Lubricant additive composition and method of use thereof

Abstract

Provided are an additive composition for lubricating oil and a method for using the same. 【Solution means】 The present invention relates to (A) a (per)fluoropolyether polymer [PFPE polymer add having a first chain end and a second chain end respectively bonded to both ends of a (per)fluoropolyether chain [PFPE chain add , wherein at least one (per)fluoropolyether polymer [PFPE polymer add contains a first chain end having a group of the formula -C(O)NR a R b (wherein R a and R b are each independently selected from hydrogen, a linear or branched C1-C6 alkyl group), and the second chain end is a C1-C6 (per)fluoroalkyl group, -CF2C(O)CF3, and -C(OH)2CF3, -C(O)NR a R b (wherein R a and R b are each independently selected from hydrogen, a linear or branched C1-C6 alkyl group), -C(O)OR c (wherein R c is a linear or branched C1-C6 alkyl group), and relates to an additive composition containing at least one (per)fluoropolyether polymer [PFPE polymer add ; and (B) a fluorescent dye of the formula (I) (e.g., a rhodamine dye) in an amount of 0.01 to 25.0% by weight based on the weight of component (A). The present invention also relates to the use of the additive composition in a mixture with a hydrogenated or fluorinated lubricating oil. This additive composition can impart both rust prevention properties and fluorescent properties to the lubricating oil.

Description

[Technical Field]

[0001] Priority This application claims priority under European Patent Application No. 24205671.1, filed in Europe on 9 October 2024, and the entire contents of this application are incorporated herein by reference for all purposes.

[0002] The present invention relates to the field of lubricating oils, and more specifically to an additive composition for use in mixture with hydrogenated or fluorinated lubricating oils. This additive composition can impart both rust-preventive and fluorescent properties to the lubricating oil. [Background technology]

[0003] Certain hydrogen-based lubricants, whether natural or synthetic, are known to possess excellent lubricating properties and are readily available on the market at reasonable prices. Examples of hydrogen-based lubricants include hydrocarbon-type mineral oils, hydrogenated animal and vegetable oils, synthetic hydrogenated oils such as polyalphaolefins (PAOs), dibasic acid esters, polyol esters, phosphate esters, polyesters, alkylated naphthalenes, polyphenyl ethers, polybutenes, multiple alkylated cyclopentanes, silane hydrocarbons, siloxanes, and polyalkylene glycols.

[0004] A possible alternative to hydrogen-based lubricants is (per)fluoropolyether (PFPE) lubricants, which contain (per)fluorooxyalkylene chains in which monomers consisting of (per)fluoroalkyl groups are linked by ether bonds. In particular, PFPE lubricants exhibit excellent heat and chemical resistance, making them useful in applications characterized by harsh conditions such as very high temperatures, the presence of oxygen, and the use of aggressive chemicals and radiation.

[0005] Lubricants such as oils and greases are generally compositions containing a base oil (e.g., hydrogenated oil or fluorinated oil) and one or more additives, and in the case of greases, at least one thickener. The base oil determines the basic properties of the lubricant. Additives can not only compensate for and improve the performance defects of the base oil, but can also impart additional properties such as rust prevention, oxidation prevention, wear resistance, thermal stability, and visual effects (e.g., color or fluorescence).

[0006] Depending on its chemical composition, PFPE polymers can be used as the main component of lubricating oil (i.e., base oil) or as an additive added to lubricating oil to improve its properties.

[0007] For example, (Patent Document 1) (Ausimont Srl) discloses the use of a PFPE polymer having specific functionalized end groups as an additive for imparting rust-preventive properties to a PFPE-based lubricant.

[0008] Patent Document 2 (Solvay Solexis SpA) discloses a lubricating composition containing a fluorinated lubricating oil and a solvent for this oil that can form a lubricating film by depositing a thin lubricating layer on the surface after evaporation of the solvent. In one embodiment, the lubricating composition disclosed in Patent Document 2 contains a fluorescent dye as a non-fluorinated additive, namely 2,5-bis(5-tert-butylbenzoxazole-2-yl)thiophene (commercially available as BBOT), in combination with a functional (per)fluoropolyether polymer having terminal groups of the type where T is -CF3 and T' is -CF2C(CF3)(OH)2 (75 mol%) and -CF2COOH (25 mol%), i.e., PFPE having acidic chain end groups.

[0009] Lubricants containing fluorescent dyes are particularly useful in applications where leak detection is critical, such as hydraulic and refrigerant equipment. In fact, by irradiating the outer surface of the equipment with ultraviolet light capable of exciting the fluorescence emission of the dye, it is possible to observe the fluorescence emission of leaked lubricant and identify the location of the leak within the equipment.

[0010] The fluorescence properties of a lubricating oil composition can also be advantageously utilized to determine the presence or uniformity of a lubricating oil coating on a surface. In fact, by irradiating the coating with ultraviolet light, it is easy to confirm that the coating is uniformly applied to the surface, has not moved from its original position, or is present on the surface as desired, even if the lubricating oil composition is applied in such a thin layer that it is almost impossible to see with the naked eye.

[0011] In many applications, it is desirable for lubricating oils to exhibit two or more additional properties to those of the base oil, such as fluorescent properties or rust-preventive properties. In principle, this can be achieved by adding two or more additives to the base oil, each exhibiting its own effect. However, in practice, it is not easy to predict the overall effect of an additive composition mixed with a base oil, and it often does not correspond to the sum of the effects that each additive can achieve individually. Furthermore, the applicant has observed that this problem becomes particularly pronounced when fluorescent dyes and PFPE polymers with functional group ends are present simultaneously in the additive composition or lubricating oil, because these two compounds may interact and inhibit the effects of one or both of them. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] U.S. Patent No. 5190681 [Patent Document 2] U.S. Patent Application Publication No. 2006 / 163532A1 [Patent Document 3] International Publication No. 2008 / 065163 Pamphlet [Patent Document 4] International Publication No. 2015 / 177857 Brochure [Patent Document 5] International Publication No. 2007 / 082829 Brochure [Patent Document 6] International Publication No. 2023 / 078890 Brochure [Overview of the Initiative]

[0013] Taking the above prior art into consideration, the applicant faced the challenge of providing an additive composition that, when mixed with a base oil of either hydrogenated oil or (fully) fluorinated oil, can impart both fluorescent properties and rust-preventive properties.

[0014] This time, it was discovered that this technical challenge can be solved by an additive composition that combines a fluorescent dye belonging to the xanthene dye classification with a functional PFPE polymer having non-acidic functional groups at the chain ends of the PFPE polymer backbone.

[0015] When this additive composition is mixed with a base oil, a lubricating oil such as oil or grease is obtained that has rust-preventive properties and a fluorescence response when irradiated with ultraviolet light.

[0016] Furthermore, if non-acidic functional groups are present instead of acidic groups at the chain ends of the PFPE polymer backbone, the corrosiveness of the additive and the lubricating oil composition containing it to metal surfaces is reduced. [Modes for carrying out the invention]

[0017] According to the first aspect, the present invention is (A)(Per)fluoropolyether chain [PFPE chain] add A PFPE chain having a first chain end and a second chain end attached to both ends of ] add [PFPE polymer] contains at least one (per)fluoropolyether polymer. add ] The first chain end is of formula -C(O)NR a R b (In the formula, R a and R b Each independently comprises a hydrogen group (selected from linear or branched C1-C6 alkyl groups), The second chain end is a C1-C6 (per)fluoroalkyl group, -CF2C(O)CF3, and -C(OH)2CF3, -C(O)NR a R b (wherein R a and R b are each independently selected from hydrogen, a linear or branched C1-C6 alkyl group), -C(O)OR c (wherein R c is a linear or branched C1-C6 alkyl group), and at least one (per)fluoropolyether polymer [PFPE polymer add] containing a group selected from; (B) A fluorescent dye of formula (I) in an amount of 0.01 to 25.0% by weight based on the weight of component (A):

Chemical formula

[0018] According to a second aspect, the present invention relates to a lubricating oil composition containing a base oil and an additive composition according to the first aspect, wherein the base oil is selected from a hydrogenated oil or a (fully) fluorinated oil.

