WO2016158304A1

WO2016158304A1 - Defoaming-agent composition

Info

Publication number: WO2016158304A1
Application number: PCT/JP2016/057649
Authority: WO
Inventors: 剛辰巳; 洋平薄田; 耕平増田; 中村　俊貴
Original assignee: Ｊｘエネルギー株式会社
Priority date: 2015-03-31
Filing date: 2016-03-10
Publication date: 2016-10-06
Also published as: JP6572302B2; JPWO2016158304A1

Abstract

The present invention provides a defoaming-agent composition containing a defoaming agent, at least one diluent oil selected from the group consisting of mineral oils and synthetic oils, and a gelling agent.

Description

Antifoam composition

The present invention relates to an antifoaming composition.

Conventionally, in mechanical devices such as engines and automatic transmissions, lubricating oil is used to improve lubricity between members. Generally, a lubricating oil contains a base oil and various additives that are added according to desired properties. Examples of such additives include an antifoaming agent for preventing foaming in a lubricating oil (see Patent Document 1).

When an automatic transmission or the like is filled with lubricating oil having poor antifoaming properties, there may be a problem that foamy lubricating oil leaks from the breather to the outside. In addition, if there is much foaming, the efficiency of the hydraulic pump may be reduced and seizure may occur due to running out of oil.

Especially in recent transmissions, etc., multistage and miniaturization are progressing for the purpose of improving fuel efficiency, and it is structurally difficult to prevent leakage of lubricating oil from the breather. In addition, since the viscosity of lubricating oil has been reduced for the purpose of improving fuel efficiency, and the lubricating oil itself is easily foamed, a technique capable of maintaining defoaming properties over a long period of time is required.

On the other hand, for example, when an organic silicone-based antifoaming agent is used as the antifoaming agent, the defoaming property gradually disappears due to the acidic component generated with the deterioration of the lubricating oil. In addition, when a fluorine-based antifoaming agent such as fluorine-modified silicone or perfluoropolyether is used, since the specific gravity of the defoaming agent is relatively large, not only storage stability but also sedimentation in a device such as a transmission, The uneven distribution tends to occur, and the defoaming properties gradually disappear.

JP 2010-132792 A

An object of the present invention is to provide an antifoaming agent composition that can suitably maintain the antifoaming property of a lubricating oil.

First, the inventors of the present invention have a low-solubility in a lubricating oil of a high-viscosity and gel-like antifoaming agent, or a gelling or semisolid product obtained by adding a gelling agent to an antifoaming agent. The antifoaming composition of the above was studied, and the antifoaming property was maintained by gradually releasing the antifoaming agent into the lubricating oil by contacting with the lubricating oil.

However, in the case of an antifoaming agent that is simply a high-viscosity and gel-like material or an antifoaming agent composition in which a gelling agent is added to the antifoaming agent, strong shear or strong flow due to stirring or the like does not occur in the lubricating oil. And an effective amount of antifoam was found not to be released and dispersed in the lubricating oil. In other words, in the environment where the lubricating oil is actually used, the strong shear and the strong flow as described above usually do not occur. When the antifoam composition is used, the lubricating oil is not necessarily consumed. The foamability cannot be maintained.

Therefore, as a result of further studies by the present inventors, the antifoaming agent composition in which the antifoaming agent is dissolved in a predetermined diluent oil and then the gelling agent is added has the strong shear and strong flow as described above. The present inventors have found that it is possible to effectively release an antifoaming agent into a lubricating oil even under a use environment without any water, and the present invention has been completed.

That is, the present invention provides an antifoaming agent composition comprising an antifoaming agent, at least one diluent oil selected from the group consisting of mineral oil and synthetic oil, and a gelling agent.

In this antifoaming agent composition, a predetermined diluent oil that is easily soluble in the lubricating oil is used, and dissolution of the diluent oil in the lubricating oil serves as a driving force for releasing the antifoaming agent. It is possible to effectively release and disperse the antifoaming agent in the lubricating oil even in an environment where there is no strong shear or strong flow.

An antifoaming composition that does not contain a gelling agent is an antifoaming composition in which an antifoaming agent is contained in a solid paraffin wax or microwax, and the antifoaming composition is brought into contact with a lubricating oil. Although it is thought that a foaming agent can be discharge | released, in this case, the solubility with respect to the lubricating oil of an antifoamer composition is too high, and there exists a problem in the point which cannot always maintain an antifoaming property. Paraffin wax and microwax are difficult to maintain in a gel-like form in an apparatus such as an automatic transmission that is exposed to high temperatures. These problems also occur when an antifoaming agent is contained in a high viscosity additive such as a viscosity index improver or a dispersant generally used as a lubricating oil additive.

