JP2014065848A - Dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant used in a method for removing deposits formed inside an engine.SOLUTION: A dispersant contains a carboxylic acid and an amine.

Description

  The present invention relates to a dispersant used in a method for removing deposits formed inside an engine.

  It is known that when sediment such as sludge is formed inside the engine, the engine function is deteriorated. Therefore, the formation of deposits is suppressed by adding various additives to fuel and lubricating oil.

  For example, Patent Document 1 discloses a diesel engine lubricating oil additive made of oxycarboxylic acids having a function of dispersing water-containing calcium sulfate in oil. The additive has a function of dispersing calcium sulfate, which is a component of sludge, in the lubricating oil, and can reduce sludge accumulation. Moreover, the apparatus and composition for cleaning the combustion chamber of an engine are also known (for example, patent documents 2 and 3).

JP-A-9-13065 JP-A-1-301923 JP 2003-214268 A

  The additive described in Patent Document 1 suppresses the formation of deposits by dispersing calcium sulfate, which is a component of the deposits, in the lubricating oil, and removes deposits that have already been formed. It does not have a function. In particular, when the deposit formed is in solid form, it is difficult to remove the deposit.

  Therefore, an object of this invention is to provide the dispersing agent used for the method for removing the deposit formed in the engine inside.

  As a result of intensive studies by the present inventors, it has been found that deposits can be efficiently removed by using a combination of carboxylic acid and amine.

[1] That is, the present invention includes the following inventions.
[1-1]
A carboxylic acid and an amine, the amine having the general formula:
NR ¹ R ² R ³
[Where:
R ¹ is C ₈ -C ₁₈ alkyl;
R ² and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl]
A dispersant which is an aliphatic amine represented by:
[1-2]
The dispersant according to [1-1], wherein R ² and R ³ are hydrogen.
[1-3]
The dispersant according to [1-1] or [1-2], wherein the carboxylic acid is an aliphatic polycarboxylic acid having 18 to 36 carbon atoms.
[1-4]
The amine value of the mixture of carboxylic acid and amine contained in the dispersant is 40 to 260 mgKOH / g, and the acid value is 10 to 160 mgKOH / g. The dispersant described.
[2] Moreover, the washing performance can be further improved by using the dispersant in combination with a chelating agent, a glycol solvent, and naphthenic oil. That is, the present invention includes the following inventions.
[2-1]
A dispersant comprising a carboxylic acid and an amine;
Chelating agents;
Glycol solvents; and naphthenic oils;
An engine cleaning composition comprising:
[2-2]
Amines have the general formula:
NR ¹ R ² R ³
[Where:
R ¹ is C ₈ -C ₁₈ alkyl;
R ² and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl]
The engine cleaning composition according to [2-1], which is an aliphatic amine represented by the formula:
[2-3]
The engine cleaning composition according to [2-2], wherein R ² and R ³ are hydrogen.
[2-4]
The engine cleaning composition according to any one of [2-1] to [2-3], wherein the carboxylic acid is an aliphatic polycarboxylic acid having 18 to 36 carbon atoms.
[2-5]
The amine value of the mixture of carboxylic acid and amine contained in the dispersant is 40 to 260 mgKOH / g, and the acid value is 10 to 160 mgKOH / g, and any one of [2-1] to [2-4] The composition for engine cleaning as described.
[2-6]
The engine cleaning composition according to any one of [2-1] to [2-5], wherein the chelating agent further contains an amine.

  The dispersant of the present invention can be used in a method for removing deposits formed inside an engine.

<Dispersant>
The present invention relates to a dispersant containing a carboxylic acid and an amine.
In this specification, “cleaning” means removing deposits that have already been formed. In Patent Document 1, the term “cleaning” is used as an effect of suppressing the formation of deposits (ie, a preventive effect). In this specification, “cleaning” and “cleaning” are clear. Are distinguished. Since the cleaning agent and the cleaning agent are different in use situation, purpose, and effect, they can be clearly distinguished in use.