[0019] According to a third aspect, the present invention is a method for detecting leakage of a lubricating oil composition from a device, comprising: - preparing a device containing the lubricating oil composition according to the second aspect; - irradiating the outer surface of the device with ultraviolet light capable of exciting the fluorescence of the dye of formula (I); - To determine the leakage of the lubricating oil composition by observing the fluorescence emission of the fluorescent dye of formula (I) from the leaked lubricating oil composition on the aforementioned outer surface; This includes methods.

[0020] According to a fourth aspect, the present invention is a method for detecting the presence or uniform application of a lubricating oil coating on a substrate, - To obtain a coated surface by coating the surface of a substrate with a lubricating oil composition according to a second embodiment; - Irradiating the coated surface with ultraviolet light to excite the fluorescence of the dye of formula (I) present in the lubricating oil composition; - Determining the presence or uniformity of a lubricating oil coating on a surface based on the fluorescence response from the coated surface; Regarding methods including

[0021] In this specification: - The acronym "PFPE" stands for "(per)fluoropolyether," and when used as a noun, it is intended to mean either singular or plural depending on the context; - The prefixes "(per)" and "(complete)" in the terms "(per)fluoropolyether" and "(complete)fluorinated oil" mean that the polyether and oil may be completely or partially fluorinated.

[0022] The additive composition according to the present invention comprises at least one (per)fluoropolyether polymer [PFPE polymer]. add It contains ] (component (A)) and a fluorescent dye of formula (I) (component (B)).

[0023] The PFPE polymer add functions substantially as a fluid medium into which the fluorescent dye of formula (I) is dispersed or solubilized.

[0024] Component (A) is a (per)fluoropolyether polymer [PFPE polymer]. add In this, the first chain end is preferably of formula -C(O)NR a R bIncluding the terminal group of the group, R a and R b Each is independently selected from hydrogen and C1-C3 alkyl groups (linear or branched), more preferably from hydrogen and methyl; preferably, a PFPE polymer. add The second chain end is a C1-C3 perfluoroalkyl group (e.g., -CF3). 、 It contains a group selected from -CF2C(O)CF3 and -C(OH)2CF3.

[0025] PFPE polymer add Because it lacks acidic functional end groups, i.e., -COOH groups, the additive composition has low aggressiveness, resulting in good compatibility with a variety of materials, especially metal surfaces.

[0026] PFPE polymer add Preferably, (per)fluoropolyether chain [PFPE chain] add ] is a partially or completely fluorinated chain [chain(R)] which includes, preferably consists of, a repeating unit R°. f ) add ] and the repeating unit R° is, (i)-CFXO-(wherein X is F or CF3), (ii)-CFXCFXO-(wherein X is the same or different in each existence, and at least one of X is F or CF3, provided that -F), (iii)-CF2CF2CW2O-(wherein each W is either the same as or different from each other, and is F, Cl, or H), (iv)-CF2CF2CF2CF2O-, (v)-(CF2) w -CFZ-O-(where w is an integer from 0 to 3, and Z is the general formula -OR) (f-a) -Y is the basis, R (f-a)(1) is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, wherein the repeating units are selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O- (wherein each of X is independently F or CF3), and Y is a C1-C3 perfluoroalkyl group. It is selected independently of others.

[0027] Preferably, chain (R f ) add It follows the following formula: (R f - add -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- (In the formula, - X 1 It is selected independently of -F and -CF3, - X 2 , X 3 They are the same or different from each other and in each existence, X 2 and X 3 Provided that at least one of them is -F, independently -F, -CF3, - g1, g2, g3, and g4 are either equal to or different from each other, and each independently is ≥ 0 such that g1+g2+g3+g4 is in the range of 2 to 300, preferably 10 to 250, and more preferably 15 to 200, and if at least two of g1, g2, g3, and g4 are different from zero, then the different repeating units are generally statistically distributed along the chain.

[0028] more preferably, chain (R f -CF add -I) In X 2 and X 3 They are the same or different from each other and in each existence, X 2 and X3 Independently, they are either -F or -CF3, provided that at least one of them is -CF3.

[0029] More preferably, the chain (R f ) add The formula follows this equation: (R f - add -II) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 -(CF(CF3)O) g5 (CF2CF(CF3)O) g6 ]- (In the formula, - X 1 It is selected independently of -F and -CF3, - X 2 , X 3 They are the same or different from each other and in each existence, X 2 and X 3 On the condition that at least one of them is -F, independently, they are -F or -CF3, - g1, g2, g3, g4, g5, and g6 are either equal to or different from each other, and independently g1+g2+g3+g4+g5+g6 is ≥ 0 such that g1+g2+g3+g4+g5+g6 is in the range of 2 to 300, preferably 10 to 250.

[0030] More preferably, the above chain (R f - add -II) In: - g1, g5, and g6 are numbers that are equal to or different from each other, independently greater than 0, and g1+g5+g6 is in the range of 2 to 300, preferably 10 to 250, and the different repeating units are statistically distributed along the chain. - g2, g3, and g4 are 0.

[0031] Preferably, the (per)fluoropolyether polymer [PFPE polymer add is (1) a PFPE chain add having a first chain end and a second chain end respectively bonded to both ends of the PFPE chain add , preferably a chain (R f - add -II) according to the formula (R f ) add comprising at least one polymer compound, - the first chain end contains a group of the formula -C(O)NR a R b (wherein R a and R b are each independently selected from hydrogen, a linear or branched C1-C6 alkyl group), - the second chain end is a C1-C6 perfluoroalkyl group, -CF2C(O)CF3, -C(OH)2CF3, -C(O)NR a R b (wherein R a and R b are each independently selected from hydrogen, a linear or branched C1-C6 alkyl group), -C(O)OR c (wherein R c is selected from a linear or branched C1-C6 alkyl group), a polymer compound containing a group selected from; (2) a branched PFPE polymer chain add having a first chain end and a second chain end respectively bonded to both ends of the PFPE chain add , preferably a chain (R f - add -II) according to the formula (R f ) add comprising at least one polymer compound, each chain end being a C1-C6 perfluoroalkyl group, -CF2C(O)CF3, -C(OH)2CF3, -C(O)NR a R b (wherein R a and R b are each independently selected from hydrogen, a linear or branched C1-C6 alkyl group), -C(O)OR c (wherein Rc A polymer compound comprising a group selected from linear or branched C1-C6 alkyl groups; It is a polymer compound mixture containing [the specified compound].

[0032] Preferably, the polymer compound having at least one chain end containing a -C(O)NH2 group is a PFPE polymer. add PFPE polymer in an amount ranging from 1 to 85% by weight, more preferably 5 to 60% by weight, and even more preferably 10 to 40% by weight, based on the weight of the mixture. add It is present in the mixture.