The gelling agent preferably contains an amide compound.

The content of the diluent oil is preferably 60% by mass or more based on the total amount of the antifoam composition.

The melting point of the gelling agent is preferably 120 ° C. or higher.

The antifoam composition preferably has a consistency of 475 or less.

According to the present invention, it is possible to provide an antifoaming agent composition that can suitably maintain the antifoaming property of the lubricating oil.

It is a schematic diagram which shows the homogenizer testing machine used in the Example.

Hereinafter, embodiments of the present invention will be described.

The antifoaming composition according to this embodiment contains an antifoaming agent, at least one diluent oil selected from the group consisting of mineral oil and synthetic oil, and a gelling agent.

Examples of antifoaming agents include organic silicone antifoaming agents and fluorine antifoaming agents. Examples of the organic silicone antifoaming agent include dimethyl silicone and organically modified silicone. Examples of the fluorine-based antifoaming agent include fluorine-modified silicone (fluorosilicone) and perfluoropolyether. Antifoaming agents other than those described above, such as alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, methyl salicylate, o-hydroxybenzyl alcohol, aluminum stearate, potassium oleate, N -Dialkyl-allylamine nitroaminoalkanols, aromatic amine salts of isoamyloctyl phosphate, alkylalkylene diphosphates, metal derivatives of thioethers, metal derivatives of disulfides, fluorine compounds of aliphatic hydrocarbons, triethylsilane, dichlorosilane, alkylphenyl polyethylene glycol Ether sulfide, fluoroalkyl ether and the like may be used.

The content of the antifoaming agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more based on the total amount of the antifoaming agent composition from the viewpoint of defoaming properties. It is. The content of the antifoaming agent is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, based on the total amount of the antifoaming agent composition, from the viewpoint of dispersibility in the lubricating oil. is there. The content of the antifoaming agent is preferably 0.1 to 20% by mass, 0.1 to 15% by mass, 0.1 to 10% by mass from the viewpoint of achieving both defoaming properties and dispersibility in the lubricating oil. 0.5 to 20% by mass, 0.5 to 15% by mass, 0.5 to 10% by mass, 1 to 20% by mass, 1 to 15% by mass, or 1 to 10% by mass.

Dilution oil is an oil that functions as an auxiliary agent when the antifoaming agent is released into the lubricating oil from the antifoaming agent composition. Such diluent oil is at least one selected from the group consisting of mineral oil and synthetic oil. Examples of the mineral oil include solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil, and solvent dewaxed oil. Synthetic oils include, for example, poly α-olefin or hydride thereof, isobutene oligomer or hydride thereof, isoparaffin, alkylbenzene, alkylnaphthalene, monoester, diester, polyol ester, polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl ether, and the like. Can be mentioned. The diluent oil is preferably a mineral oil or synthetic oil that does not contain silicon and fluorine as constituent elements from the viewpoint of excellent compatibility with the lubricating oil to which antifoaming properties should be imparted.

The kinematic viscosity at 100 ° C. of the diluted oil is preferably 1 mm ² / s or more, more preferably 1.5 mm ² / s from the viewpoint of the flash point of the lubricating oil when dissolved in the lubricating oil to which antifoaming properties should be imparted. That's it. The kinematic viscosity at 100 ° C. of the diluted oil is preferably 20 mm ² / s or less, more preferably 10 mm ² / s or less, and still more preferably 5 mm ² / s or less, from the viewpoint of dispersibility in the lubricating oil.

The content of the diluent oil is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably from the viewpoint that the defoaming agent can be more suitably released into the lubricating oil based on the total amount of the antifoaming agent composition. 80% by mass or more. The content of the diluent oil may be, for example, 98% by mass or less based on the total amount of the antifoaming agent composition.

The gelling agent is a compound that can form a gel-like or semi-solid antifoaming agent composition. Examples of the gelling agent include amide compounds, urea compounds, and metal soap compounds.

An amide compound is a compound having at least one amide group (—NH—CO—). The amide compound may be a monoamide compound having one amide group, a bisamide compound having two amide groups, or a triamide compound having three amide groups. Among these, the triamide compound is most preferable because the antifoaming agent composition can be gelled even in a relatively small amount, and adverse effects on the lubricating oil can be minimized. The monoamide compound may be a monoamine acid amide or a monocarboxylic acid amide. The bisamide compound may be a diamine acid amide or a dicarboxylic acid amide.

