JP2010132792A - Antifoaming agent composition, lubricant composition and method for producing lubricant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lubricant composition that has high dispersibility in a base oil, exhibits excellent initial anti-foaming performance and excellent durability thereof and maintains initial anti-foaming performance even in storage in the case of using a fluorinated silicone antifoaming agent and a method for producing the lubricant composition. <P>SOLUTION: The lubricant composition comprises a lubricant base oil, and (A) a fluorine-containing-based organic compound, (B) a fluorinated silicone and (C) an organic solvent that are mixed in the lubricant base oil. The antifoaming agent composition comprises (A) the fluorine-containing-based organic compound, (B) the fluorinated silicone and (C) the organic solvent, used as the components of the lubricant composition. The method for producing the lubricant composition comprises a step of preparing the antifoaming agent composition and a step of mixing the antifoaming agent composition with a base oil. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

    The present invention relates to an antifoaming agent composition, a lubricating oil composition, and a method for producing the lubricating oil composition, and more specifically, obtained by using an antifoaming agent composition and the antifoaming agent composition. Performance that is excellent in initial defoaming performance and its durability and that can maintain the initial defoaming performance for a long time even after storage (hereinafter referred to as “stability” or “storage stability”). And a method for producing the same.

The present invention also provides a method for improving the initial defoaming performance and durability and storage stability of a lubricating oil composition.

  For lubrication oil used for lubrication of sliding parts of various mechanical devices and drive system fluid used in drive system devices, the occurrence of bubbles causes the occurrence of oil jets, oil film breaks or oil breakage of mechanical devices. A number of adverse effects such as malfunction, lubrication oil overflow, and oxidative deterioration of the lubrication oil occur, and there has been a need for a technique for preventing such problems. Various antifoaming agents blended in lubricating oils have been developed as one of the prevention techniques, and among various antifoaming agents, silicone is generally blended as an antifoaming agent. However, such silicone has a drawback that its defoaming performance life is short.

    The fact that the initial defoaming performance cannot be maintained for a long period of time can be a serious obstacle for mechanical devices that require long-term continuous operation, and long-life antifoaming agents have been demanded.

  Under such circumstances, as an antifoaming agent having a long life, for example, an antifoaming agent for organic solvents containing a perfluoroalkyl group-containing organosiloxane as an active ingredient has been proposed (Japanese Patent Publication No. 1992-50045 (hereinafter referred to as “JP”). Patent Literature 1 ”)). According to Patent Document 1, it is described that such an antifoaming agent exhibits an excellent defoaming effect on bubbles of an organic solvent solution in which a hydrocarbon or a fluorosurfactant is dissolved. However, Patent Document 1 does not disclose a hydrocarbon oil that exhibits low solubility in an antifoaming agent such as a lubricating oil as an organic solvent. No antifoaming effect is disclosed.

Further, as a lubricating oil composition capable of maintaining excellent defoaming properties from low temperature to high temperature, (a) a polydimethylsiloxane having a kinematic viscosity at 25 ° C. of 300,000 to 1,500,000 mm ² / s and (B) A lubricating oil composition containing a fluorinated polysiloxane having a kinematic viscosity at 25 ° C. of 500 to 9000 mm ² / s has been proposed (JP 2000-87065 A (hereinafter referred to as “Patent Document 2”)). ).

Furthermore, when a highly soluble base oil is used, the lubricating oil composition that provides stable defoaming performance even at high temperatures is a hydrocarbon-based synthetic oil having a viscosity specific gravity constant (VGC) of 0.85 or more. A lubricating oil composition in which 5 to 30 ppm of a polyfluoroalkylsiloxane having a density at 15 ° C. of 1.15 g / cm ³ or more at 15 ° C. is proposed (Japanese Patent Laid-Open No. 2000-87069 (hereinafter referred to as “patent”). Reference 3 ”)).

  In addition, US Pat. No. 7,060,662 (hereinafter referred to as “Patent Document 4”) discloses polydimethylsiloxane and a fluorinated silicone antifoaming agent as antifoaming agents used in an automatic transmission fluid for automobiles. A silicon-containing antifoaming agent comprising a mixture of

  As described above, each patent document discloses the use of fluorinated silicone as an antifoaming agent. However, fluorinated silicone is used for hydrocarbon oils having low solubility in an antifoaming agent such as a lubricating oil. On the other hand, it has been pointed out that the dispersibility is low and the defoaming performance is significantly deteriorated with storage.

There is no disclosure in any of the above-mentioned patent documents regarding the solution of the problems of such fluorinated silicone, and there is naturally no suggestion about the solution, and the practical difficulties are included.

  Therefore, in order to realize a lubricating oil composition having high antifoaming performance and excellent storage stability, particularly the antifoaming useful for maintaining dispersibility of the fluorinated silicone in the lubricating oil composition. Development of agent compositions has been eagerly desired.

Japanese Patent Publication No. 1992-50045 JP 2000-87065 A JP 2000-87069 A US Pat. No. 7,060,662

Therefore, the problem of the present invention is that when fluorinated silicone is used as an antifoaming agent for a lubricating oil composition, the dispersibility of the fluorinated silicone with respect to the lubricating base oil or the lubricating oil composition is high, and an excellent initial Antifoaming composition that imparts antifoaming performance and is excellent in its durability and is capable of imparting storage stability, initial antifoaming performance comprising the antifoaming composition as a constituent, and its durability and storage stability An object of the present invention is to provide a lubricating oil composition excellent in the above and a method for producing such a lubricating oil composition.

  Therefore, the present inventor has made extensive studies to solve the above-described problems of the present invention, and as a result, the antifoam composition comprising a combination of a fluorinated silicone, a specific fluorine-containing organic compound, and a specific organic solvent. Focusing on the fact that the product can impart good initial defoaming performance and storage stability to the lubricating oil composition, and further, by adding a fluorosurfactant, further superior defoaming performance and its durability, The inventors have found that storage stability can be obtained, and arrived at the present invention based on such knowledge.

Thus, according to the present invention,
An antifoam composition used as a component of a lubricating oil composition, comprising the following components (A), (B) and (C):
(A) at least one fluorine-containing organic compound selected from the group consisting of fluorine-containing organic compounds represented by the following general formulas (1) and (2),

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

(In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si,
(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon having 1 to 10 carbon atoms. Substituents selected from the group consisting of groups, and two or more kinds of substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 fluorine-containing hydrocarbon groups,
(Iv) m is 1-6,
(V) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents selected from the group consisting of two or more substituents may be the same or different from each other, but at least one substituent has 1 to 10 carbon atoms. A fluorine-containing hydrocarbon group,
(Vi) n is 2-5. )
There is provided an antifoam composition comprising (B) a fluorinated silicone and (C) a hydrocarbon-based or alcohol-based organic solvent.

Moreover, according to the present invention,
A lubricating oil composition comprising a lubricating base oil and an antifoam composition blended in the lubricating base oil, the antifoam composition comprising:
(A) at least one fluorine-containing organic compound selected from the group consisting of fluorine-containing organic compounds represented by the following general formulas (1) and (2),

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

(In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si,
(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon having 1 to 10 carbon atoms. Substituents selected from the group consisting of groups, and two or more kinds of substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 fluorine-containing hydrocarbon groups,
(Iv) m is 1-6,
(V) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The two types of substituents may be the same or different from each other, but at least one type of the substituent is fluorine having 1 to 10 carbon atoms. Containing hydrocarbon groups,
(Vi) n is 2-5. )
A lubricating oil composition comprising (B) a fluorinated silicone and (C) a hydrocarbon-based or alcohol-based organic solvent is provided.
Furthermore, according to the present invention,
(A) the following general formulas (1) and (2);

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

(In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si,
(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon having 1 to 10 carbon atoms. Substituents selected from the group consisting of groups, and two or more kinds of substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 A fluorine-containing hydrocarbon group of
(Iv) m is 1-6,
(V) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents selected from the group consisting of two or more substituents may be the same or different from each other, but at least one substituent has 1 to 10 carbon atoms. A fluorine-containing hydrocarbon group,
(Vi) n is 2-5. )
A mixture of at least one fluorine-containing organic compound selected from the group consisting of fluorine-containing organic compounds represented by: (B) a fluorinated silicone and (C) a hydrocarbon-based or alcohol-based organic solvent. There is provided a method for producing a lubricating oil composition comprising a step of preparing an antifoaming agent composition and a step of blending the antifoaming agent composition prepared in the step with a lubricating base oil.