[0033] The PFPE polymer suitable as component A of the present invention can be prepared according to a synthesis scheme well known to those skilled in the art. For example, formula -C(O)NR a R b (In the formula, R a and R b Polymer compounds having the terminal group (which has the meaning shown above) are perfluoropolyether polymers having -CFX-COOR (wherein, for example, R is CH3 or C2H5, and X is a halogen atom such as F and Cl, or CF3), preferably in a solvent such as ethyl ether, methanol, or 1,1,2-trichlorotrifluoroethane, ammonia or amine NR a R b It can be prepared by processing and reacting it.

[0034] The PFPE polymer and PFPE polymer mixture described above, which are suitable as component A of the present invention, are also commercially available from Solvay Specialty Polymers Italy SpA.

[0035] As compound (B), the additive composition contains a fluorescent dye which is a xanthene dye of formula (I): [ka] (In the formula, - R1~R4 and R7 are each independently selected from H, C1~C3 alkyl, -CH2COOH, and -C2H4OH. - R5 and R6 are independently selected from H and C1-C3 alkyl groups. - X is halogen, HCO2 - , and ClO4 - (Selected from)

[0036] Preferably, in the above formula (I), R1 to R7 are each independently selected from H, methyl, and ethyl.

[0037] Preferably, the fluorescent dye is selected from rhodamine B (CAS number 81-88-9), rhodamine 6G (CAS number 989-38-8), rhodamine 123 (CAS number 62669-70-9), and rhodamine 110 (CAS number 13558-31-1). More preferably, the fluorescent dye is rhodamine B.

[0038] The fluorescent dye of formula (I) may be present in component (B) of the additive composition either alone or as a mixture of two or more compounds of formula (I).

[0039] Fluorescent dyes are ultraviolet (UV) fluorescent compounds that absorb light in the ultraviolet or near-ultraviolet region of the electromagnetic spectrum. Under irradiation with ultraviolet light (e.g., Wood's lamp) emitting wavelengths in the range of 10 nm to 750 nm, fluorescent dyes produce visually detectable fluorescence. For example, rhodamine B (dissolved in ethanol) is characterized by having an excitation peak at 510 nm and an emission peak at 565 nm.

[0040] Component (B) is present in the additive composition in an amount ranging from 0.01% to 25.0% by weight, where this weight percentage is relative to the weight of component (A). Preferably, the dye of formula (I) is present in an amount ranging from 0.01% to 25.0% by weight, preferably 0.01% to 15.0% by weight, more preferably 0.02% to 10.0% by weight, and even more preferably 0.02% to 5.0% by weight, based on the weight of component (A).

[0041] The fluorescent dyes of formula (I) are well known in the art. They can be prepared using known synthesis processes and are also commercially available.

[0042] If necessary, the additive composition according to the present invention may contain one or more additional components, such as those commonly used in lubricating oil compositions.

[0043] Non-limiting examples of suitable additives include antioxidants, heat stabilizers, pour point depressants, wear inhibitors, rheology modifiers, corrosion inhibitors, pigments, dyes, and fillers. These additional components should be selected so as not to interfere with the fluorescence of the additive composition, or the fluorescent dyes should be selected on the basis that no chemical or physical reactions occur between any of the components of the additive composition that could interfere with or inhibit the fluorescence response of the dye under ultraviolet irradiation.

[0044] The additive composition of the present invention can be prepared, for example, by mixing compounds (A) and (B) by stirring at room temperature using a conventional mixer such as a Silverson-type shear mixer.

[0045] To facilitate the dispersion of the fluorescent dye of component (B) in the PFPE polymer of component (A), compound (B) can be dissolved in a solvent such as ethanol, methanol, water, or other common solvents in an amount of, for example, 0.5 to 20% by weight based on the weight of the solvent, before mixing with component (A). The solvent used as a solubilizer can then be removed, for example, by stripping with an inert gas under reduced pressure and / or by distillation by heat (e.g., about 100°C).

[0046] When preparing the additive composition, optional components may be mixed with components (A) and (B), but optional components may also be added later to the additive composition formed by components (A) and (B). If necessary, optional components may be added when preparing the lubricating oil composition by adding the additive composition to the base oil or thereafter.

[0047] The additive composition is preferably added to the base oil in an amount ranging from 0.05% to 30.0% by weight, more preferably 0.1% to 15.0% by weight, and even more preferably 1% to 10.0% by weight, based on the weight of the base oil. Most preferably, the additive composition contains about 0.1% by weight of a fluorescent dye and is added to the base oil in an amount of about 5.0% by weight.

[0048] According to a second aspect, the present invention relates to a lubricating oil composition comprising a base oil and an additive composition described herein. The base oil is selected from hydrogenated oil or (fully) fluorinated oil.

[0049] The base oil may be a mixture of one or more hydrogenated oils or one or more (fully) fluorinated oils. When an oil mixture is used, the oils are selected so as to be mutually compatible and form a homogeneous mixture that is stable over time.

[0050] Preferably, the hydrogenated oil is selected from mineral oil or synthetic oil, and more preferably from polyalphaolefin (PAO), dibasic acid ester, polyol ester, phosphate ester, polyester, alkylated naphthalene, polyphenyl ether, polybutene, multiple alkylated cyclopentane, silane hydrocarbon, siloxane, and polyalkylene glycol. The above base oils may be used alone or in combination of two or more.

[0051] Preferably, the base oil is a (fully) fluorinated base oil.

[0052] More preferably, the (fully) fluorinated base oil is a (per)fluoropolyether base oil [PFPE base oil].