  The dispersant of the present invention can be used to remove deposits inside the engine. The kind of deposit to be removed is not particularly limited, and deposits such as a semi-solid shape (viscous shape) and a solid shape can be removed. In particular, since the solid-form deposits, which are organic soils solidified by heat, are difficult to remove by conventional methods, the dispersant of the present invention is used in applications for removing such solid-form deposits. Preferably used.

  The components of the deposit are not limited to those containing calcium sulfate, and the dispersant of the present invention can be widely applied as long as it is a deposit formed inside the engine.

  In this specification, carboxylic acid means a compound having one or more carboxyl groups in one molecule. Although it does not specifically limit, it is preferable that it is an aliphatic carboxylic acid, and it is especially preferable that it is a C18-C36 aliphatic carboxylic acid. Further, a polycarboxylic acid having 2 or more (for example, 2 to 6) carboxyl groups in one molecule is preferable, and a dicarboxylic acid having two carboxyl groups in one molecule is particularly preferable. These carboxylic acids may be saturated carboxylic acids or unsaturated carboxylic acids. A carboxylic acid having no hydroxyl group in the molecule can also be used.

  Specific carboxylic acids include dimer acid, ricinoleic acid, citric acid, mellitic acid, gluconic acid, adipic acid, 1,8-octanedicarboxylic acid, 1,10-decanedicarboxylic acid, eicosadioic acid, tartaric acid, malic acid. Phthalic acid, maleic acid, terephthalic acid, stearic acid, lauric acid, myristic acid, behenic acid, salicylic acid and the like. Carboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

In the present invention, the amine is preferably an aliphatic amine. In particular, represented by the general formula: NR ¹ R ² R ³ , wherein R ¹ is C ₈ -C ₁₈ alkyl, and R ² and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl. It is preferable to use aliphatic amines. Aliphatic amines in which R ¹ is C ₈ -C ₁₈ alkyl and R ² and R ³ are both hydrogen are particularly excellent in cleaning performance.

  Specific amines include octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, and octadecylamine (stearyl). Amine), and amines in which one or both of hydrogen bonded to nitrogen atoms in these compounds are substituted with methyl. An amine may be used individually by 1 type and may be used in combination of 2 or more type.

  The dispersant of the present invention may further contain a solvent. The kind of solvent is not specifically limited, What is generally used can be used. In particular, an organic solvent is preferably used, and examples thereof include aroma oil, xylene, mineral spirit, isoparaffin, hexane, butyl cellosolve, and the like. A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

  In the dispersant of the present invention, the cleaning performance can be further improved by adjusting the amine value and the acid value within a certain range.

  Specifically, the amine value of the dispersant is preferably 20 to 130 mgKOH / g, more preferably 50 to 120 mgKOH / g, and particularly preferably 80 to 110 mgKOH / g. The acid value is preferably 5 to 80 mgKOH / g, more preferably 10 to 60 mgKOH / g, and particularly preferably 15 to 40 mgKOH / g. The amine value and acid value of the dispersant can be changed by the presence of optional components other than the carboxylic acid and the amine.

  On the other hand, the amine value of the mixture of carboxylic acid and amine contained in the dispersant is preferably 40 to 260 mgKOH / g, more preferably 100 to 240 mgKOH / g, and 160 to 220 mgKOH / g. Particularly preferred. The acid value is preferably 10 to 160 mgKOH / g, more preferably 20 to 120 mgKOH / g, and particularly preferably 30 to 80 mgKOH / g.

  The amine value can be measured according to the method defined in JIS K7237. The acid value can be measured according to a method defined in JIS K0070.

  The weight ratio of carboxylic acid to amine is preferably 1: 0.5 to 1: 4, particularly preferably 1: 1 to 1: 3.

  The total amount of carboxylic acid and amine is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and 40 to 60% by weight in the dispersant. Is particularly preferred.

<Engine cleaning composition>
The dispersant of the present invention can be used as a component of an engine cleaning composition. In addition to the dispersant, the engine cleaning composition includes a chelating agent, a glycol solvent, and naphthenic oil. By using these components in combination, the cleaning performance can be further improved. In addition, as long as the effect of the dispersant of the present invention is not adversely affected, other components may be included.