The monoamide compound is represented, for example, by the following formula (1). The bisamide compound is represented by, for example, the following formula (2) or (3). The triamide compound is represented, for example, by the following formula (4).
R ¹ —CO—NH—R ² (1)
R ³ —CO—NH—A ¹ —NH—CO—R ⁴ (2)
R ⁵ —NH—CO—A ² —CO—NH—R ⁶ (3)
R ⁷ -MA ³ -CH (A ⁴ -MR ⁸ ) -A ⁵ -MR ⁹ (4)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrocarbon group having 5 to 25 carbon atoms. The hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group. R ² may be a hydrogen atom. A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. M represents an amide group.

In the formula (1), R ² is preferably a hydrogen atom or a saturated or unsaturated chain hydrocarbon group having 10 to 20 carbon atoms. In the formulas (2) and (3), A ¹ and A ² are each preferably a divalent saturated chain hydrocarbon group having 1 to 4 carbon atoms. In the formulas (2) and (3), in the hydrocarbon groups represented by R ³ , R ⁴ , R ⁵ , R ⁶ , A ¹ or A ² , some hydrogen atoms are each substituted with a hydroxyl group (—OH). May be.

As the amide compound, an amide compound in which A ¹ , A ² , A ³ , A ⁴ and A ⁵ are chain hydrocarbon groups is preferable. When A ¹ , A ² , A ³ , A ⁴ and A ⁵ are chain hydrocarbon groups, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R in the same molecule as A ⁹ is preferably a saturated or unsaturated chain hydrocarbon group having 10 to 20 carbon atoms.

When at least one of A ¹ , A ² , A ³ , A ⁴ and A ⁵ is an aromatic hydrocarbon group, R ³ , R ⁴ , R ⁵ in the same molecule as A, which is an aromatic hydrocarbon group, R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably a saturated or unsaturated chain hydrocarbon group having 10 to 20 carbon atoms or an aromatic hydrocarbon group.

Specific examples of monoamide compounds include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide and hydroxystearic acid amide, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide, And amides of saturated or unsaturated long-chain fatty acids and long-chain amines such as stearyl stearamide, oleyl oleate, oleyl stearate, stearyl oleamide, and the like.

Specific examples of the acid amide of the diamine represented by the formula (2) include ethylene bis stearic acid amide, ethylene bis isostearic acid amide, ethylene bis oleic acid amide, methylene bis lauric acid amide, and hexamethylene bis oleic acid amide. And hexamethylene bishydroxystearic acid amide. Specific examples of the acid amide of the dicarboxylic acid represented by the formula (3) include N, N′-bisstearyl sebacic acid amide.

Among these bisamide compounds, R ¹ , R ² , R ³ and R ⁴ in formula (2) and formula (3) are each independently a saturated or unsaturated chain hydrocarbon group having 12 to 20 carbon atoms. Is preferred.

Specific examples of the triamide compound include N-acylamino acid diamide compounds represented by the following formula (5).

In the formula (5), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrocarbon group preferably having 1 to 30 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 3 to 16 carbon atoms. N represents 1 or 2.

The N-acyl group (R ¹⁰ —CO—) in the N-acylamino acid diamide compound may be a linear or branched saturated or unsaturated aliphatic acyl group or aromatic acyl group having 1 to 30 carbon atoms. Preferably a caproyl group, a capryloyl group, a lauroyl group, a myristoyl group, or a stearoyl group. R ¹¹ and R ¹² may be a linear or branched saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably a butyl group, an octyl group, a lauryl group, an isostearyl group, stearyl. Group. The N-acylamino acid diamide compound represented by the formula (5) is preferably N-lauroyl-L-glutamic acid-α, γ-di-n-butyramide.

The melting point of the gelling agent is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and still more preferably 140 ° C. or higher, from the viewpoint of maintaining the shape even in a high temperature environment where the antifoaming agent composition is used. The melting point of the gelling agent may be 180 ° C. or lower, for example.