[0053] Preferably, the PFPE base oil is the following PFPE polymer oil (AI) and [PFPE copolymer] oil ](A-II): (AI)(per)fluoropolyether chain [PFPE chain] oilPFPE chain having two chain ends attached to both ends of ] oil (Per)fluoropolyether polymer [PFPE polymer] oil ] comprising a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms at both chain ends, the PFPE polymer oil but, 19 (Per)fluoropolyether polymers [PFPE polymers] having a number-average molecular weight of 500 to 100,000, preferably 2,000 to 50,000, as measured by F-NMR. oil ]; (A-II) First and second (per)fluoropolyether chains [PFPE chains] each having two chain ends. oil [PFPE copolymer] containing at least one block copolymer [PFPE copolymer] oil ] and the first and second PFPE chains oil The first chain end contains a perfluoroalkyl group, and the first and second PFPE chains oil The second end of the chain is - At least one first block [block(1)] that follows formula (I): [ka] (In the formula, n is an integer between 0 and 3; R1 to R4 are each independently a fluorine atom, a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, formula (II): (II) -(R 10 ) t [C(R 11 )(R 12 )-C(R 13 )(R 14 )(R 15 )] z (In the formula: R 10 is an oxygen atom, or a divalent / trivalent / tetravalent perfluoroalkyl chain containing 1 to 24 carbon atoms with at least one oxygen atom optionally interposed and / or containing at least one oxygen atom, t is either zero or 1, z is an integer between 1 and 3. R 11 ~R 15 Each of these is independently selected from the group comprising a fluorine atom and a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. The basis of, and formula (III): (III) -[(A^) a^ -(B^) v^ -(E^) L^ ] u^ -(C^)-T (In the formula, a^ is either 0 or 1, v^ is an integer from 0 to 3. L^ is an integer from 0 to 250. u^ is an integer from 0 to 50. A^ is a PFPE chain, B^ is the formula: -[C(R 1^ )(R 2^ )-C(R 3^ )(R 4^ )]- It is the basis of R 1^ ~R 4^ Each of these independently has the meaning defined above for each of R1 to R4. E^ is the formula -(CR 100^ R 101^ CR 102^ R 103^ )- is the basis of, During the ceremony, R 100^ and R 101^ Each of these is independently selected from a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, R 102^ and R 103^ This includes a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms and at least one heteroatom optionally selected from O, N, and S, -OR 200 Selected independently from, R 200This refers to a straight or branched perfluoro chain containing 1 to 6 carbon atoms or a compound of the formula -CF2OR 201 It is the basis of R 201 This is a perfluoroalkyl chain containing 1 to 6 carbon atoms, which may optionally have one or more oxygen ether atoms sandwiched between them, or R 100^ and R 101^ One of the two, and R 102^ and R 103^ One of them is a fluorine atom, R 100^ and R 101^ The other side and R 102^ and R 103^ The other side forms together a fully halogenated ring having 4 to 6 members, which may optionally contain heteroatoms such as oxygen atoms. C^ is a PFPE chain, T is a perfluoroalkyl group. A group containing the group, preferably selected from the group consisting of these groups), - At least one second block [block(2)] following equation (IV): (IV) -[(CR 1* R 2* CR 3* R 4* ) n* -(E) L ]- (In the formula, n* is an integer from 0 to 250. L is an integer from 0 to 250. The sum of n* and L is 0 or between 1 and 250. R 1* and R 2* This is independently selected from hydrogen atoms, halogen atoms, more preferably fluorine atoms or chlorine atoms, R 3* and R 4* -OR 200 Selected independently from, R 200This is a linear or branched perfluoro chain containing 1 to 6 carbon atoms, or a chain of the formula -CF2OR 201 It is the basis of R 201 This is a perfluoroalkyl chain containing 1 to 6 carbon atoms, which may optionally have one or more oxygen ether atoms sandwiched between them, or R 1* and R 2* One of the two, and R 3* and R 4* One of them is a fluorine atom, R 1* and R 2* The other side and R 3* and R 4* The other side forms together a fully halogenated ring having 4 to 6 members, which may optionally contain heteroatoms such as oxygen atoms. E has the same meaning as E^ shown above. - Optionally, at least one third block [block(3)] containing a PFPE chain; At least one block copolymer [PFPE copolymer] is bonded to each other via a mediated linkage. oil ]; Selected from, however, In the PFPE copolymer, - At least one of n, n*, and L is different from 0. - The aforementioned block (1), the aforementioned block (2), and the aforementioned block (3) if present are statistically distributed, In the above equation (I), - At least one of R1 to R4 is a base of equation (II), - Either R11 or R12 and one of R13 to R15 are the bases of equation (III); In equations (III) and (IV) above, - The repeating units are statistically distributed. In the above formula (III), - If a^ is 1, then at least one of v^ and L^ is different from 0. This is a condition.

[0054] Preferably, PFPE polymer oil and PFPE copolymer oil In both cases, the PFPE chain oil Each of these is a partially or completely fluorinated chain [chain(R)] which includes, preferably consists of, a repeating unit R°. f-oil )] and the repeating unit R° is, (i)-CFXO-(wherein X is F or CF3), (ii)-CFXCFXO-(wherein X is the same or different in each existence, and at least one of X is F or CF3, provided that -F), (iii)-CF2CF2CW2O-(wherein each W is either the same as or different from each other, and is F, Cl, or H), (iv)-CF2CF2CF2CF2O-, (v)-(CF2)w-CFZ-O-(where w is an integer from 0 to 3, and Z is the general formula -OR) (f-a) -Y is the basis, R (f-a) (I) is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, wherein the repeating units are selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O- (wherein each of X is independently F or CF3), and Y is a C1-C3 perfluoroalkyl group. It is selected independently of others.

[0055] Preferably, PFPE chain oil This is a partially or completely fluorinated chain [chain(R°] which includes, preferably consists of, a repeating unit R°. f )] and the repeating unit R° is, (i)-CFXO-(wherein X is F or CF3), (ii)-CFXCFXO-(wherein X is the same or different in each existence, and at least one of X is F or CF3) It is selected independently of others.

[0056] Preferably, the above psiPE chain oil Each of these is a PFPE polymer oil and PFPE copolymer oil In both cases, the following equation (R f - oil -I) and (R f - oil A chain (R) that follows one of the following (II) f-oil ) including: (R f - oil -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- (In the formula, - X 1 It is selected independently of -F and -CF3, - X 2 , X 3 Independently, -F, -CF3, provided that they are the same or different from each other and in each existence, and at least one of X is -F; - If g1, g2, g3, and g4 are equal to or different from each other, and each independently has a value of ≥ 0 such that g1+g2+g3+g4 is in the range of 2 to 300, preferably 10 to 250, and more preferably 15 to 200, and at least two of g1, g2, g3, and g4 are different from zero, then the different repeating units are generally statistically distributed along the chain. (R f - oil -II) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 -(CF(CF3)O) g5 (CF2CF(CF3)O) g6 ]- (In the formula, - X 1 It is selected independently of -F and -CF3, - X 2 , X 3 Independently, -F, -CF3, provided that they are the same or different from each other and in each existence, and at least one of X is -F; - g1, g2, g3, g4, g5, and g6 are either equal to or different from each other, and independently g1+g2+g3+g4+g5+g6 is ≥ 0 such that g1+g2+g3+g4+g5+g6 is in the range of 2 to 300, preferably 10 to 250.

[0057] In a preferred embodiment, the chain (R f - oil ) is the above equation (R f - oil Follow -I).

[0058] Preferably, the PFPE base oil is a PFPE polymer oil It is (AI).

[0059] Preferably, the hydroxyPE polymer oil (Al) has a viscosity at 25°C of 10 to 3000 cSt, more preferably 15 to 2000 cSt, and even more preferably 100 to 500 cSt.

[0060] Preferably, the PFPE chain in the PFPE base oil oil This is the above formula (R f - oil- Chain R according to II) f-oil Includes.

[0061] Preferably, the chain (R f - oil- II) In X 1 is -F.

[0062] Preferably, the chain (R f - oil- II) In X 2 and X 3Both are F.

[0063] Preferably, the chain (R f - oil- II) In this case, g1 and g2 are either the same or different, and both are greater than 0.

[0064] Preferably, the chain (R f - oil- In (II), both g3 and g4 are 0.

[0065] Preferably, the chain (R f - oil- II) In this case, g1+g2 is in the range of 20 to 200.

[0066] Preferably, the PFPE base oil is a PFPE copolymer. oil (A-II)

[0067] Preferably, PFPE copolymer oil (A-II) is, 19 It has a number-average molecular weight of 500 to 100,000, preferably 2,000 to 50,000, as measured by F-NMR.

[0068] The first chain end of the first and second PFPE chains is a PFPE copolymer. oil It will be understood by those skilled in the art that this corresponds to the two ends of the chain.

[0069] Preferably, the first and second PFPE chains oil The first chain end of the above-mentioned molecule contains a linear perfluoroalkyl group having 1 to 3 carbon atoms.

[0070] Preferably, the linear perfluoroalkyl group is the same at both the first and second chain ends.

[0071] Preferably, the first and second PFPE chains oilThe first chain end and the T in formula (III) are either the same as or different from each other, and are perfluoroalkyl groups having 1 to 3 carbon atoms.

[0072] For example, T and T' are the same or different from each other and are fluorine atoms or groups selected from CF3, -CF2CF3, -CF2CF2CF3, and -CF(CF3)2. Other halogenated groups, such as -CF2Cl and -CF2CF2Cl, may also be present.

[0073] Preferably, the first and second PFPE chains oil Therefore, A^ and C^ are either the same or different.

[0074] Preferably, PFPE copolymer oil Now, the first PFPE chain oil It is bonded to block (1) via a sigma bond or a group selected from -CF2-, -CF2CF2-, or -O- -(C)-.