  The kind of chelating agent is not particularly limited, and those generally used can be used. For example, an aminocarboxylate can be used as a chelating agent. Examples of the aminocarboxylate include ethylenediaminetetraacetate, nitrilotriacetate, diethylenetriaminepentaacetate, hydroxyethylethylenediamine triacetate, and the like. A chelating agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The chelating agent is preferably contained in the engine cleaning composition in an amount of 3 to 30% by weight, more preferably 4 to 20% by weight, and particularly preferably 5 to 10% by weight. preferable.

  The kind of glycol-type solvent is not specifically limited, What is generally used can be used. Examples of the glycol solvent include ethylene oxide (EO) glycol ether, propylene oxide (PO) glycol ether, and dialkyl glycol ether.

  E. O. As the glycol ethers, methyl glycol (MG), methyl diglycol (MDG), methyl triglycol (MTG), methyl polyglycol (MPG), isopropyl glycol (iPG), isopropyl diglycol (iPDG), butyl glycol (BG) ), Butyl diglycol (BDG), butyl triglycol (BTG), isobutyl glycol (iBG), isobutyl diglycol (iBDG), hexyl glycol (HeG), hexyl diglycol (HeDG), 2-ethylhexyl glycol (EHG), 2-ethylhexyl diglycol (EHDG), allyl glycol (AG), allyl glycol-H (AG-H), phenyl glycol (PhG), phenyl diglycol (PhDG), phenyl glycol -H (PhG-H), benzyl glycol (BZG), can be exemplified as benzyl diglycol (BzDG).

  P. O. As the system glycol ether, methylpropylene glycol (MFG), methylpropylene diglycol (MFDG), methylpropylene triglycol (MFTG), propylpropylene glycol (PFG), propylpropylene diglycol (PFDG), butylpropylene glycol (BFG) Butylpropylene diglycol (BFDG), butylpropylene triglycol (BFTG), phenylpropylene glycol (PhFG), methylpropylene glycol acetate (MFG-AC) and the like.

  Dialkyl glycol ethers include dimethyl glycol (DMG), dimethyl diglycol (DMDG), dimethyl triglycol (DMTG), methyl ethyl diglycol (MEDG), diethyl diglycol (DEDG), dibutyl diglycol (DBDG), dimethylpropylene A diglycol (DMFDG) etc. can be mentioned.

  Moreover, ethylene glycol (EG), propylene glycol (PG), etc. can be mentioned.

  In particular, it is preferable to use a glycol solvent that is compatible with the engine cleaning composition. By using such a glycol solvent, the cleaning effect of the engine cleaning composition can be sufficiently exerted.

  Further, it is preferable to use a glycol solvent having a boiling point of 220 ° C. or higher, preferably 250 ° C. or higher, particularly preferably 270 ° C. or higher. As an upper limit of a boiling point, 400 degreeC, 370 degreeC, 340 degreeC etc. can be mentioned, for example. Since such a glycol solvent does not evaporate even under high temperature conditions, gelation of the dispersant and the chelating agent can be prevented. Thereby, the cleaning effect of the engine cleaning composition can be maintained.

  A glycol solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The glycol solvent is preferably contained in the engine cleaning composition in an amount of 30 to 80% by weight, more preferably 35 to 70% by weight, and more preferably 40 to 60% by weight. Particularly preferred.

The kind of naphthenic oil is not specifically limited, What is generally used can be used. For example, kinematic viscosity 5 to 50 mm ² / s at 40 ° C., preferably from 5 to 30 mm ² / s, particularly preferably can be used naphthenic oil is 5 to 15 mm ² / s. Naphthenic oil may be used alone or in combination of two or more.

  The naphthenic oil is preferably contained in the engine cleaning composition in an amount of 10 to 50% by weight, more preferably 15 to 40% by weight, and particularly preferably 20 to 30% by weight. preferable.

  The total amount of carboxylic acid and amine contained in the dispersant is preferably 3 to 30% by weight, more preferably 4 to 20% by weight in the engine cleaning composition. 10% by weight is particularly preferable.

