example 12)
Fluoropolyether-containing compound B (product name: Fomblin DA306VAC): 0.5 part by weight base oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 77.3 parts by weight Thickener Lithium soap (12 -Lithium hydroxystearate): 7.0 parts by weight Antioxidant Hindered phenol antioxidant: 0.2 parts by weight Solid lubricant A Polytetrafluoroethylene (average particle size 6.5 μm): 5.0 parts by weight Solid lubricant B Melamine cyanurate (average particle size 3.1 μm): 5.0 parts by weight Solid lubricant C Ultra high molecular weight polyethylene (average particle size 30 μm): 5.0 parts by weight Dust (JIS Z 8901 1 type, 2 Seeds, 7 kinds, 8 kinds mixed at 1: 1: 1: 1): 2.0 parts by weight

(Example 13)
Fluoropolyether-containing compound B (Product name: Fomblin DA306VAC): 10.0 parts by weight Base oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 67.8 parts by weight Thickener Lithium soap (12 -Lithium hydroxystearate): 7.0 parts by weight Antioxidant Hindered phenol antioxidant: 0.2 parts by weight Solid lubricant A Polytetrafluoroethylene (average particle size 6.5 μm): 5.0 parts by weight Solid lubricant B Melamine cyanurate (average particle size 3.1 μm): 5.0 parts by weight Solid lubricant C Ultra high molecular weight polyethylene (average particle size 30 μm): 5.0 parts by weight Dust (JIS Z 8901 1 type, 2 Seeds, 7 kinds, 8 kinds mixed at 1: 1: 1: 1): 15.0 parts by weight

(Comparative Example 4)
Base oil Polyalphaolefin (kinematic viscosity (40 ° C.): 30 mm ² / s): 79.8 parts by weight Thickener Lithium soap (lithium 12-hydroxystearate): 10.0 parts by weight Antioxidant Hindered phenol Antioxidant: 0.2 parts by weight of solid lubricant D Ultra high molecular weight polyethylene (average particle size 10 μm): 10.0 parts by weight of dust (JIS Z 8901 1 type, 2 types, 7 types, 8 types 1: 1: 1: 1 mixing): 2.0 parts by weight

  Lithium soap was synthesized in the presence of base oil and the temperature was raised with stirring. Next, after cooling to 80 ° C. or lower, various additives were formulated, and a uniform grease composition could be obtained by using a three-stage roll mill, a disper mill, a colloid mill, or the like.

  The mixing penetration was adjusted between 280 and 310. The test method is based on JIS K 2220. After adjusting the blending consistency, a specified amount of dust was mixed into the grease.

<Grease evaluation method>
Since grease is a viscous substance, it cannot be evaluated by sedimentation of dust such as lubricating oil. Therefore, the friction coefficient was evaluated.

<Experimental conditions for friction coefficient>
Test piece: PA66GF30 pin (φ4 mm) / Al plate load: 1000 gf
Grease coating thickness: 0.2mm
Test temperature: room temperature sliding speed: 10 mm / sec
Sliding width: 20 mm / one-way sliding: 10 reciprocations

  FIG. 5 is a schematic diagram for explaining the reciprocating sliding test method. Reference numeral 3 shown in FIG. 5 indicates a fixed pin, and reference numeral 4 indicates an Al plate. The Al plate 4 was slid back and forth in the A direction.

  In each sample, the respective dynamic friction coefficients before and after the addition of dust were measured, and the rate of change of the friction coefficient was calculated using the following formula.

  That is, the dynamic friction coefficient after dust mixing after 10 reciprocating slides was μ1, and the dynamic friction coefficient before dust mixing after 10 reciprocating slidings was μ0. Then, the coefficient of friction change (%) was determined by {(μ1-μ0) / μ0} × 100. The experimental results are shown in Table 4 below.

  Here, “◯” in the “change rate” column shown in Table 4 indicates that the change rate is less than 40%, and “x” indicates that the change rate is 40% or more.

  As shown in Table 4, it was found that the rate of change of the friction coefficient at the initial stage can be suppressed to less than 40% in the examples. Here, the coefficient of friction was measured with the number of sliding times reciprocated 10 times, that is, the initial state was slightly slid for the first few times. This is because the variation in the friction coefficient is large.

  Next, using the samples of Example 11 and Comparative Example 4, the relationship between the number of reciprocating sliding operations and the friction coefficient when the sliding speed was changed to 10 mm / s was examined. The experimental conditions for the friction coefficient were the same except for the above sliding speed and sliding times.