[0075] Preferably, in the PFPE copolymer, the block (2) is connected to the second PFPE chain via a sigma bond or a group selected from -CF2-, -CF2CF2-, or -O- -(C)- oil It is connected to

[0076] Preferably, if both block (1) and block (2) are present, they are connected via a sigma coupling.

[0077] Preferably, PFPE copolymer oil Therefore, the sum of (n+n*+v^) is between 1 and 15, preferably between 1 and 11, and more preferably between 1 and 9.

[0078] Preferably, PFPE copolymer oil Therefore, the sum of (L + L^) is between 1 and 500, preferably between 2 and 500, and more preferably between 2 and 300.

[0079] According to a preferred embodiment, PFPE copolymer oil These are the first and second PFPE chains, each having two chain ends. oil Including the first and second PFPE chains oil The first chain end comprises a perfluoroalkyl group, preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, and the second chain end of the first and second PFPE chains is - At least one block (2) that follows equation (IV): (IV) -[(CR 1 *R 2 *C R 3*R 4 *) n *-(E) L ]- (In the formula, n* is an integer between 1 and 250. L is an integer between 1 and 250, and the sum of n* and L is between 1 and 250. R 1 * and R 2 * represents a fluorine atom, R 3 * and R 4 * is a halogen atom, more preferably a fluorine or chlorine atom; a linear or branched alkyl chain containing 1 to 6 carbon atoms and at least one heteroatom optionally selected from O, N, and S; -OR 200 Selected independently from, R 200 This refers to a straight or branched perfluoro chain containing 1 to 6 carbon atoms or a compound of the formula -CF2OR 201 It is the basis of R 201 This is a perfluoroalkyl chain containing 1 to 6 carbon atoms, which may optionally have one or more oxygen ether atoms sandwiched between them. E is the base of the equation -(CR100^R101^CR102^R103^)-, (In the formula, R 100^ and R 101^ This is independently selected from halogen atoms, preferably fluorine or chlorine atoms. R 102^ and R 103^ is a halogen atom, preferably a fluorine or chlorine atom, -OR200 Selected independently from, R 200 This refers to a straight or branched perfluoro chain containing 1 to 6 carbon atoms or a compound of the formula -CF2OR 201 It is the basis of R 201 This is a perfluoroalkyl chain containing 1 to 6 carbon atoms, which may optionally have one or more oxygen ether atoms sandwiched between them. and, - At least one block (3) containing an optional PFPE chain They are connected to each other via [a certain mechanism].

[0080] Preferably, the PFPE copolymer oil This is measured at 25℃ and is 1,000mm 2 / s or more, more preferably 2,000mm 2 / s or more, more preferably 3,000 mm 2 It has a viscosity greater than / s.

[0081] Preferably, the PFPE copolymer oil This is 5,000,000 mm measured at 25°C. 2 Less than / s, more preferably 2,500,000 mm 2 Less than / s, more preferably 2,000,000 mm 2 It has a viscosity of less than / s.

[0082] Preferably, the PFPE copolymer oil This refers to a measurement of 3,000 to 1,500,000 mm² / s, more preferably 3,500 to 1,000,000 mm² / s, at 25°C. 2 / s, more preferably 4,000 to 950,000 mm 2 It has a viscosity of / s.

[0083] In this specification, the viscosity of PFPE polymers and copolymers is intended to be measured at 1 rad / s and 25°C using an Anton Paar MCR 502 parallel-plate rheometer equipped with 25 mm parallel plates.

[0084] PFPE copolymeroil This can be prepared by known methods, such as those disclosed in (Patent Document 3) (SOLVAY SOLEXIS SPA), or by supercritical fluid fractionation.

[0085] Comfortable, PFPE copolymer oil teeth, (a) - At least one (per)fluoropolyether polymer [PFPE peroxy] containing a peroxide group; In the presence of ultraviolet light or while heating, - At least one perfluoro compound of formula (Xp): [ka] (In the formula, R 21 ~R 23 and R 31 ~R 33 Each of them is independently a perfluoroalkyl group having a fluorine atom and 1 to 3 carbon atoms. R 10 This is a perfluoroalkyl chain containing 2 to 18 carbon atoms, which is an oxygen atom, or optionally and preferably contains at least one oxygen atom sandwiched between them. t is 0 or 1, preferably 1. z* and z** are independently either 1 or 2. and / or - At least one compound [compound (O)], (i) Hydrogenated or (completely) halogenated olefins containing 2 to 8 carbon atoms, preferably ethylene (E), propylene (PP), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), and 1,1-difluoroethylene (VDF), (ii) CF2 = CFOR f (In the formula, R fThis is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7 (hereinafter also called "PAVE"), containing a catenary oxygen atom C1-C 12 [(per)fluoro]-oxyalkyl, preferably a perfluoro-2-propoxypropyl group (hereinafter also called "perfluorooxy-alkyl-vinyl ether"), group -CF2OR f2 (Hereafter also referred to as "perfluoro-methoxy-vinyl ether" or "MOVE"), R f2 The is selected from the group consisting of C1-C6 perfluoroalkyl, C5-C6 cyclic perfluoroalkyl, and C2-C6 perfluorooxyalkyl, which contain at least one catenary oxygen atom, and preferably R f2 (This is -CF2CF3(MOVE1), -CF2CF2OCF3(MOVE2), or -CF3(MOVE3)), (iii) The following formula: [ka] (In the formula, R f3 , R f4 , R f5 , R f6 Each of them is either the same as or different from one another, and is independently selected from the group consisting of C1-C6 perfluoroalkyl groups containing a fluorine atom and optionally one or more oxygen atoms, for example, in particular -CF3, -C2F5, -C3F7, -OCF3, and -OCF2CF2OCF3. Perfluorodioxole having A group including, preferably consisting of, at least one compound [compound (O)] selected from this group. To bring into contact with It can be prepared by a method including [Method (P)], The amount of compound (Xp) is limited to less than 5% by weight of the amount of PFPE peroxy.

[0086] A fluorination step may be optionally performed.

[0087] PFPE polymer oil These can be prepared by methods well known to those skilled in the art. They are also commercially available from Solvay Specialty Polymers Italy SpA under trade names such as Fomblin® Y, Fomblin® M, and Fomblin® Z.

[0088] The lubricating oil composition may be in the form of a lubricating oil or a lubricating grease. If the lubricating oil composition is in the form of a grease, it contains at least one thickening agent (i.e., a viscosity enhancer).

[0089] Preferably, the thickener has an average particle size (d) in the range of 1 to 15 micrometers, more preferably 2 to 12 micrometers, and even more preferably 3 to 10 micrometers, when measured as a volume particle size distribution by laser diffraction particle size analysis. 50 It is in the form of a powder having ).

[0090] According to one embodiment, the thickening agent is selected from soap-based thickening agents.

[0091] Examples of soap-based thickeners include simple soaps, which are organic salts of long-chain organic acids and alkali metals (such as lithium, calcium, sodium, aluminum, and barium), and complex soaps containing simple soaps and complexing agents. Suitable examples include lithium 12-hydroxystearate, lithium complexes, calcium complexes, and aluminum complexes.

[0092] According to one embodiment, the thickening agent is selected from non-soap-based thickening agents.

[0093] Examples of non-soap-based thickeners include polyurea, clay, fumed silica, fluorinated polymers, and / or aromatic polymers.

[0094] Preferably, the thickener is a fluorinated polymer.

[0095] According to this embodiment, the fluorinated polymer is poly(tetrafluoroethylene) (PTFE).