  The engine cleaning composition of the present invention may contain additional components as long as the effects of the present invention are not impaired.

<Flushing oil>
The engine cleaning composition can be used by mixing with a flushing oil that is compatible with the composition. When the engine is cleaned using the engine cleaning composition, it is necessary to clean the engine after it is disassembled. However, when using the engine cleaning composition mixed with flushing oil, the mixture is injected into the engine instead of the engine oil, and the deposit formed inside the engine is removed by operating for a certain period of time. can do. Since this method does not require the engine to be disassembled, deposits can be easily removed.

  Flushing oils include ashless dispersants, metal detergents, zinc dialkyldithiophosphates, antifoam agents, and base oils. In addition, as long as the effect of the composition for engine cleaning is not adversely affected, other components may be included.

  The type of the ashless dispersant is not particularly limited, and those generally used can be used. Examples of the ashless dispersant include succinimide, succinic acid ester, benzylamine, succinic acid amide, and a copolymer polymer. One ashless dispersant may be used alone, or two or more ashless dispersants may be used in combination.

  The kind of metal detergent is not specifically limited, What is generally used can be used. For example, as a metal detergent, an alkaline earth metal salt of an organic acid, and more specifically, neutral or overbased metal (Ba, Ca, Mg) sulfonate, overbased metal (Ba, Ca, Mg) phenate And an overbased metal (Ca, Mg) salicylate, phosphonate, and the like. A metal detergent may be used individually by 1 type, and may be used in combination of 2 or more type.

  One zinc dialkyldithiophosphate may be used alone, or two or more zinc dialkyldithiophosphates may be used in combination.

  The kind of antifoaming agent is not specifically limited, What is generally used can be used. For example, examples of the antifoaming agent include silicone oil, oil alcohol, cetyl alcohol, tributyl phosphate, higher alcohol, alkyl ester, and polymethacrylate. An antifoamer may be used individually by 1 type and may be used in combination of 2 or more type.

  The type of the base oil is not particularly limited as long as it is compatible with the engine cleaning composition. For example, as a base oil, natural mineral oil, synthetic oil, etc., more specifically, paraffinic hydrocarbons, aromatic hydrocarbons, naphthenic hydrocarbons, olefin oligomers, polybutenes, alkylbenzenes, cycloalkanes, diesters, polyol esters, phosphorus Examples include acid esters, polyglycols, phenyl ethers, polysiloxanes, silicate esters, and halocarbons. One type of base oil may be used alone, or two or more types may be used in combination.

  The flushing oil preferably has a viscosity index of 150 or less. More specifically, 0-150, 30-140, 60-130, 90-120 etc. can be mentioned. The viscosity index can be measured according to a method defined in JIS K2283. By using the flushing oil having the above viscosity index, the compatibility with the engine cleaning composition can be further improved.

  The flushing oil preferably has a phosphorus content of 0.09% by weight or more. More specifically, examples include 0.09 to 1% by weight, 0.1 to 0.5% by weight, 0.11 to 0.2% by weight, and the like. By increasing the phosphorus content, engine wear can be prevented.

  The engine cleaning composition can be used in combination with the flushing oil. The engine cleaning composition and the flushing oil can be provided as an engine cleaning compounding agent in a mixed state. In the case of a compounding agent, the volume ratio between the engine cleaning composition and the flushing oil is, for example, preferably 5: 1 to 1: 1, and particularly preferably 4: 1 to 2: 1. The phosphorus content in the engine cleaning compounding agent is, for example, 0.025 wt% or more, more specifically 0.025 to 0.3 wt%, 0.03 to 0.1 wt%, or the like. preferable.

  Further, the engine cleaning composition and the flushing oil can be provided as an engine cleaning kit in a state where they are separated from each other. The consumer can use the engine cleaning composition and the flushing oil provided in the kit immediately before use by appropriately mixing them. In the case of a kit, the content of phosphorus in the engine cleaning compound obtained by mixing the engine cleaning composition and the flushing oil is, for example, 0.025% by weight or more, more specifically 0.025%. The engine cleaning composition and the flushing oil are preferably provided so as to be 0.3% by weight, 0.03 to 0.1% by weight, or the like.