The content of the gelling agent is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3%, based on the total amount of the antifoaming agent composition, from the viewpoint that the antifoaming agent composition can be suitably gelled. It is at least mass%. The content of the gelling agent is preferably 20% by mass or less, more preferably 10% by mass based on the total amount of the antifoaming agent composition, from the viewpoint that the adverse effect on the lubricating oil after releasing the antifoaming agent can be minimized. Hereinafter, it is more preferably 5% by mass or less. The content of the gelling agent can favorably gel the antifoam composition. In view of minimizing adverse effects on the lubricating oil after the release of the antifoaming agent, it is preferably 1 to 20% by weight, 1 to 10% by weight, and 1 to 5% by weight based on the total amount of the antifoaming agent composition. 2 to 20% by mass, 2 to 10% by mass, 2 to 5% by mass, 3 to 20% by mass, 3 to 10% by mass, or 3 to 5% by mass.

The defoamer composition is a gel or semi-solid composition at normal temperature (25 ° C.). The consistency of the antifoam composition is preferably 475 or less, more preferably 430 or less, from the viewpoint of maintaining the shape over a long period of time even in an environment where the antifoam composition is used. In other words, the consistency of the antifoam composition is preferably No. 000 consistency or harder consistency, and more preferably No. 00 consistency or harder consistency. The consistency of the antifoam composition may be 175 or more, for example.

“Consistency” in the present invention means a penetration consistency measured in accordance with JIS K2220. Specific measurement conditions are as follows. The sample is packed in a penetration measuring pot and kept at 25 ° C., and then mixed 60 times in 1 minute using a specified mixer. Next, after removing the excess sample with a spatula and flattening the surface of the sample, the specified cone is dropped into the sample for 5 seconds, and the blending consistency is 10 times the depth (mm) of penetration. .

The antifoam composition may further contain other additives in addition to the above components. Examples of other additives include extreme pressure agents, metallic detergents, ashless dispersants, antioxidants, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, ashless friction modifiers, and the like. It is done. The content of other additives may be, for example, 20% by mass or less based on the total amount of the antifoaming agent composition.

As described above, a composition containing an antifoaming agent, at least one diluent oil selected from the group consisting of mineral oil and synthetic oil, and a gelling agent is suitably used as an antifoaming agent composition. The The antifoam composition is preferably used as an additive for lubricating oil. The application of the lubricating oil is not particularly limited, and an application requiring maintenance of defoaming properties is preferable. Lubricating oils include, for example, gasoline engine oils for motorcycles, automobiles, ships, power generation, etc .; diesel engine oils; gas engine oils; automatic transmissions, manual transmissions, final reduction gears, gear drives, etc. A lubricating oil for a system; a wet brake oil; a hydraulic fluid; a turbine oil; a compressor oil; a bearing oil;

The defoamer composition releases the defoamer into the lubricating oil by contacting the lubricating oil in some way. The method of bringing the antifoam composition into contact with the lubricating oil is not particularly limited. For example, the antifoam composition is disposed at a predetermined position on the wall surface of the oil tank (for example, a position reached when a predetermined amount of lubricating oil is bubbled). The antifoaming agent is released into the lubricating oil as necessary. Further, for example, by installing an antifoaming agent composition in the lubricating oil of the oil tank, the antifoaming agent is released into the lubricating oil over time. By these methods, it becomes possible to maintain the antifoaming property of the lubricating oil over a long period of time. Further, for example, by installing the antifoaming composition in a circuit near the breather, it is possible to prevent leakage from the breather due to foaming. The release rate of the antifoaming agent can be adjusted, for example, by adjusting the type and content of each component contained in the antifoaming agent composition based on the above embodiment.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.

Using the following diluent oil, antifoaming agent, gelling agent, and other additives, antifoaming compositions having the compositions shown in Tables 1 to 3 were prepared. The composition in a table | surface is shown by the mass% on the defoamer composition whole quantity basis.