[0096] Preferably, the thickening agent is an aromatic polymer.

[0097] According to this embodiment, the aromatic polymer has a melting point of at least 150°C.

[0098] Preferably, the aromatic polymer has a volume particle size distribution in the range of 1 to 15 micrometers, which is measured by laser diffraction particle size analysis. 50 , and 0.5m 2 / g to 5m 2 It is a powder form with a surface area in the range of less than / g (determined by gas adsorption using the BET method in accordance with ISO 9277).

[0099] The at least one aromatic polymer is advantageously, (a) Poly(arylene sulfide) (PAS) polymer; (b) Poly(phenylene oxide) (PPO) polymer; (c) Poly(aryl ether ketone) (PAEK) polymer; and (d) Poly(aryl ether sulfone) (PAES) polymer Selected from the group including, preferably consisting of, the same.

[0100] Preferably, the at least one aromatic polymer is a PAS polymer such as those described in (Patent Document 4), (Patent Document 5), and (Patent Document 6).

[0101] Preferably, the total amount of thickener in the grease composition is in the range of 0.1 to 50.0% by weight, more preferably 1.0 to 35% by weight, based on the weight of the grease composition.

[0102] The additive composition of the present invention is stable; that is, it has a long shelf life over a wide range of temperatures without any apparent separation of its components.

[0103] The additive composition of the present invention can be used to impart both rust-preventive and fluorescent properties to a base oil. The rust-preventive effect can be determined by performing a test in accordance with ASTM D665 described in the following examples on a lubricating oil containing the additive composition.

[0104] The fluorescence properties of lubricating oil can be used to detect leaks of lubricating oil from equipment containing lubricating oil, such as hydraulic equipment, refrigeration equipment, and containers. In fact, when lubricating oil containing the additive composition of the present invention leaks, the leak location can be detected by irradiating the outer surface of the equipment with an ultraviolet light source that emits radiation capable of exciting the fluorescence of the fluorescent dye in the additive composition. For example, a light source having a wavelength in the range of 10 nm to 750 nm, preferably 400 nm to about 600 nm, can be used. The leak location can be detected by observing the fluorescence emission of the leaked lubricating oil on the outer surface.

[0105] Similarly, the fluorescence properties of lubricating oil compositions, particularly grease-type lubricating oil compositions, can be used to determine their presence or uniform application on the surface of a substrate, such as bearings, pins, shafts, and gears, allowing the end user to confirm the overall lubrication status of the surface or to know when replusion is needed.

[0106] The present invention will be described in more detail below with reference to examples, but the purpose of this description is merely explanatory and does not limit the scope of the invention.

[0107] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with any description in this application to such an extent that it obscures certain terms, the description herein shall prevail. [Examples]

[0108] Determination of rust prevention properties The rust-preventive properties of the lubricating oil composition were determined according to the tests described in ASTM D665. The test results are expressed as "pass" or "fail".

[0109] Determination of fluorescence properties The fluorescence properties of the additive composition and lubricating oil composition were evaluated visually by placing a drop of the additive composition onto a paper sheet and then irradiating it with ultraviolet light using a Wood's lamp. If the droplet became brighter, the additive composition was considered to be fluorescent.

[0110] The results of the fluorescence test are expressed as either "present" (i.e., fluorescence was observed) or "absent" (i.e., fluorescence was not observed).

[0111] Materials used - Rhodamine B (Sigma Aldrich); - Fluorescein sodium salt (Sigma Aldrich); - 2,5-Bis(5-tert-butylbenzoxazole-2-yl)thiophene (BBOT-Sigma Aldrich) - Polymer 1: PFPE mixture of the following formula TO(CF2CF(CF3)O) n (CF2O) m (CF(CF3)O) r CF2-T' (In the formula, T is a group selected from -C(O)NH2, CF3, -CF2C(O)CF3, -C(OH)2CF3, and -C(O)OCH3; T' is a group selected from -C(O)NH2, -F, CF3, -CF2C(O)CF3, -C(OH)2CF3, and -C(O)OCH3; the ratio n / (m+r) is approximately 15; the number average molecular weight is approximately 2600; and the total amount of polymer compounds having at least one -C(O)NH2 group is approximately 30% by weight of the PFPE mixture. - Polymer 2: PFPE mixture of the following formula TO(CF2CF(CF3)O) n (CF2O) m (CF(CF3)O) r CF2-T' (wherein T is a group selected from CF3, -CF2C(O)CF3, -C(OH)2CF3, -C(O)OCH3; T' is a group selected from -C(O)OH, -F, CF3, -CF2C(O)CF3, -C(OH)2CF3, -C(O)OCH3; the ratio n / (m + r) is about 15; the number average molecular weight is about 2600; the total amount of the polymer compound having at least one -C(O)OH group is about 30% by weight of the weight of the PFPE mixture); - Base oil Fomblin® L-VAC Y25 / 6 (Solvay Specialty Polymers) according to the following formula: CF3O(CF(CF3)CF2O) m (CF2O) n CF3 (wherein m / n = 40 / 1, the number average molecular weight (Mn) is 2400, and the kinematic viscosity at 20 °C is 250 cSt (measured in accordance with ASTM D445).

[0112] Preparation of the additive composition The additive composition AC1 according to the present invention was prepared by stirring a mixture of 500 g of Polymer 1 (Component (A)) and 0.5 g of rhodamine B (CAS No. 81 - 88 - 9) as a fluorescent dye (Component (B)) at ambient temperature (about 25 °C) using a Silverson type shear mixer. The additive composition AC1 contains 0.1% by weight of the fluorescent additive of Component (B) based on the weight of Component (A).

[0113] For comparison purposes, three additive compositions (AC2* to AC5*) were prepared according to the same procedure, using Polymer 2 instead of Polymer 1 and / or a fluorescent dye selected from fluorescein and BBOT instead of rhodamine B.

[0114] The comparative additive composition AC�* substantially corresponds to the composition disclosed in (Patent Document 2) and contains a PFPE polymer (A) having an acidic chain end and a compound BBOT (2,5 - bis(5 - tert - butylbenzoxazol - 2 - yl)thiophene) as a fluorescent dye (B).

[0115] Preparation of Lubricating Oil Composition The lubricating oil composition according to the present invention was prepared by mixing the additive composition AC1 prepared above with a base oil at a concentration of 5% by weight of AC1 with respect to the weight of the base oil while stirring at ambient temperature.

[0116] For comparison purposes, in accordance with the same procedure, the comparative lubricating oil compositions were prepared using the above additive compositions AC2* to AC5* instead of AC1 and the same base oil.

[0117] The compositions of the materials tested and the results of their property evaluations are reported in Table 1.

[0118] [Table 1]

[0119] The results in Table 1 show that the additive composition of the present invention imparts both rust prevention properties and fluorescence properties to the base oil. Replacing the fluorescent dye of formula (I) with a prior art fluorescent dye and / or a PFPE polymer will result in the lubricating oil showing neither or only one of these two properties.