<How to clean the engine>
By using the dispersant of the present invention as a component of an engine cleaning composition, deposits inside the engine can be removed. The deposit is not limited to a semi-solid deposit, but may be a solid deposit that is difficult to remove.

  The engine can be cleaned by applying the engine cleaning composition to the engine taken out by decomposition. The method of cleaning is not particularly limited, and may be performed so that the engine and the engine cleaning composition are in contact with each other. For example, the engine can be cleaned by immersing the engine in a container containing the engine cleaning composition. Moreover, cleaning efficiency can be improved by cleaning under high temperature conditions. For example, it is preferable to wash at 50 to 200 ° C, 70 to 150 ° C, and 90 to 120 ° C.

  The engine cleaning compounding agent obtained by mixing the engine cleaning composition and the flushing oil can be directly injected into the engine instead of the engine oil. And the deposit formed in the engine can be removed by operating for a certain period of time. In this embodiment, since it is not necessary to disassemble and take out the engine, the cleaning operation can be greatly simplified. Further, since engine disassembly is not required, engine damage can be prevented. Furthermore, since the washing operation is simple, a general consumer can perform it independently without relying on a person with specialized skills.

  The time for which the engine is operated for cleaning varies depending on the state and amount of the deposit, but may be, for example, 1 to 10 hours, 1.5 to 7 hours, or 2 to 4 hours.

  Moreover, the deposit formed in the combustion chamber can be removed by directly spraying the engine cleaning composition into the combustion chamber. By spraying the engine cleaning composition into the combustion chamber in combination with injection of the engine cleaning composition into the engine, the crankcase and combustion chamber deposits can be removed simultaneously.

  Hereinafter, the present invention will be described in more detail using examples and comparative examples, but the technical scope of the present invention is not limited thereto.

<Preparation of dispersant>
(1) Laurylamine (20 parts by weight), dimer acid (29 parts by weight), and aroma oil (51 parts by weight) were stirred and mixed at 60 ° C. for 3 hours. The amine value of the obtained dispersant (o) was 56 mgKOH / g, and the acid value was 59 mgKOH / g.

  (2) Dispersants (p) to (x) were prepared in the same manner as described above. The composition, amine value, and acid value of each dispersant are as shown in Table 1. The dispersing agent (n) is Floren G-600 manufactured by Kyoeisha Chemical Co., Ltd. Dimer acid is a dimer of conjugated linoleic acid.

<Cleaning test 1>
Each of the dispersants prepared above was mixed with naphthenic oil, glycol solvent (HeG), and a chelating agent in the proportions shown in Table 2 to prepare a cleaning composition. The chelating agent (b) is MZ-2 manufactured by Chubu Kirest Co., Ltd., and the solvent content is 35% by weight.

  The oil ring of the piston of the gasoline engine to which the deposit was adhered was immersed in the cleaning composition and left at 100 ° C. The time required for complete removal of the deposit was measured. The results are shown as cleaning performance in Table 1.

  Further, the effect of the dispersant was examined by the above method. As shown in Table 3, when the dispersant (n) was not used, the oil ring deposit was not removed even after 11 hours or longer. The chelating agent (a) is MZ-8 manufactured by Chubu Kirest Co., Ltd., and the solvent content is 50% by weight.

Claims (4)

A carboxylic acid and an amine, the amine having the general formula:
NR ¹ R ² R ³
[Where:
R ¹ is C ₈ -C ₁₈ alkyl;
R ² and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl]
A dispersant which is an aliphatic amine represented by: The dispersant of claim 1, wherein R ² and R ³ are hydrogen.   The dispersant according to claim 1 or 2, wherein the carboxylic acid is an aliphatic polycarboxylic acid having 18 to 36 carbon atoms.   The dispersant according to any one of claims 1 to 3, wherein the amine value of the mixture of carboxylic acid and amine contained in the dispersant is 40 to 260 mgKOH / g, and the acid value is 10 to 160 mgKOH / g.