Moreover, according to the present invention, an antifoaming composition comprising a mixed solution of the component (A), the component (B) and the component (C) is prepared, and this is added to the lubricating base oil. A method for improving the initial defoaming performance and durability and storage stability of a lubricating oil composition is provided.

    The defoamer composition according to the present invention comprises a homogeneous mixed solution of a fluorine-containing organic compound, a fluorinated silicone, and a hydrocarbon-based or alcohol-based organic solvent, and comprises a defoaming active ingredient, particularly a transparent solution of the fluorinated silicone. It is to provide. By blending such a homogeneous mixed solution into the lubricating base oil, it is possible to provide a lubricating oil composition that prevents separation and white turbidity of the antifoam active ingredient and improves its dispersibility.

    Further, the lubricating oil composition according to the present invention has excellent initial defoaming performance and in particular, durability against deterioration due to oxidation or the like of the fluorinated silicone, and maintains the initial defoaming performance even upon storage. It can be used for various applications under a wide range of use conditions of lubricating oil. For example, the formation of bubbles can be prevented or the formed bubbles can be easily destroyed even under high-speed rotation conditions where there is a high possibility of air contamination, so that smooth lubrication is possible. Lubricating oil compositions suitable as transmission oil, hydraulic oil, compressor oil, engine oil and the like can be provided. In particular, the lubricating oil composition according to the present invention is suitable as a driving fluid for driving system devices, particularly as an automatic transmission oil for automobiles, CVT fluid, and the like.

Furthermore, according to the method for producing a lubricating oil composition according to the present invention, an antifoam having excellent stability can be obtained by combining the preparation process of the antifoam composition and the blending process of the antifoam composition into the base oil. A lubricating oil composition having foam characteristics can be produced efficiently and stably, and the production efficiency can be increased.

  According to the present invention, there is provided an antifoaming composition obtained by mixing (A) a fluorine-containing organic compound, (B) a fluorinated silicone, and (C) a hydrocarbon-based or alcohol-based organic solvent. Further, according to the present invention, as described above, the lubricating base oil and (A) a fluorine-containing organic compound, (B) a fluorinated silicone, and (C) a hydrocarbon-based or alcohol-based compound blended in the lubricating base oil. The present invention provides a lubricating oil composition comprising an antifoaming composition obtained by mixing an organic solvent. Furthermore, according to the present invention, a preparation process of an antifoaming composition comprising (A) a fluorine-containing organic compound, (B) a fluorinated silicone, and (C) a hydrocarbon-based or alcohol-based organic solvent; The present invention provides a method for producing a lubricating oil composition comprising a blending step of blending the antifoam composition obtained in the preparation step with a lubricating base oil.

  Further, an antifoaming agent composition is prepared from a mixed solution of (A) a fluorine-containing organic compound, (B) a fluorinated silicone, and (C) a hydrocarbon-based or alcohol-based organic solvent, which is used as a lubricating base oil or lubricating oil. The present invention provides a method for improving the antifoaming performance of a lubricating oil composition comprising adding to the composition, and further preferred embodiments include the following (1) to (14).

(1) The said antifoamer composition whose fluorine-containing organic compound of the said component (A) is a compound which has a structure represented by following General formula (11) or General formula (22).

R ₁₁ -XR ₁₂ (11)

R ₂₁ -YR ₂₂ (22)

(In the general formulas (11) and (22),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group having at least one hetero atom of O or S,
(Iii) R ₁₁ and R ₁₂ are each a fluorine atom substituted with two hydrogen atoms of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. The substituent is selected from the group consisting of 10 fluorine-containing hydrocarbon groups, and the substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 fluorine-containing hydrocarbon groups,
(Iv) R ₂₁ and R ₂₂ are each a substituent bonded to the group containing a heteroatom, and are composed of a hydrocarbon group having 1 to 10 carbon atoms and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. A substituent selected from the group, which may be the same or different from each other, but at least one substituent is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. )

(2) In the general formula (11), R ₁₁ and R ₁₂ are each selected from the group consisting of an aliphatic hydrocarbon group having 1 to 5 carbon atoms and a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms. The substituents may be the same or different, but at least one substituent is a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms, and X is The said antifoamer composition which is an aromatic hydrocarbon group.

(3) In the general formula (22), R ₂₁ and R ₂₂ are each selected from the group consisting of an aliphatic hydrocarbon group having 1 to 5 carbon atoms and a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms. The substituents may be the same or different, but at least one substituent is a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Y is The antifoaming composition, which is a group having an oxygen atom or a sulfur atom.

(4) Component (A) 2 to 98% by weight of component (A), component (B) and component (C) in the defoamer composition based on the total weight of the defoamer composition (B) The said antifoamer composition which is 0.01 to 10 weight% and a component (C) 2 to 98 weight%.

(5) Component (A) 20-80% by weight of component (A), component (B) and component (C) in the defoamer composition based on the total weight of the defoamer composition, The said antifoamer composition which is 0.1 to 8 weight% of a component (B), and 20 to 80 weight% of a component (C).

(6) The said defoamer composition whose component further added to the component which consists of said (A), (B) and (C) is component (D) fluorine-type surfactant.

(7) The said lubricating oil composition which consists of lubricating oil base oil and the antifoamer composition in any one of said (1)-(6) mix | blended with this lubricating oil base oil.

(8) The method for producing the lubricating oil composition, wherein the fluorine-containing organic compound is a compound having a structure represented by the following general formula (11) or general formula (22).

R ₁₁ -XR ₁₂ (11)

R ₂₁ -YR ₂₂ (22)

(In the general formulas (11) and (22),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group having at least one hetero atom of O or S,
(Iii) R ₁₁ and R ₁₂ are each a fluorine atom substituted with two hydrogen atoms of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. The substituent is selected from the group consisting of 10 fluorine-containing hydrocarbon groups, and the substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 fluorine-containing hydrocarbon groups,
(Iv) R ₂₁ and R ₂₂ are substituents bonded to the group containing a hetero atom, and are a group consisting of a hydrocarbon group having 1 to 10 carbon atoms and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents may be the same or different, and at least one substituent is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. )

(9) In the general formula (11), R ₁₁ and R ₁₂ are each selected from the group consisting of an aliphatic hydrocarbon group having 1 to 5 carbon atoms and a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms. The substituents may be the same or different, but at least one substituent is a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms, and X is The manufacturing method of the said lubricating oil composition which is an aromatic hydrocarbon group.

(10) In the general formula (22), R ₂₁ and R ₂₂ are each selected from the group consisting of an aliphatic hydrocarbon group having 1 to 5 carbon atoms and a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms. The substituents may be the same or different, but at least one substituent is a fluorine-containing aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Y is The manufacturing method of the said lubricating oil composition which is group which has an oxygen atom or a sulfur atom.

(11) The method for producing the lubricating oil composition, wherein the component further added to the component consisting of (A), (B) and (C) is component (D) a fluorosurfactant.

(12) The said lubricating oil composition whose kinematic viscosity in 100 degreeC of the said lubricating base oil is 2-10 mm < ² > / _S.

(13) The lubricating oil composition, wherein a blending ratio of the lubricating base oil is 99.5 to 50% by weight based on the total weight of the lubricating oil composition.

(14) Initial stage by adding an antifoam composition comprising a mixed solution of (A) a fluorine-containing organic compound, (B) a fluorinated silicone, and (C) a hydrocarbon-based or alcohol-based organic solvent to a lubricating base oil How to improve defoaming performance and durability.

Antifoam composition The antifoam composition according to the present invention is a constituent used as a component of a lubricating oil composition, and comprises (A) a fluorine-containing organic compound, (B) a fluorinated silicone, and (C) carbonization. It is a mixed solution comprising a hydrogen-based or alcohol-based organic solvent and having (D) a fluorosurfactant added as an optional component. Such a mixed solution is preferably homogeneous and transparent. The antifoam composition can also be used as a component of an additive package or in the form of an additive masterbatch.