  FIG. 6 is a graph showing the relationship between the number of reciprocating slides and the coefficient of friction with respect to the sliding speed between Example 11 and Comparative Example 4 in a state in which no foreign matter is included. On the other hand, FIG. 7 is a graph showing the relationship between the number of reciprocating slides and the coefficient of friction with respect to the sliding speed between Example 11 and Comparative Example 4 in a state including foreign matter.

  As shown in FIG. 6, in a state in which no foreign matter is included, in both Example 11 and Comparative Example 4, the friction coefficient does not change greatly depending on the sliding speed, but in Example 11, the friction coefficient is higher than that in Comparative Example 4. I found that I could keep it low.

  Next, as shown in FIG. 7, it was found that the friction coefficient did not change greatly depending on the sliding speed in Example 11 even in the state including foreign matter. On the other hand, in Comparative Example 4, it was found that the coefficient of friction becomes more unstable as the sliding speed becomes lower.

  The foreign matter removing lubricating composition in the present invention is preferably applied as a lubricating oil or grease for a member having a sliding part in a door lock mechanism, a window regulator, a seat rail, a sunroof and other automobile parts, and various devices. be able to.

1 Application surface 3 Fixing pin 4 Al plate

Claims (14)

  A foreign matter-removing lubricating composition comprising a fluoropolyether-containing compound.   2. The foreign matter according to claim 1, wherein the fluoropolyether-containing compound is contained in a range of 0.01 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the foreign matter removing lubricant composition. Removal lubricating composition. 3. The foreign matter removing lubricating composition according to claim 1, comprising the fluoropolyether-containing compound represented by the following general formula (1) or (2).
Here, m + n = 3 to 500, m: n = 10 to 90:90 to 10, and one or both of X is a functional group, and when the functional group X is attached to one end, X on the opposite side is fluorine. (F), and the functional groups are carboxylate, alkylamide, carboxylate triethanolamine, dinitrobenzene, alcohol, methyl ester, ethoxylated alcohol, alkylamide, polyamide, alkoxysilane, phosphate, urethane methacrylate, and urethane. A compound comprising at least one of alkylates.   A foreign matter removing lubricating composition comprising the fluoropolyether-containing compound according to any one of claims 1 to 3 and a lubricating component of lubricating oil or grease.   The lubricating component is selected from at least one of mineral oil, synthetic hydrocarbon oil, diester oil, polyol ester oil, ether oil, glycol oil, silicone oil, and fluorine oil. The foreign matter removing lubricating composition according to claim 4.   Thickeners contained in the grease are lithium soap, calcium soap, sodium soap, aluminum soap, lithium composite soap, calcium composite soap, aluminum composite soap, urea compound, organic bentonite, polytetrafluoroethylene, silica gel, sodium terephthalate. 6. The foreign matter removing lubricating composition according to claim 4 or 5, wherein the lubricating composition is selected from at least one of taramate.   When the foreign substance removing lubricant composition containing the fluoropolyether-containing compound and the lubricating oil is added with foreign substances having at least 7 or 8 types as defined in JIS Z 8901, 5. The foreign matter removing lubricating composition according to claim 4, wherein sedimentation is observed.   Friction coefficient measured by adding at least one or two foreign substances defined in JIS Z 8901 to the foreign substance removing lubricating composition containing the fluoropolyether-containing compound and the lubricating component of the grease. 7. The foreign matter-removing lubricating composition according to claim 4, which does not include the fluoropolyether-containing compound and is smaller than a friction coefficient of the lubricating composition to which the foreign matter is added. .   An initial time measured by adding a foreign substance having at least one or two kinds as defined in JIS Z 8901 to the foreign substance removing lubricating composition containing the fluoropolyether-containing compound and the lubricating component of the grease. The friction coefficient change rate (%) represented by {(μ1−μ0) / μ0} × 100, where μ1 is the friction coefficient and the initial friction coefficient measured without adding the foreign matter is μ0, It is less than 40%, The foreign material removal lubricating composition in any one of Claims 4-6 or Claim 8 characterized by the above-mentioned.   The foreign matter removing lubricating composition according to any one of claims 1 to 9, wherein the foreign matter removing lubricating composition is placed in an environment containing dust.   The foreign matter removing lubricating composition according to claim 10, wherein the dust has a volume ratio of 50% or less of the foreign matter removing lubricating composition. The foreign matter removing lubricating composition according to claim 10 or 11, wherein the dust contains SiO ₂ as a main component.   A member applied with the foreign matter removing lubricating composition according to any one of claims 1 to 9, wherein the member coated with the foreign matter removing lubricating composition is placed in an environment containing dust. A method for using a foreign matter removing lubricating composition, wherein the member coated with the foreign matter removing lubricating composition according to any one of claims 1 to 9 is used in an environment containing dust.