Claims

1. An additive composition, (A) (Per)fluoropolyether chain [PFPE chain] ａｄｄ The PFPE chain having a first chain end and a second chain end attached to both ends of the ] ａｄｄ At least one (per)fluoropolyether polymer [PFPE polymer] containing ａｄｄ ] and: The first chain end is of the formula -C(O)NR ａ R ｂ (wherein R ａ and R ｂ are each independently hydrogen, a linear or branched C １ to C ６ alkyl group). The second chain end is C １ ~C ６ (Per)fluoroalkyl group, -CF ２ C(O)CF ３ , and -C(OH) ２ CF ３ ;-C(O)NR ａ R ｂ (In the formula, R ａ and R ｂ These are, independently, hydrogen, linear or branched carbon atoms. １ ~C ６ (Selected from alkyl groups); -C(O)OR ｃ (In the formula, R ｃ C is a linear or branched C １ ~C ６ A group selected from (which is an alkyl group), At least one (per)fluoropolyether polymer [PFPE polymer] ａｄｄ ]and; (B) 0.01 to 25.0% by weight of component (A), the fluorescent dye of formula (I): 【Chemistry 1】 (In the formula, - R1 to R4 and R7 are each independently H, C １ ~C ３ Alkyl, -CH ２ COOH, -C ２ H ４ Selected from OH, - R5 and R6 are H and C, respectively, independently. １ ~C ３ Selected from alkyl groups, - X is halogen, HCO ２ － , and ClO ４ － (The anion selected from) and; An additive composition containing the following:

2. The (per)fluoropolyether chain [PFPE chain] ａｄｄ ] is a partially or completely fluorinated chain [chain (R) which includes a repeating unit R°, preferably consisting of a repeating unit R° ｆ ) ａｄｄ ] and the repeating unit R° is, (i) -CFXO-(wherein X is F or CF) ３ (It is) (ii) -CFXCFXO-(wherein X is the same or different in each existence, and at least one of X is -CF ３ F or CF under the condition that ３ (It is) (iii)-CF ２ CF ２ CW ２ O - (wherein each W is either the same as or different from each other, and is F, Cl, or H), (iv)-CF ２ CF ２ CF ２ CF ２ O-、 (v) - (CF ２ ) ｗ -CFZ-O-(wherein w is an integer from 0 to 3, and Z is the general formula -O-R) （ｆ－ａ） - It is the basis of Y, R （ｆ－ａ） This is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, wherein the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O - (wherein each of X is independently F or CF) ３ Y is selected from among the following, and C １ ~C ３ (It is a perfluoroalkyl group.) An additive composition according to claim 1, independently selected from the above.

3. The chain (R ｆ ) is given by the following equation (R ｆ - ａｄｄ -I) The additive composition according to claim 1 or 2: (R ｆ - ａｄｄ -I) -[(CFX １ O) ｇ１ (CFX ２ CFX ３ O) ｇ２ (CF ２ CF ２ CF ２ O) ｇ３ (CF ２ CF ２ CF ２ CF ２ O) ｇ４ ]- (In the formula, - X １ -F and -CF ３ Selected independently from, -X ２ , X ３ are the same or different from each other and in each instance, provided that at least one of X ２ and X ３ is -F, independently, -F, -CF ３ ; - g1, g2, g3, and g4 are equal to or different from each other, and each independently has a value ≥ 0 such that g1 + g2 + g3 + g4 is in the range of 2 to 300, preferably 10 to 250, and more preferably 15 to 200, and if at least two of g1, g2, g3, and g4 are different from zero, then different repeating units are statistically distributed along the chain.

4. The chain (R ｆ ) is given by the following equation (R ｆ - ａｄｄ -II) Additive composition according to any one of claims 1 to 3: () ｆ  ａｄｄ .)) -[(CFX １ O) ｇ１ (CFX ２ CFX ３ O) ｇ２ (CF ２ CF ２ CF ２ O) ｇ３ (CF ２ CF ２ CF ２ CF ２ O) ｇ４ -(CF(CF ３ )O) ｇ５ (CF ２ CF(CF ３ )O) ｇ６ ]- (In the formula, - X １ -F and -CF ３ Selected independently from, - X ２ , X ３ They are the same or different from each other and in each existence, X ２ and X ３ Provided that at least one of them is -F, independently, -F or -CF ３ And, - g1, g2, g3, g4, g5, and g6 are either equal to or different from each other, and independently g1 + g2 + g3 + g4 + g5 + g6 is ≥ 0 such that g1 + g2 + g3 + g4 + g5 + g6 is in the range of 2 to 300, preferably 10 to 250).

5. Formula (R ｆ - ａｄｄ -II) In, - g1, g5, and g6 are numbers that are equal to or different from each other, independently greater than 0, and g1 + g5 + g6 is in the range of 2 to 300, preferably 10 to 250, and different repeating units are statistically distributed along the chain. - g2, g3, and g4 are 0. The additive composition according to claim 4.

6. The PFPE polymer ａｄｄ but, (1) PFPE chain ａｄｄ A PFPE chain having a first chain end and a second chain end attached to both ends. ａｄｄ Preferably the above formula (R ｆ ) ａｄｄ -II) Chain (R ｆ ) ａｄｄ A polymer compound comprising at least one such compound, - The first chain end is of formula -C(O)N ａ R ｂ (In the formula, ａ and R ｂ These are, independently, hydrogen, linear or branched carbon atoms. １ ~C ６ Includes a group (selected from alkyl groups), - The second chain end is C １ ~C ６ Perfluoroalkyl groups, -CF ２ C(O)CF ３ -C(OH) ２ CF ３ , -C(O)NR ａ R ｂ (In the formula, R ａ and R ｂ These are, independently, hydrogen, linear or branched carbon atoms. １ -C ６ Selected from alkyl groups), -C(O)OR ｃ (In the formula, R ｃ C is a linear or branched C １ ~C ６ A polymer compound comprising a group selected from alkyl groups; (2) The branched PFPE polymer chain ａｄｄ A PFPE chain having a first chain end and a second chain end attached to both ends. ａｄｄ Preferably the above formula (R ｆ - ａｄｄ -II) Chain (R ｆ ) ａｄｄ A polymer compound comprising at least one polymer compound, wherein each chain end is C １ ~C ６ Perfluoroalkyl groups, -CF ２ C(O)CF ３ -C(OH) ２ CF ３ , -C(O)NR ａ R ｂ (In the formula, R ａ and R ｂ These are, independently, hydrogen, linear or branched carbon atoms. １ ~C ６ Selected from alkyl groups), -C(O)OR ｃ (In the formula, R ｃ C is a linear or branched C １ ~C ６ A polymer compound comprising a group selected from alkyl groups; The additive composition according to any one of claims 1 to 5, which is a mixture of polymer compounds containing

7. The additive composition according to any one of claims 1 to 6, wherein the dye of formula (I) is selected from rhodamine B, rhodamine 6G, rhodamine 123, and rhodamine 110, and preferably the dye of formula (I) is rhodamine B.

8. The additive composition according to any one of claims 1 to 7, wherein the amount of the dye of formula (I) is in the range of 0.01 to 25.0% by weight, preferably 0.01 to 15.0% by weight, more preferably 0.02 to 10.0% by weight, and even more preferably 0.02 to 5.0% by weight, based on the weight of component (A).

9. A lubricating oil composition comprising a base oil and an additive composition according to any one of claims 1 to 8, wherein the base oil is selected from a hydrogenated oil or a (fully) fluorinated oil.