  The additive masterbatch is a mixture of mineral oil base oil, synthetic oil base oil or mixed oil base oil in a high proportion of antifoam composition. This may be used after appropriately diluted with a medium.

  In the component of the defoamer composition according to the present invention, the fluorine-containing organic compound of component (A) and the organic solvent of component (C) are prepared in order to prepare a transparent solution of the fluorinated silicone of component (B). In particular, the fluorine-containing organic compound of component (A) is a compound represented by the general formula (1) or (2).

    The mixing ratio of the respective components of the defoamer composition is 2 to 98% by weight of component (A), 0.01 to 10% by weight of component (B), and component (B) based on the total weight of the defoamer composition. C) It is 2-98 weight%, and a preferable mixing ratio is 20-80 weight% of a component (A), 0.1-8 weight% of a component (B), and 20-80 weight% of a component (C). More preferable mixing ratios include components (A) 30 to 70% by weight, components (B) 1 to 3% by weight, and components (C) 30 to 70% by weight.

    Moreover, a component (D) can be used in 0.005 to 5 weight%, Preferably it is 0.01 to 1 weight%, More preferably, it is 0.05 to 0.5 weight%.

  In the lubricating oil composition, the coexistence of the component (A) and the component (C) in the antifoam composition is important in order to maintain the dispersibility of the fluorinated silicone of the component (B) and the stability in storage. In particular, when the component (A) does not reach 2% by weight, the defoamer composition becomes cloudy / separated even if the component (C) is present. Even if it mix | blends with, dispersibility of a component (B) is inferior and sufficient defoaming effect is not acquired. On the other hand, even when the component (A) is included, when the component (C) is not included, particularly when it does not reach 2% by weight, the antifoaming composition is homogeneous and transparent, but not separated. In order to exhibit the initial performance and storage stability of the component (B), the initial defoaming performance of the component (B) cannot be maintained, and problems such as lack of storage stability occur. ) And component (C) are essential, and therefore the coexistence of components (A), (B) and (C) is important.

    The antifoam composition becomes transparent without causing cloudiness and separation by satisfying all of the components (A), (B) and (C) and their mixing ratios, and this is blended into the base oil. By doing so, the lubricating oil composition having significantly superior initial defoaming performance and storage stability as compared with the case where the component (A), the component (B) and the component (C) are each added alone to the base oil. It can contribute to formation of.

  Moreover, antifoaming performance and its storage stability can be further improved by adding component (D).

(A) Fluorine-containing organic compound The fluorine-containing organic compound that is a constituent of the lubricating oil composition according to the present invention has the following general formulas (1) and (2):

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si.
(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon having 1 to 10 carbon atoms. A substituent selected from the group consisting of a group, wherein the substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a fluorine-containing hydrocarbon having 1 to 10 carbon atoms Group,
(Iv) m is 1-6,
(V) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents selected from the group consisting of two or more substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 fluorine-containing hydrocarbon groups,
(Vi) n is 2-5.

  Among the fluorine-containing organic compounds, more preferable compounds are those having a structure represented by the following general formula (11) or general formula (22).

R ₁₁ -XR ₁₂ (11)

_{R 21 -Y-R 22 (22} )

The fluorine-containing organic compounds represented by the general formulas (11) and (22) each have a di-substituent on an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a group having a divalent heteroatom. is there. Of the hydrocarbon groups, aromatic hydrocarbon groups are preferred.

  The hydrocarbon group having 1 to 10 carbon atoms includes an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Is. Among these hydrocarbon groups, a particularly preferred hydrocarbon group is an aliphatic hydrocarbon group, which has an unsaturated bond, and may have a linear structure or a branched structure. Of the aliphatic hydrocarbon groups, a relatively short-chain aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferable, more preferably 1 to 6 carbon atoms, and most preferably a lower group having 1 to 5 carbon atoms. A hydrocarbon group is mentioned.

    In addition, the fluorine-containing hydrocarbon group having 1 to 10 carbon atoms may have a structure in which all or part of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, but may have a different hydrocarbon structure.

Accordingly, in the general formulas (1), (2), (11) and (12), preferred substituents R ^1, R ₁₁ , R _12, R ² , R ₂₁ and R ₂₂ are each a fluorine atom, A substituent selected from the group consisting of 7 aliphatic hydrocarbon groups and 1 to 7 fluorine-containing aliphatic hydrocarbon groups, and these two or more types of substituents are the same or different from each other One of these substituents may be a fluorine-containing aliphatic hydrocarbon group having 1 to 7 hydrocarbons.

Further, suitable substituents R ^1, include aliphatic hydrocarbon groups and fluorine-containing aliphatic hydrocarbon group of hydrogen containing 1-5 of 1 to 5 carbon atoms.

In the fluorine-containing organic compound, the number of fluorines in one molecule is based on the total number of carbon atoms of R ¹ in the general formula (1) or the total number of carbon atoms in R ² of the general formula (2) in the whole fluorine-containing organic compound. A large amount is preferable. The fluorine-containing organic compound preferably has at least one trifluoromethyl group (CF ₃ —).

    In the general formulas (1) and (2), X is an aromatic hydrocarbon group or alicyclic hydrocarbon group, and Y is a group having at least one hetero atom of O, S, N, P or Si. Specifically, it can be selected from groups belonging to the following groups 1 to 3.

1. Aromatic hydrocarbon group An aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a benzene ring, a benzene ring having at least one alkyl group or an alkenyl group, such as alkylbenzene, stilbene, xylene, etc. In addition, a condensed ring such as a naphthalene ring can be mentioned. From the viewpoint of maintaining the solubility of the fluorinated silicone, a benzene ring and a naphthalene ring are preferable, and a benzene ring is particularly preferable. Particularly preferred are those having two substituents, for example, a benzene ring having two alkyls.

2. Alicyclic hydrocarbon group Examples of the alicyclic hydrocarbon group include a cycloalkyl group having 3 to 10 carbon atoms or a cycloalkyl group having a side chain. , Cyclopentane, cyclohexane and the like are preferable. In particular, a cycloalkyl group having two substituents is more preferable.
Of the aromatic hydrocarbon group and the alicyclic hydrocarbon group, the aromatic hydrocarbon group is preferable.

3. A group having a heteroatom of O, S, N, P or Si As a group having a heteroatom of O, S, N, P or Si, oxygen (—O—), carbonyl group (—CO—), carboxyl group (—CO ₂ —), carbonate (—CO ₃ —), sulfur (—S—), sulfoxide group (—SO—), sulfone group (—SO ₂ —), sulfonic acid group (—SO ₃ —), sulfuric acid Group (—SO ₄ —), —O (R ⁴ O) n— (wherein R ⁴ is a divalent hydrocarbon group or fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 10). When n is 2 or more, R ⁴ may be the same or different.), Nitrogen (—N═), phosphoryl group (—PO═), phosphonic acid group (—PO ₃ ═ ), Phosphoric acid groups (—PO ₄ =) and the like.

    Among the groups having a heteroatom, groups having oxygen (—O—), sulfur (—S—) and nitrogen (—N═) are preferable, and in particular, oxygen (—O—), sulfur (—S Groups having-) are preferred.

    Specific examples of the fluorine-containing organic compound include those described below.