[Defoaming agent]
A1: Dimethyl silicone (25 ° C. kinematic viscosity 50000 mm ² / s)
A2: Dimethyl silicone (25 ° C. kinematic viscosity 500000 mm ² / s)
A3: Fluorine-modified silicone (25 ° C. kinematic viscosity 2000 mm ² / s)
[Diluted oil]
B1: Hydrorefined mineral oil (40 ° C. kinematic viscosity 7.1 mm ² / s, 100 ° C. kinematic viscosity 2.2 mm ² / s, viscosity index 109, sulfur content less than 1 ppm)
B2: Hydrorefined mineral oil (40 ° C. kinematic viscosity 19.4 mm ² / s, 100 ° C. kinematic viscosity 4.2 mm ² / s, viscosity index 125, sulfur content less than 1 ppm)
B3: poly α- olefin (40 ° C. kinematic viscosity 5.4mm ² / s, 100 ℃ kinematic viscosity 1.7 mm ² / s)
B4: Poly α-olefin (40 ° C. kinematic viscosity 66 mm ² / s, 100 ° C. kinematic viscosity 10 mm ² / s, viscosity index 136)
[Gelling agent]
C1: Triamide compound (melting point 150 ° C., “GP-1 (N-lauroyl-L-glutamic acid-α, γ-di-n-butyramide)” manufactured by Ajinomoto Co., Inc.)
C2: Diamide compound (melting point: 145 ° C., Nippon Kasei Co., Ltd. “Sripax E (ethylene bis stearamide)
C3: Diamide compound (melting point 119 ° C., Nippon Kasei Co., Ltd. “Sripacs O (ethylenebisoleic acid amide)”
[Other additives]
D1: Phosphite ester antiwear agent (phosphorous addition amount (composition basis) 300 mass ppm), overbased Ca sulfonate (Ca addition amount (composition basis) 100 mass ppm), non-borated succinimide ( Bis type, addition amount (composition basis) 2.0 mass%), boronated succinimide (bis type, addition amount (composition basis) 2.0 mass%, boron addition amount (composition basis) 50 mass ppm ), Additive package for transmission oil containing antioxidant, oil seal swelling agent, etc.

The following off-site release test was conducted using each of the obtained antifoam compositions. Further, the following on-site release test was conducted using the antifoaming compositions of Examples 3, 6, 7, and 9 and Comparative Example 1. The results are shown in Tables 1 to 3, respectively.

[Offsite release test]
The antifoam composition 5 g was immersed for 72 hours at 80 ° C. with respect to 200 g of the reference oil from which the antifoam was removed from the lubricating oil (“ENEOS FINE AT FLUID” manufactured by JX Nippon Oil & Energy Corporation). A homogenizer test was performed on the supernatant of the reference oil (sample oil) after immersion in the antifoaming agent, and the amount of foaming was evaluated.

FIG. 1 is a schematic diagram showing a homogenizer testing machine. As shown in FIG. 1, a homogenizer testing machine 10 includes a homogenizer 1, a heating cylindrical heater 2, a temperature controller 3, a thermocouple 4 for oil temperature measurement, a heater heating power source 5, and a glass cylinder 6 corresponding to an oil tank (scale). A lunar cylindrical glass container, an inner diameter of 40 mm, a depth of 300 mm, a scale: 0 to 250 mL at 2 mL intervals), and an air blowing pipe (air inflow rate of 30 mL / min) 7 are provided.

In the homogenizer test, 150 mL of sample oil was placed in the glass cylinder 6 and the sample oil was heated to 120 ° C. with the heating cylindrical heater 2. The oil level of the sample oil at this time was defined as the reference oil level 8. The sample oil was stirred at 20000 rpm by the homogenizer 1, and the amount of foaming (mL) was calculated from the difference between the oil level 9 and the reference oil level 8 10 minutes after the start of stirring.

[On-site release test]
When the homogenizer test (120 ° C., 20000 rpm, 10 minutes) was performed on the above-mentioned reference oil, 2 g of the antifoam composition encapsulated in Swagelok (15 μm hole) was removed from the reference oil surface 8 on the wall surface of the glass cylinder 6. Was installed at a height corresponding to 80 mL of foaming volume, and the foaming volume after the homogenizer test was evaluated.

DESCRIPTION OF SYMBOLS 1 ... Homogenizer, 2 ... Cylindrical heater for heating, 3 ... Temperature controller, 4 ... Thermocouple for oil temperature measurement, 5 ... Power supply for heater heating, 6 ... Glass cylinder, 7 ... Air blowing pipe, 8 ... Reference oil level , 9 ... Oil level after 10 minutes from the start of stirring.

Claims

An antifoam,
At least one diluent oil selected from the group consisting of mineral oil and synthetic oil;
A gelling agent;
A defoamer composition containing
The antifoaming composition according to claim 1, wherein the gelling agent contains an amide compound.
The antifoaming composition according to claim 1 or 2, wherein the content of the diluent oil is 60% by mass or more based on the total amount of the antifoaming composition.
The antifoaming composition according to any one of claims 1 to 3, wherein the gelling agent has a melting point of 120 ° C or higher.
The antifoam composition according to any one of claims 1 to 4, having a consistency of 475 or less.