10. The (fully) fluorinated base oil comprises (per)fluoropolyether polymer (A-I) and (per)fluoropolyether block copolymer (A-II): (A-I)(per)fluoropolyether chain [PFPE chain] ｏｉｌ The PFPE chain having two chain ends attached to both ends of ] ｏｉｌ (Per)fluoropolyether polymer [PFPE polymer] ｏｉｌ ] comprising a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms at both chain ends, the PFPE polymer ｏｉｌ but, １９ (Per)fluoropolyether polymer [PFPE polymer] having a number average molecular weight of 500 to 100,000, preferably 2,000 to 50,000, as measured by F-NMR. ｏｉｌ ]; (A-II) First and second (per)fluoropolyether chains having two chain ends each [PFPE chain] ｏｉｌ ] containing at least one block copolymer [PFPE copolymer ｏｉｌ ] and the first and second PFPE ｏｉｌ The first chain end of the chain contains a perfluoroalkyl group, and the first and second PFPE chains ｏｉｌ The second end of the chain is - At least one first block [block (1)] according to formula (I): 【Chemistry 2】 (In the formula, n is 0, or an integer from 1 to 3; R １ ~R ４ Each of these independently comprises a fluorine atom, a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, formula (II): (().) .(() １０ ) ｔ [() １１ () １２ )?|() １３ () １４ () １５ ) ｚ (In the formula: R １０ is an oxygen atom, or a divalent / trivalent / tetravalent perfluoroalkyl chain containing 1 to 24 carbon atoms, with at least one oxygen atom optionally interposed and / or containing at least one oxygen atom. t is either zero or 1. z is an integer between 1 and 3. R １１ ~R １５ Each of these is independently selected from the group comprising a fluorine atom and a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. The basis of, and formula (III): -[(A^) ａ＾ -(B^) ｖ＾ -(E^) Ｌ＾ ] ｕ＾ -(C^)-T (III) (In the formula, a^ is either 0 or 1, v^ is an integer from 0 to 3. L^ is an integer from 0 to 250, u^ is an integer from 0 to 50, A^ is a PFPE chain, B^ is expressed by: -[C(R １＾ )(R ２＾ )-C(R ３＾ )(R ４＾ )]- It is the basis of R １＾ ~R ４＾ Each of them is independent of R １ ~R ４ Each of these has the meaning defined above, E^ is the formula - (CR １００＾ R １０１＾ CR １０２＾ R １０３＾ ) - is the basis of, During the ceremony, R １００＾ and R １０１＾ Each of these is independently selected from a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, R １０２＾ and R １０３＾ This includes a linear or branched alkyl chain containing a hydrogen atom, a halogen atom, more preferably a fluorine or chlorine atom, and at least one heteroatom optionally selected from O, N, and S, comprising 1 to 6 carbon atoms, -OR ２００ Selected independently from, R ２００ This refers to a straight or branched perfluoro chain containing 1 to 6 carbon atoms or the formula -CF ２ OR ２０１ It is the basis of R ２０１ This is a perfluoroalkyl chain containing 1 to 6 carbon atoms, which may optionally have one or more oxygen ether atoms sandwiched between them, or R １００＾ and R １０１＾ One of the two, and R １０２＾ and R １０３＾ One of them is a fluorine atom, R １００＾ and R １０１＾ The other side and R １０２＾ and R １０３＾ The other side forms together a fully halogenated ring having 4 to 6 members, which may optionally contain heteroatoms such as oxygen atoms. C^ is a PFPE chain, T is a perfluoroalkyl group. A group containing the group, preferably selected from the group consisting of these groups), - At least one second block [block (2)] following formula (IV): -[(CR １＊ R ２＊ CR ３＊ R ４＊ ) ｎ＊ -(E) Ｌ ]- (IV) (In the formula, n* is an integer from 0 to 250. L is an integer from 0 to 250. The sum of n* and L is 0 or between 1 and 250; R １＊ and R ２＊ This is independently selected from hydrogen atoms, halogen atoms, more preferably fluorine atoms or chlorine atoms, R ３＊ and R ４＊ is a hydrogen atom, a halogen atom, more preferably a fluorine atom or a chlorine atom; a linear or branched alkyl chain containing 1 to 6 carbon atoms, optionally containing at least one heteroatom selected from O, N, and S; -OR ２００ Selected independently from, R ２００ is a linear or branched perfluoro chain containing 1 to 6 carbon atoms, or formula -CF ２ OR ２０１ It is the basis of R ２０１ This is a perfluoroalkyl chain containing 1 to 6 carbon atoms, which may optionally have one or more oxygen ether atoms sandwiched between them, or R １＊ and R ２＊ One of the two, and R ３＊ and R ４＊ One of them is a fluorine atom, R １＊ and R ２＊ The other side and R ３＊ and R ４＊ The other side forms together a fully halogenated ring having 4 to 6 members, which may optionally contain heteroatoms such as oxygen atoms. E has the same meaning as E^ shown above; - Optionally, at least one third block [block (3)] containing a PFPE chain; At least one block copolymer [PFPE copolymer oil] bonded to each other via a veto; Includes at least one of the following: however, In the PFPE copolymer, - At least one of n, n*, and L is different from 0, - The aforementioned block (1), the aforementioned block (2), and the aforementioned block (3) if present are statistically distributed, In the above formula (I), - At least one of R1 to R4 is a base of equation (II), - Either R11 or R12 and one of R13 to R15 are the bases of formula (III); In formulas (III) and (IV) above, - The repeating units are statistically distributed. In the above formula (III), - If a^ is 1, then at least one of v^ and L^ is different from 0. The lubricating oil composition according to claim 9, provided that the following conditions are met.

11. PFPE chains in the PFPE polymer and PFPE copolymer ｏｉｌ Each of these is a partially or completely fluorinated chain [chain (R)] which contains a repeating unit R°, preferably consisting of a repeating unit R°. ｆ－ｏｉｌ )] and the repeating unit R° is, (i) -CFXO-(wherein X is F or CF) ３ (It is) (ii) -CFXCFXO- (wherein X is the same or different in each existence, and F or CF is provided that at least one of X is -F) ３ (It is) (iii)-CF ２ CF ２ CW ２ O - (wherein each W is either the same as or different from each other, and is F, Cl, or H), (iv)-CF ２ CF ２ CF ２ CF ２ O-、 (v) - (CF ２ ) ｗ -CFZ-O-(wherein w is an integer from 0 to 3, and Z is the general formula -O-R) （ｆ－ａ） - It is the basis of Y, R （ｆ－ａ） This is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, wherein the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ O (wherein each of X is independently F or CF) ３ Y is selected from among the following, and C １ ~C ３ (It is a perfluoroalkyl group.) An additive composition according to claim 9 or 10, independently selected from the above.

12. The PFPE chain ｏｉｌ However, a partially or completely fluorinated chain [chain (R°] which includes, preferably consists of, a repeating unit R°. ｆ ] and the repeating unit R° is, (i) -CFXO-(wherein X is F or CF) ３ (It is) (ii) -CFXCFXO-(wherein X is the same or different in each existence, and at least one of X is -CF ３ F or CF under the condition that ３ (It is) The additive composition according to claim 11, which is independently selected from the above.

13. A lubricating oil composition according to any one of claims 9 to 12, which is a lubricating oil or lubricating grease.

14. A method for detecting leakage of a lubricating oil composition from a device, - To prepare an apparatus containing the lubricating oil composition described in any one of claims 9 to 13; - Irradiating the outer surface of the apparatus with ultraviolet light to excite the fluorescence of the dye of formula (I) in the lubricating oil composition; - Determining the leakage of the lubricating oil composition based on the fluorescence response from the leaked lubricating oil composition on the outer surface; Methods that include...

15. A method for detecting the presence or uniform application of a lubricating oil coating on a substrate, - To obtain a coated surface by coating the surface of a substrate with the lubricating oil composition described in any one of claims 9 to 13; - Irradiating the coated surface with ultraviolet light to excite the fluorescence of the dye of formula (I) present in the lubricating oil composition; - Determining the presence or uniform application of the lubricating oil coating on the surface based on the fluorescence response from the coated surface; A method that includes this.

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