Trifluoromethylbenzene tris (trifluoromethyl) benzene bis (trifluoromethyl) benzene methylpentafluorobenzene pentafluorotoluene hexafluorobenzene perfluorotoluene benzotrifluoride o-bis (trifluoromethyl) benzene m-bis (trifluoromethyl) ) Benzene p-bis (trifluoromethyl) benzene perfluorocyclopentane perfluorocyclohexane 2,2,3,3-tetrafluoro-1-propanol octafluoropentanol perfluorobutyl methyl ether perfluorobutyl ethyl ether perfluorobutyl butyl ether Perfluorobutylbenzyl ether Perfluorobutylphenyl ether Pentafluoroanisole Pentafluoro Acetophenone pentafluorobenzonitrile perfluorotributylamine perfluorotripropylamine perfluoro (2-butyl tetrahydrofuran)
Bis (heptafluoroisopropyl) ketone F-DPC _{[C 2 F 5 CH 2 O (} C = O) OCH 2 C 2 H 5 ]
F-DEC [CF ₃ CH ₂ O (C═O) OCH ₂ C ₂ F ₃ ]
Fluoroethylene carbonate,
Preferred examples of the fluorine-containing organic compound include tris (trifluoromethyl) benzene, bis (trifluoromethyl) benzene, bis (trifluoromethyl) ether, methylpentafluorobenzene, and trifluoromethylpentafluoroethyl ether. , Trifluoromethyl ethyl ether, trifluoromethyl trifluoro ether, bis (pentafluoroethyl) ether, bis (tetrafluoroethyl) ether, trifluoroethyl tetrafluoroethyl ether, bis (trifluoroethyl ether), trifluoromethyl isopropyl Examples include ether, bis (heptafluoro n-propyl) ether, ethyl isononafluorobutyl ether, and the like.

    Among the commercially available products that can be used as the fluorine-containing organic compound, 3FE HFE-7100 is used as perfluorobutyl methyl ether, and HFE-7200 is used as perfluorobutyl ethyl ether. Can do. Other products include FC-72, FC-84, FC-77, FC-75, PF-5080, PF-5052 and the like. Further, MTF-TFM from Central Glass Co. can be obtained as bis (trifluoromethyl) benzene, and fluorine-containing organic compounds such as Asahi Clean AE-3000 from Asahi Glass Co. can be obtained from trifluoroethyl tetrafluoroethyl ether. .

(B) Fluorinated Silicone As the fluorinated silicone that is a constituent of the antifoam composition according to the present invention, a fluorine-containing organosiloxane and a compound having an organosiloxane are used in the molecule.

    Examples of the fluorine-containing organosiloxane include a structure represented by the following general formula (3) or general formula (4), and examples of the organosiloxane include a structure represented by the general formula (5).

    The fluorinated silicone in the present invention has a fluorine-containing organosiloxane structure represented by the general formulas (3) and (4) and an organosiloxane structure represented by the general formula (5) in the molecule. It can be illustrated by the following general formula (6).

In the general formulas (3) and (4), A represents a monovalent group represented by RfR ⁷ —, a hydrogen atom, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.

Rf is a perfluoroalkyl group having 1 to 14 carbon atoms, ^{R 7} is a divalent hydrocarbon group having 1 to 8 carbon atoms.
Specific examples of Rf include, for example, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoropeptyl group, perfluorooctyl group, Examples thereof include a perfluorononyl group, a perfluorodecyl group, a perfluoroundecyl group, a perfluorododecyl group, a perfluorotridecyl group, and a perfluorotetradecyl group.

Such a perfluoroalkyl group may be linear or branched.
Specific examples of R ⁷ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group and phenylene group.

R ⁵ in the general formulas (3) and (6) is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, and a propyl group. Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and other alkyl groups, cyclohexyl group and other cycloalkyl groups, vinyl group and allyl group and other alkenyl groups, phenyl group and tolyl group and the like And an aralkyl group such as a phenylethyl group.

R ⁶ in the general formula (5) and general formula (6) is also a hydrocarbon group of the R ⁵ and similarly a hydrogen atom or 1 to 10 carbon atoms, similarly to R ⁵ Specific examples of the hydrocarbon group R ⁶ Is a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a tolyl group; An aralkyl group such as ethyl;

M and n in the general formula (6) are each an integer of 1000 or less, and are determined by a desired viscosity. As the viscosity, one having a kinematic viscosity at 25 ° C. of 100 to 2500 mm ² / s, preferably 300 to 2000 mm ² / s can be employed. If the 25 ° C. kinematic viscosity does not reach 100 mm ² / s, it is difficult to obtain an antifoaming effect. On the other hand, when it exceeds 2500 mm ² / s, there is a possibility that sedimentation separation or the like may occur in the antifoam composition.

    Commercially available products of such fluorinated silicones include FL-5, X-22-821, X-22-822, FL-100-100cs, FL-100-450cs, FL-100-1000cs, FL-100-10000cs, FA630. (The above is made by Shin-Etsu Chemical Co., Ltd.), FS1265 (300 cs), FS1265 (1000 cs), FS1265 (10000 cs), (above, made by Toray Dow Corning) and the like can be obtained. Among these, as a component of the lubricating oil composition according to the present invention, FL-100-450cs, FA630, FS1265 (300cs) and the like are preferable, and it is particularly preferable to select FL-100-450cs, FA630.

(C) Hydrocarbon-based or alcohol-based organic solvent The organic solvent as a constituent of the defoamer composition according to the present invention is a medium used for stabilizing the dispersibility of the fluorinated silicone. The organic solvent can be arbitrarily selected without particular limitation as long as it effectively acts for dispersion of the fluorinated silicone and maintenance of the dispersion state, for example, even if it contains a carbonyl group. Particularly preferred organic solvents are hydrocarbon solvents, specifically, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, etc., alcohol solvents such as methanol and ethanol, ethers, etc. And oxygen-containing compounds including More preferable organic solvents include aliphatic hydrocarbons and aromatic hydrocarbons. In particular, those having a flash point of −10 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., more preferably 10 ° C. to 100 ° C. can be used. When the flash point is less than −10 ° C., in the production of a lubricating oil composition using the antifoam composition according to the present invention, it may be necessary to introduce a cooling device to ensure safety, When exceeding, there exists a possibility that the problem that favorable defoaming performance cannot be obtained may arise.

The (D) a fluorine-containing surfactant fluorosurfactants, perfluoroalkyl group, can be employed oligomers comprising lipophilic and hydrophilic groups, such oligomers, the carbon atom of the hydrophobic group in the molecule Instead of the bonded hydrogen atoms, all or part of them are substituted with fluorine atoms.

As a constituent component of the lubricating oil composition according to the present invention, a fluorinated surfactant having an oxy C _2-3 alkylene group and a fluorinated hydrocarbon group in the molecule is used. The oxy C _2-3 alkylene group is represented by the formula; —R—O— (where R is a linear or branched alkylene group having 2 or 3 carbon atoms). By having an oxy _C2-3 alkylene group, the dispersibility of the fluorinated silicone in the lubricating base oil can be improved. The fluorosurfactant is not particularly limited as long as it has an oxy _C2-3 alkylene group and a fluorinated hydrocarbon group, but a nonionic surfactant is preferred from the viewpoint of dispersibility in a lubricating base oil. Further, the molecule may have any one kind of oxyethylene group (—CH ₂ CH ₂ O—), oxypropylene group [—CH ₂ CH (CH ₃ ) O—], etc. You may have. In addition, a fluorine-type surfactant can be used individually or in combination of 2 or more types.

Although it does not specifically limit as a fluorinated hydrocarbon group, A perfluoro group is suitable, This perfluoro group may be monovalent and may be bivalent or more polyvalent. Further, the fluorinated hydrocarbon group may have a double bond or a triple bond, and may be linear or have a branched structure or a cyclic structure. It does not specifically limit as carbon number of a fluorinated hydrocarbon group, It is 1 or 2 or more, Preferably it is 3-30, More preferably, it is 4-20. One or two or more of these fluorinated hydrocarbon groups are introduced into the surfactant molecule. Examples of the oxy C _2-3 alkylene group include alcohols in which a hydrogen atom is bonded to a terminal oxygen atom, ethers bonded to other hydrocarbon groups, and esters bonded to other hydrocarbon groups through a carbonyl group. Form may be sufficient. Moreover, the form which has this structure in a part of cyclic structure, such as cyclic ethers and lactones, may be sufficient.

The structure of the fluorosurfactant is not particularly limited. For example, a copolymer containing a monomer having an oxy _C2-3 alkylene group and a monomer having a fluorinated hydrocarbon group as a monomer component is preferably used. Can be used. As such a copolymer, various structures such as a block copolymer and a graft copolymer can be considered, and any of these structures is preferably used.

Examples of the block copolymer (copolymer having an oxy C _2-3 alkylene group and a fluorinated hydrocarbon group in the main chain) include, for example, polyoxyethylene perfluoroalkyl ether, polyoxyethylene perfluoroalkylate, polyoxyethylene Examples thereof include propylene perfluoroalkyl ether, polyoxyisopropylene perfluoroalkyl ether, polyoxyethylene sorbitan perfluoroalkylate, polyoxyethylene polyoxypropylene block copolymer perfluoroalkylate, and polyoxyethylene glycol perfluoroalkylate.

The graft copolymer as the (a copolymer having an oxy- (C _2-3) alkylene group and a fluorinated hydrocarbon group in side chains), at least as a monomer component, a vinyl compound having a polyoxyalkylene group and a fluorinated hydrocarbon group A copolymer containing a vinyl-based compound having, particularly an acrylic copolymer, is preferably used. Examples of the vinyl compound having a polyoxyalkylene group include polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and polyoxyethylene polyoxypropylene (meth) acrylate. Can be mentioned. Examples of vinyl compounds having a fluorinated hydrocarbon group include perfluoroalkyl (meth) acrylates such as perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, and perfluoropentyl (meth) acrylate, fluorine And (meth) acrylic acid ester containing a fluorinated hydrocarbon group.

  The fluorosurfactant may have a structure such as an alicyclic hydrocarbon group or an aromatic hydrocarbon group in addition to the above structure in the molecule, and does not impair dispersibility in the lubricating base oil. It may have various functional groups such as carboxyl group, sulfonic acid group, cyano group, amide group, amino group. For example, when the fluorosurfactant is a vinyl copolymer, a monomer component copolymerizable with a vinyl compound having a polyoxyalkylene group and a vinyl compound having a fluorinated hydrocarbon group is used as the monomer component. May be. Such monomers can be used alone or in combination of two or more.

Examples of the copolymerizable monomer component include (meth) acrylic acid C _1-20 alkyl esters such as undecyl (meth) acrylate and dodecyl (meth) acrylate; and alicyclic carbonization such as cyclopentyl (meth) acrylate. A (meth) acrylic acid ester having a hydrogen group; a (meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate is preferably used. In addition, carboxyl group-containing monomers such as maleic acid and crotonic acid; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins and dienes such as ethylene and butadiene Vinyl ethers such as vinyl alkyl ethers; amide group-containing monomers such as acrylamide; amino group-containing monomers such as (meth) acryloylmorpholine; glycidyl group-containing monomers such as methyl glycidyl (meth) acrylate; 2 -Isocyanate group-containing monomers such as methacryloyloxyethyl isocyanate. Furthermore, polyfunctional copolymerizable monomers (polyfunctional monomers) such as dipentaerythritol hexa (meth) acrylate and divinylbenzene may be used.

Specific examples of the fluorosurfactant include trade names “Megafac F-477”, “Megafac F-483”, “Megafac F-470” (manufactured by DIC Corporation), and trade names “Surflon S”. -381 "(manufactured by Sey Chemical Co., Ltd.), trade name" Surflon S-383 "(manufactured by Sey Chemical Co., Ltd.), trade name" Surflon S-393 "(manufactured by Sey Chemical Co., Ltd.), trade name" Surflon KH-20 " (Sei Chemical Co., Ltd.), trade name "Surflon KH-40" (Sey Chemical Co., Ltd.), and the like. As a specific example of the fluorosurfactant having an oxy C _2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of 20000 or more, a trade name “F-top EF-352” (manufactured by Gemco Co., Ltd.) ), Trade name “F-top EF-801” (manufactured by Gemco Co., Ltd.), trade name “Unidyne TG-656” (manufactured by Daikin Industries, Ltd.), etc., and any of them can be suitably used in the present invention. In particular, in order to achieve the object of the present invention, it is preferable to employ “Megafac F-477” and “Megafac F-483” manufactured by DIC.

Lubricating oil base oil The base oil that is a component of the lubricating oil composition according to the present invention is not particularly limited as long as it is used as a normal lubricating oil base oil and can be used. What can disperse | distribute without fully melt | dissolving the fluorinated silicone used as a structural component of the lubricating oil composition which concerns on invention is suitable. Specifically, a mineral base oil, a GTL (Gas to liquid) base oil, a synthetic oil base oil, or a mixed oil base oil that satisfies such requirements is used.

  Mineral oil base oils include solvent refining, hydrocracking, and lubricating oil fractions or residual oils obtained as distillate by vacuum distillation of residual oil from paraffinic, intermediate base or naphthenic crude oil distillation equipment. Solvent-refined mineral oil or hydrotreated mineral oil obtained by processing by arbitrarily selecting and using various purification processes such as hydrotreating, hydrorefining, solvent dewaxing, catalytic dewaxing, and clay treatment, and solvent refining and hydrogen Mineral oil obtained by a combined process of mineralization, or mineral oil obtained by treating the defoamed oil obtained by solvent defoaming treatment of vacuum distillation residue oil by the above purification process, or mineral oil obtained by isomerization of the wax These mixed oils can be used as a base oil base material.

    In the solvent refining, an aromatic extraction solvent such as phenol, furfural, N-methyl-2-pyrrolidone or the like is used, a denitrification solvent such as liquefied propane is used for the solvent desulfurization treatment, and a solvent dewaxing solvent is used. As such, liquefied propane, MEK / toluene and the like are used.

    On the other hand, in catalytic dewaxing, for example, shape selective zeolite or the like is used as a dewaxing catalyst.

    Examples of the refined base oil base material obtained as described above include light neutral oils, medium neutral oils, heavy neutral oils, bright stocks, and the like having different viscosity levels. A mineral oil-based base oil can be produced by appropriately blending so as to satisfy the required properties such as kinematic viscosity according to the application.

  The GTL oil base oil includes a lubricating oil fraction separated from a liquid product obtained by using a natural gas or the like by a GTL process, or a lubricating oil obtained by hydroisomerization or hydrocracking of the produced wax. A fraction etc. can be mentioned. Further, a lubricating oil fraction separated from a liquid product oil obtained by an ATL (Asphalt to Liquid) process using a heavy residual oil component such as asphalt as a raw material can be used.

  On the other hand, synthetic base oils include polyalphaolefin oligomers (for example, poly (1-hexene), poly (1-octene), poly (1-decene) and mixtures thereof); polybutene; ethylene-alkylene Copolymer; alkylbenzene (eg, dodecylbenzene, tetradecylbenzene, di (2-ethylhexyl) benzene, dinonylbenzene, etc.); polyphenyl (eg, biphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ether and alkylated diphenyl Sulfides and their derivatives; dibasic acids (eg, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, speric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.). And various alcohols For example, esters with butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc .; monocarboxylic acids having 5 to 18 carbon atoms and polyols (for example, neopentyl glycol, Ester with trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.); other examples include polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxyalkylene glycol ether, and phosphate ester.

Lubricating base oils may be used alone or in combination so that the above-mentioned mineral base oil, synthetic base oil and GTL base oil satisfy the desired viscosity and other properties depending on the use of the lubricating oil composition. It is manufactured by mixing the above base oils.
As the lubricating base oil, a mixed base oil of a synthetic base oil and a mineral base oil is particularly suitable, a mixed base oil of a GTL base oil and a mineral base oil, two kinds Preferred is a mixed oil base oil composed of the above mineral oil base oil or a mixed oil base oil composed of two or more GTL oil base oils, and further a mixed oil of GTL oil base oil and mineral oil base oil. A mixed base oil composed of a base oil and two or more mineral base oils is preferred from the viewpoint of balancing the viscosity characteristics and the economy.

The viscosity of the lubricating base oil as a constituent in the lubricating oil composition according to the present invention is determined according to the use of the lubricating oil composition, but under circumstances where low viscosity oil is required from the viewpoint of environmental conservation. The kinematic viscosity at 100 ° C. of the lubricating base oil is in the range of ² to 10 mm ² / s, and preferably in the range of 3 to 7 mm ² / s.

  When the viscosity of the lubricating base oil is too high, there is a problem that the frictional resistance is increased, the friction coefficient in the fluid lubrication region is increased, and the fuel saving characteristics are deteriorated. On the other hand, when the viscosity is too low, there is a problem that wear increases in sliding parts, for example, a valve system of an internal combustion engine, a piston ring and a bearing.

    The content of the lubricating base oil is 99.5 to 50% by weight, preferably 99 to 60% by weight, more preferably 95 to 70% by weight, based on the total weight of the lubricating oil composition.

Lubricating oil composition The lubricating oil composition according to the present invention comprises a lubricating base oil and an antifoaming composition blended in the lubricating base oil, depending on the use of the lubricating oil composition. Various other additives are optionally blended to satisfy the required performance. The antifoam composition is as described above, and comprises a fluorine-containing organic compound of component (A), a fluorinated silicone of component (B) and a hydrocarbon-based or alcohol-based organic solvent of component (C). And containing a fluorosurfactant as the optional component (D).

  An antifoaming agent comprising a lubricating base oil and an antifoaming composition comprising components (A), (B) and (C) and (D) blended in the lubricating base oil. The content of the composition is employed in the range of 0.05 to 10% by weight based on the total weight of the lubricating oil composition.

    The content of the fluorine-containing organic compound of component (A) is 0.001 to 5% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0%, based on the total weight of the lubricating oil composition. .5% by weight. If the content is less than 0.001% by weight, good defoaming performance may not be obtained. On the other hand, if the content exceeds 5% by weight, precipitation may occur in the lubricating oil.

  Moreover, content of the fluorinated silicone of a component (B) is 0.0005 to 1 weight%, Preferably it is 0.005 to 0.8 weight%, More preferably, it is 0.05 to 0.3 weight%.

    The content of the hydrocarbon-based or alcohol-based organic solvent of component (C) is 0.001 to 5% by weight, preferably 0.005 based on the total weight of the lubricating oil composition. -1% by weight, more preferably 0.01-0.5% by weight. If the content is less than 0.001% by weight, precipitation may occur when the antifoam composition is blended with the base oil, while if it exceeds 5% by weight, good defoaming properties can be obtained. It may not be possible.

    The content of the fluorosurfactant of component (D) is 0.000005 to 0.5% by weight, preferably 0.00001 to 0.1% by weight, more preferably 0.005% by weight based on the total weight of the lubricating oil composition. 00005 to 0.05% by weight.

Method for Producing Lubricating Oil Composition The method for producing a lubricating oil composition according to the present invention preferably comprises the following Step I and Step II.
Step I includes (A) the following general formulas (1) and (2);

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

(In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si.

(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon having 1 to 10 carbon atoms. A substituent selected from the group consisting of a group, wherein the substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a fluorine-containing hydrocarbon having 1 to 10 carbon atoms Group,
(Iv) m is 1-6,
(V) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents may be the same or different from each other, and at least one substituent is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. Yes,
(Vi) n is 2-5. )
And (B) a fluorinated silicone and (C) a hydrocarbon-based or alcohol-based organic solvent are mixed to prepare a defoamer composition.

Operation of the mixing method of components (A), (B) and (C) is not particularly limited and may be arbitrarily determined. However, after components (A) and (B) are mixed in advance, C) is preferably added to dissolve the whole. Even in the case of adding the component (D), when mixing them, the component (A), the component (B), and the component (D) are dissolved in advance, and then the component (C) is added to dissolve the whole. It is preferable. The mixing conditions are not particularly limited and may be ambient temperature, but may be appropriately heated within a necessary range.
Step II is a step of blending an antifoam composition composed of components (A), (B) and (C), preferably (D), prepared in Step I above, into a lubricating base oil. The operation and conditions for blending are not particularly limited, and ordinary additive blending methods may be employed. In addition, other additives may be added to the mixed solution of the components (A), (B) and (C) in the step I. However, in step II, the additive may be added to the base oil in advance or in the antifoam composition. You may add simultaneously.

Other additives The lubricating oil composition according to the present invention is suitable as an automatic transmission oil, continuously variable transmission oil, hydraulic oil, gear oil, turbine oil, compressor oil, engine oil, etc. Various additives such as viscosity index improvers, ashless dispersants, organic acid metal salts (metal-based detergents), friction modifiers are used to adjust the necessary viscosity and meet the required performance depending on the application. Antifriction agents, antioxidants, extreme pressure agents, metal deactivators, pour point depressants, rust inhibitors, colorants and the like can be added as appropriate.

As viscosity index improvers, generally non-dispersed polymethacrylate, dispersed polymethacrylate, non-dispersed olefin copolymer (polyisobutylene, ethylene-propylene copolymer), dispersed olefin copolymer, polyalkylstyrene, styrene-butadiene Examples thereof include hydrogenated copolymers, styrene-maleic anhydride ester copolymers, and star-shaped isoprene. The non-dispersed olefin copolymer has a dispersion performance without containing oxygen or nitrogen in the molecule. The molecular weight of polyisobutylene or ethylene-propylene copolymer is preferably 100,000 or more in terms of weight average molecular weight (polystyrene equivalent in GPC analysis). This may be used alone or in combination. Usually, it is used in a proportion of 0.01% to 30% by weight.

Ashless dispersants include succinimides, succinamides, benzylamines, succinic acid esters, succinic acid esters-amides and the like and their boron content, but succinimides and borons A succinimide system is preferably used. The compounding quantity of a succinimide type | system | group and a boron containing succinimide type | system | group is 0.05 to 8 weight% normally.

Examples of the metal detergent include those containing a compound selected from sulfonates such as calcium, magnesium and barium, phenates, salicylates, and carboxylates, such as overbased salts, basic salts, and neutral salts. Those having different base numbers can be arbitrarily selected and used. These compounding amounts are usually preferably used in the range of 0.05% by weight to 5% by weight as the amount of metal element.

Examples of the friction modifier include organic molybdenum compounds, fatty acids, higher alcohols, fatty acid esters, oils and fats, amines, polyamides, sulfurized esters, phosphate esters, acidic phosphate esters, phosphite esters, phosphate ester amine salts. Etc. These are usually used in a proportion of 0.05 to 5% by weight.

Antiwear agents generally include zinc dithiophosphate, metal dithiophosphate (Pb, Sb, Mo, etc.), metal dithiocarbamate (Zn, Pb, Sb, Mo, etc.), metal naphthenate (Pb, etc.), fatty acid metal salt, etc. (Pb, etc.), boron compounds, phosphate esters, phosphite esters, phosphate ester amine salts, and the like, and are usually used at a ratio of 0.1 wt% to 5 wt%.

As the antioxidant, amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, 2,6-di-t-butylphenol, 4,4′-methylenebis (2 , 6-di-t-butylphenol), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like, and dilauryl-3,3′-thiodipropionate. Sulfur-based antioxidants such as phosphites, molybdenum-based antioxidants, molybdenum-based antioxidants, and zinc dithiophosphate, among others, amine-based antioxidants, phenol-based antioxidants, and combinations thereof Is preferably used. These are usually used in a proportion of 0.05 to 5% by weight.

Examples of extreme pressure agents generally include ashless sulfide compounds, sulfurized fats and oils, phosphate esters, phosphite esters, phosphate ester amine salts, etc., and these are usually in a proportion of 0.05% to 3% by weight. Used in.

Examples of the metal deactivator include benzotriazole, triazole derivatives, benzotriazole derivatives, thiadiazole derivatives and the like, and these are usually used in a proportion of 0.01% by weight to 3% by weight.

  Pour point depressants generally include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene, etc. Methacrylate is preferably used. These are usually used in a proportion of 0.01% to 5% by weight.

Examples of the rust inhibitor include fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonic acid group, polyhydric alcohol fatty acid ester, fatty acid amine, oxidized paraffin, alkyl polyoxyethylene ether, and the like. Used in a proportion of 0.01% to 3% by weight.

In particular, as an additive package for automatic transmission fluid (ATF), a useful additive is selected from the above-mentioned additive group so as to exhibit performance such as slip control as a drive system fluid of the automatic transmission. Can be used, but usually contains an antioxidant, detergent dispersant, metal deactivator, antiwear agent, viscosity index improver, rust inhibitor, corrosion inhibitor, etc. in addition to the friction modifier It is. Specific examples of the amount of each additive are as described below. The lubricating oil composition formulated with the antifoam composition according to the present invention can suppress foaming or destroy the formed bubbles, and any additive formulation has a problem in suppressing foaming. Does not occur.

  Also, a commercially available additive package for automatic transmission fluid (ATF) can be used in practicing the present invention. For example, an ATFWS package can be used.

Preferred content (wt%)
Metal detergent 0.05-5.0
Viscosity index improver 4.0 to 30.0
Ashless dispersant 0.1-5.0
Antioxidant 0.1-3.0
Extreme pressure agent 0.1-2.0
Metal deactivator 0.01-2.0
Antiwear agent 0.1-3.0
Friction modifier 0.1-5.0
Pour point depressant 0.01-8.0
Corrosion inhibitor 0.01-5.0

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples.

  In addition, about the composition of a base oil and the antifoamer mixed solution which were used by the Example and the comparative example, a performance evaluation test, etc. are shown next. Further, “%” in Examples and the like indicates% by weight.

Base oil (1) Mineral oil base oil Solvent refined and hydrotreated mineral oil 100 ° C kinematic viscosity; 3mm ² / s
(2) Synthetic oil base oil Polyalphaolefin oligomer 100 ° C. kinematic viscosity; 3 mm ² / s

Antifoam mixed solution The antifoam mixed solution is a mixed solution of the following components (A), (B) and (C), and the mixing ratio of each component is shown in Table 1.

Component (A); fluorine-containing organic compound (1) Central Glass Co. _{MTF-TFM; CF 3 -C 6} H 4 -CF 3
(2) Asahi-CleanAE3000 manufactured by Asahi Glass;
CF ₃ —CH ₂ —O—CF ₂ —CHF ₂
(3) manufactured by 3M _{HFE7200; C 4 F 9 -O-} C 2 H 5
(4) Vertrel manufactured by DuPont; C ₅ H ₂ F ₁₀

Component (B); fluorinated silicone (1) FL-100-450CS manufactured by Shin-Etsu Chemical Co., Ltd.
(2) FA-630 manufactured by Shin-Etsu Chemical Co., Ltd.

Component (C): hydrocarbon-based or alcohol-based organic solvent n-heptane, kerosene, light oil, alkene L (alkylbenzene manufactured by Nippon Oil Co., Ltd.), toluene, methanol

Component (D). Fluorosurfactant (1) MegaFuck F-477 manufactured by DIC
(2) Megafuck F-483 manufactured by DIC

Other Additive Package for ATF Additive Package without ATFWS Antifoam
Metal detergent Afton Chemical Company Hitech 614 (calcium sulfonate)

Performance evaluation method Appearance observation test and defoaming performance were evaluated by the following method: (1) Appearance observation test A sample was taken 100CC in a 200CC beaker and held in a constant temperature air oven adjusted to 20 ° C for 24 hours, and then a white light source was used. Visual observation is performed in the state of being installed behind the beaker. At that time, the presence or absence of the transmittance that can be clearly confirmed by the white light source is further observed for the presence or absence of separation and cloudiness.
(2) Defoaming performance test 200 CC was sampled in a 500 CC tall beaker, heated to 120 ° C. with a hot plate, and then stirred for 3 minutes with a homogenizer (manufactured by IKA) while blowing air at 100 ml / min. The liquid level is measured and used as the amount of foaming.

In the following examples and comparative examples, an antifoam mixed solution is blended, and after the preparation of the trial oil and after standing for 7 days, an antifoaming performance test is performed, and the former is initially set for each test result (foaming amount). Defoaming performance, the latter is called storage stability.
Example 1
Fluorinated silicone FL-100-450cs was dissolved in fluorine-containing organic compound MTF-TFM (bis (trifluoromethyl) benzene), and then the whole was further dissolved in a hydrocarbon solvent (n-heptane) to obtain fluorinated silicone 3 %, 68% of bis (trifluoromethyl) benzene and 29% of n-heptane were prepared as an antifoam mixed solution M1 (see Table 1-1). When the mixed solution M1 was subjected to the performance evaluation test and the appearance was observed, it was transparent.

    The antifoam mixed solution M1 having a transparent appearance prepared as described above was blended with the mineral oil base oil to prepare a trial oil 1 having the composition shown in Table 2-1.

    Except for Examples 16 to 19 and Comparative Example 9, the ATF additive package is used as an additive in addition to the prototype oils prepared in all of the following Examples and Comparative Examples, based on the total weight of the prototype oil. 20%. In Examples 16 to 19 and Comparative Example 7, the metal detergent was blended at 5% by weight based on the total weight of the trial oil.

  When the trial oil 1 was subjected to the defoaming performance test, the defoaming performance immediately after preparation of the trial oil was 12 mm, the defoaming performance after standing for 7 days was 14 mm, and the level of defoaming performance was high. There was almost no decrease, indicating excellent storage stability.

Example 2
Except for using Asahi-clean AE-3000 (CF ₃ CH ₂ OCF ₂ CHF ₂ ) in place of the fluorine-containing organic compound MTF-TFM (bis (trifluoromethyl) benzene), all are the same as the components of Example 1 An antifoam mixed solution M2 containing the same components at the same ratio was prepared. According to the appearance observation of the mixed solution M2, it was transparent.

  The antifoam mixed solution M2 prepared as described above was blended with the base oil to prepare a trial oil 2 having the composition shown in Table 2-1.

  When the trial oil 2 was subjected to the defoaming performance test, the defoaming performance immediately after preparation was 12 mm, and the defoaming performance after standing for 7 days was 12 mm, which was excellent as in the trial oil 1 of Example 1. Defoaming performance and storage stability were shown.

Example 3
Example 1 except that a fluorine-containing organic compound HFE7200 perfluoroptylethyl ether (C ₄ F ₉ OC ₂ H ₅ ) was used instead of the fluorine-containing organic compound MTF-TFM (bis (trifluoromethyl) benzene) A defoaming agent mixed solution M3 containing the same component as the above component in the same proportion was prepared. The mixed solution M3 was transparent according to the appearance observation.

  The antifoam mixed solution M3 prepared as described above was blended with the base oil to prepare a trial oil 3 having the composition shown in Table 2-1.

  When the trial oil 3 was subjected to the defoaming performance test, the defoaming performance immediately after preparation was 12 mm, the defoaming performance after standing for 7 days was 13 mm, and excellent initial defoaming performance and storage stability thereof were shown. It was done.

Examples 4-6
As shown in Table 1-1, antifoam mixed solutions M4 to M6 were prepared using fluorinated silicone FA-630 and using a fluorine-containing organic compound and a hydrocarbon solvent in the proportions shown in the same table.

    Mixed solutions M4 to M6 were blended with the base oil, respectively, to prepare trial oils 4 to 6 having the compositions shown in Table 2-1. The results of performance evaluation are shown in the same table.

Examples 7-11
Fluorinated silicone FL-100-450cs and fluorine-containing organic compound MTF-TFM and various hydrocarbon solvents shown in Table 1-1 and Table 1-2 are mixed at a ratio shown in the same table, and mixed solutions M7 to M11 are mixed. Prepared. These mixed solutions were transparent according to the above-mentioned appearance observation.

Mixed solutions M7 to M11 were blended with the base oil, respectively, to prepare trial oils 7 to 11 having the compositions shown in Table 2-1. The defoaming performance is shown in the same table.
Examples 12-15
Fluorinated surfactant F-477 or F-483 mixed with fluorinated silicone FA-630, fluorine-containing organic compound MTF-TFM, and a mixture of kerosene as a hydrocarbon solvent as shown in Table 1-2 M12 to M15 were blended in the base oil, respectively, and trial oils 12 to 15 having the compositions shown in Table 2-1 were prepared.
The performance evaluation of the prototype oil was performed by the above performance evaluation test, and the results shown in Table 2 were obtained.

Examples 16-19
All the examples except that each of the antifoam mixed solutions M12 to M15 shown in Table 1-2 was added to the base oil containing the metal detergent instead of the ATF package as shown in Table 2-1. Sample oils 16 to 19 were prepared in the same manner as in Example 1. The results of performance evaluation are shown in Table 2-2.

Example 20
Sample oil 20 was prepared using the same antifoam mixed solution M1 in the same manner as in Example 1 except that synthetic oil was used instead of mineral oil as the base oil.
The performance evaluation of the trial oil 20 was performed by the above performance evaluation test, and the defoaming results shown in Table 2-2 were obtained.

  According to the performance evaluation, it has been found that even if the base oil is a mineral oil or a synthetic oil, the difference does not have a great influence on the defoaming effect.

Example 21
Sample oil 21 was prepared using the same antifoam mixed solution M1 in the same manner as in Example 1 except that neither the additive package for ATF nor the additive for the metal detergent was used.
The performance evaluation of the trial oil 21 was performed by the above performance evaluation test, and the defoaming effect shown in Table 2-2 was obtained.

Comparative Example 1
After dissolving fluorinated silicone FL-100-450cs in fluorine-containing aliphatic hydrocarbon solvent C ₅ H ₂ F ₁₀ at the ratio shown in Table 1-2, the whole is dissolved in a hydrocarbon solvent (kerosene) and mixed solution M16 was prepared. The fluorine-containing aliphatic hydrocarbon solvent departs from the range of the fluorine-containing organic compound of the present invention, and the appearance of the mixed solution was cloudy. The mixed solution M16 was blended with the base oil to prepare a trial oil a having the composition shown in Table 2-2.
The results of the performance evaluation of the prototype oil a are shown in Table 2-2. From this result, it was found that the storage stability was particularly lacking.

Comparative Example 2
A mixed solution M17 was prepared by dissolving fluorinated silicone FL-100-450cs in a fluorine-containing organic compound HFE7200, but a hydrocarbon-based or alcohol-based organic solvent was not used. The appearance of the mixed solution M17 was transparent. Next, the mixed solution M17 was blended with the base oil to obtain a trial oil b having the composition shown in Table 2-2. The trial oil b lacks an organic solvent as described above, and as shown in the table, it was found that the initial defoaming performance was low and the storage stability was lacking.

Comparative Example 3
Fluorinated silicone FL-100-450cs was dissolved only in a hydrocarbon solvent (kerosene). The obtained mixed solution M18 lacked the fluorine-containing organic compound and was transparent, but when the mixed solution 18 was blended with the base oil to prepare the trial oil c, the trial oil c was separated into two layers. did.

Comparative Example 4
A mixed solution M19 containing only the fluorine-containing organic compound HFE7200 and a hydrocarbon solvent (kerosene) was prepared without using fluorinated silicone. According to the appearance observation of the mixed solution 19, it was transparent. As shown in Table 2-2, mixed solution M19 was blended with the base oil to prepare trial oil d having the composition shown in the same table.
When the prototype oil d was subjected to the performance evaluation test, no defoamer performance was obtained for both the initial defoaming performance and storage stability.

Comparative Example 5
As shown in Table 2-2, only the fluorinated silicone FL-100-450cs was blended with the lubricant base oil and the additive package for ATF to prepare trial oil e. The results evaluated by the defoaming performance test are shown in the same table. As a result of the performance evaluation, the initial defoaming performance and the storage stability were similarly inferior to those of the trial oil f containing no fluorinated silicone, even though fluorinated silicone was blended. This fact also shows the effectiveness of the antifoam mixed solution.

Comparative Example 6
As shown in Table 2-2, a trial oil f having a composition of only the base oil and the additive package for ATF was prepared. The results of performance evaluation are shown in the same table.

Comparative Example 7
A trial oil g was prepared by the same operation as in Comparative Example 6 except that the metal detergent was blended with the base oil in the ratio shown in Table 2-2 instead of the ATF additive package.

  The results of performance evaluation are shown in Table 2-2.

From the results of the above examples and comparative examples, when preparing a lubricating oil composition, a transparent defoamer mixed solution in which a fluorine-containing organic compound, a fluorinated silicone, and a hydrocarbon-based or alcohol-based organic solvent are mixed is used. As a result, it was found that the lubricating oil composition has a remarkable effect on the initial defoaming performance and its storage stability.

Claims (10)

An antifoaming agent composition used as a component of a lubricating oil composition, comprising the following components (A), (B) and (C).
(A) at least one fluorine-containing organic compound selected from the group consisting of fluorine organic compounds represented by the following general formulas (1) and (2),

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

(In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si,
(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or the alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing carbon atom having 1 to 10 carbon atoms. Substituents selected from the group consisting of hydrogen groups, and two or more kinds of substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 10 to 10 fluorine-containing hydrocarbon groups,
(Iv) m is 1-6,
(V) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents selected from the group consisting of two or more substituents may be the same or different from each other, but at least one substituent has 1 to 10 carbon atoms. A fluorine-containing hydrocarbon group,
(Vi) n is 2-5. )
(B) fluorinated silicone and (C) hydrocarbon-based or alcohol-based organic solvent.
The antifoaming composition according to claim 1, wherein the fluorine-containing organic compound of the component (A) is a compound having a structure represented by the following general formula (11) or general formula (22).

R ₁₁ -XR ₁₂ (11)

R ₂₁ -YR ₂₂ (22)

(In the general formulas (11) and (22),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O or S,
(Iii) R ₁₁ and R ₁₂ are each a fluorine atom substituted with two hydrogen atoms of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. The substituent is selected from the group consisting of 10 fluorine-containing hydrocarbon groups, and the substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 fluorine-containing hydrocarbon groups,
(Iv) R ₂₁ and R ₂₂ are substituents bonded to the group containing a hetero atom, and are a group consisting of a hydrocarbon group having 1 to 10 carbon atoms and a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. The substituents may be the same or different, and at least one substituent is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. )
The mixing ratio of the component (A), the component (B) and the component (C) of the antifoam composition is 2 to 98% by weight of the component (A) based on the total weight of the antifoam composition, and the component (B) The antifoaming composition according to any one of claims 1 to 2, which is 0.01 to 10% by weight and component (C) is 2 to 98% by weight.
The antifoaming composition according to claim 1, wherein the component further added to the component consisting of the component (A), the component (B), and the component (C) is a component (D) fluorine-based surfactant.
A lubricating oil composition comprising a lubricating base oil and the antifoam composition according to any one of claims 1 to 4 blended in the lubricating base oil.
The lubricating oil composition according to claim 5, wherein the amount of the antifoaming agent composition is 0.05 to 10% by weight based on the total amount of the lubricating oil composition.
The lubricating oil composition according to claim 5, wherein the lubricating base oil has a kinematic viscosity at 100 ° C. of ² to 10 mm ² / _S.
The lubricating oil composition according to any one of claims 5 to 7, wherein the lubricating oil composition is used for automobile automatic transmission oil, continuously variable transmission oil, and other drive system fluids.
(A) the following general formulas (1) and (2);

X- (R ¹ ) _m (1)

Y- (R ² ) _n (2)

(In general formulas (1) and (2),
(I) X is an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
(Ii) Y is a group containing at least one hetero atom of O, S, N, P or Si,
(Iii) R ¹ is a fluorine atom substituted with a hydrogen atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms, and a fluorine-containing hydrocarbon having 1 to 10 carbon atoms. Substituents selected from the group consisting of groups, and two or more kinds of substituents may be the same or different from each other, but at least one substituent is a fluorine atom or a carbon number of 1 to 10 Fluorine-containing hydrocarbon group, m is 1-6,
(Iv) R ² is a substituent bonded to the group containing a hetero atom, and is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. A substituent selected from the group consisting of two or more substituents which may be the same or different from each other, but at least one substituent is fluorine having 1 to 10 carbon atoms It is a containing hydrocarbon group, and n is 2-5. )
The reaction is stopped by mixing at least one fluorine-containing organic compound selected from the group consisting of fluorine-containing organic compounds represented by the following formula: (B) a fluorinated silicone and (C) a hydrocarbon-based or alcohol-based organic solvent. The manufacturing method of the lubricating oil composition characterized by including the process of preparing a foaming agent composition, and the process of mix | blending the said antifoamer composition prepared in the said process with lubricating base oil.
The method for producing a lubricating oil composition according to claim 9, wherein the component further added to the component consisting of the component (A), the component (B), and the component (C) is a component (D) fluorosurfactant.