JP2000309632A - Water dispersion and water-based lubricant using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion containing a polyether derivative derived from a polyether compound and a carboxylic acid excellent in storage stability and hydrolysis stability, and excellent in lubricity using the same. Provide a water-based lubricant. A compound represented by the formula (1) and a compound having 6 to 6 carbon atoms are provided.
An aqueous dispersion of a polyether derivative derived from a carboxylic acid of No. 24 and an aqueous lubricant using the same. _{R [-O- (BO) h -} (AO) l - (BO) m -H] n (1) (R is the residue or a hydrogen atom of a compound having a hydroxyl group having 1 to 24 carbon atoms, AO is an oxyethylene Group or oxypropylene group, BO is an oxybutylene group, h, l and m each represent an average number of moles added, h is 0 to 30, l is 1
~ 200, m is 1-30, n is 1-6, hn + mn = 1
６０60, ln = 1１〜200. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous dispersion. More specifically, the present invention relates to water-based lubricants such as rolling oil, forging oil, press oil, drawing oil, cutting oil, grinding oil, and hydraulic oil.

[0002]

2. Description of the Related Art An aqueous dispersion containing a polyether ester compound derived from a polyether compound and a carboxylic acid is used for lubrication, washing, dispersion, defoaming, oil-water separation, gelling, and the like. However, since the ester is hydrolyzed in water, there is a problem that the appearance of the aqueous dispersion changes during storage or use, and the performance such as lubricity and dispersibility decreases, and the range of use is limited. I was
For example, Japanese Patent Application Laid-Open No. 52-78661 discloses a rolling oil composition for a steel sheet comprising an ester of polyoxyethylene sorbitol and a carboxylic acid. JP-A-10-245581 discloses a water-soluble processing oil containing an ester compound of a block copolymer of propylene oxide and ethylene oxide and a carboxylic acid having 2 to 20 carbon atoms. These are esters of hydroxyl groups derived from oxyethylene groups or oxypropylene groups with carboxylic acids.They are hydrolyzed in aqueous solution and cannot maintain their lubricity, resulting in increased wear of processing tools and finish of work materials. Is worse. There is also a disadvantage that appearance changes such as turbidity occur during storage. JP-A-59-166595 discloses that a polyether derivative obtained by copolymerizing butylene oxide and ethylene oxide in random or block form and a polyether derivative derived from carboxylic acid can be used as a lubricant. However, no specific structure is shown.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an aqueous dispersion containing a polyether derivative derived from a polyether compound having excellent storage stability and hydrolysis stability and a carboxylic acid, and a lubrication using the same. An object of the present invention is to provide a water-based lubricant having excellent properties.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned drawbacks of the prior art, and as a result, an ester derivative of a polyether having a specific structure is excellent in hydrolysis stability and storage stability. I found that. That is, the present invention provides [1] an aqueous dispersion of a polyether compound derived from the compound represented by the formula (1) and a carboxylic acid having 6 to 24 carbon atoms, R [-O- (BO) _h- ( AO) _l- (BO) _m -H] _n . . . (1) (R is a residue or a hydrogen atom of a compound having a hydroxyl group having 1 to 24 carbon atoms, AO is an oxyethylene group or an oxypropylene group, BO is an oxybutylene group, and h, l and m are average addition moles. Represents a number, h is 0 to 30, l is 1
~ 200, m is 1-30, n is 1-6, hn + mn = 1
６０60, ln = 1１〜200. [2] The compound represented by the formula (1) has a polydispersity of 1.0.
The aqueous dispersion according to claim 1, which is 40 or less, [3].
An aqueous lubricant characterized by using the aqueous dispersion according to [1] or [2], and [4] the aqueous lubricant according to [3], in which a polyether derivative has a hydrolysis rate of 30% or less. is there.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, R in the formula (1) is a residue or a hydrogen atom of a compound having a hydroxyl group having 1 to 24 carbon atoms. Specific examples of the compound having a hydroxyl group include
Methanol, ethanol, propanol, butanol,
Pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, octadecenol, nonadecanol,
Eicosanol, hen eicosanol, docosanol,
Linear or branched monohydric alcohols such as tricosanol and tetracosanol, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-
1,2-propanediol, glycerin, diglycerin, neopentyl glycol, trimethylolethane,
Compounds having two or three hydroxyl groups, such as trimethylolpropane, and polyglycerol, pentaerythritol, sorbitol, sorbitan, glucose, sucrose, etc.
There are compounds having at least two hydroxyl groups. These may be used alone or as a mixture. R is preferably a residue or a hydrogen atom of a compound having 1 to 6 hydroxyl groups, and more preferably a residue or a hydrogen atom of a compound having 1 to 3 hydroxyl groups.

AO is an oxyethylene group or an oxypropylene group. They may be used alone or together.
When used together, either random addition or block addition may be used. BO is an oxybutylene group;
And AO are block-shaped additions.

H, l and m represent the average number of moles added.
h is 0 to 30, preferably 0 to 10, and more preferably 0 to 5. l is 1 to 200, preferably 5 to 80, and more preferably 10 to 60. m
Is 1 to 30, preferably 1 to 10, and more preferably 1 to 5. n is an integer of 1 to 6. hn
+ Mn is 1 to 60, preferably 1 to 20.
In is 1 to 200, preferably 1 to 70.
If h or m exceeds 30, the solubility or dispersibility in water becomes poor. When l or ln exceeds 200, when dissolved in water, the viscosity of the aqueous solution becomes extremely high, resulting in poor workability.

Specific examples of carboxylic acids having 6 to 24 carbon atoms include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acid, octadecanoic acid, nonadecanoic acid,
Linear or branched saturated carboxylic acids such as eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, hexadecenoic acid, octadecenoic acid, hydroxyoctadecenoic acid, eicosenoic acid, docosenic acid, octadecadienoic acid, octadecatriene And unsaturated carboxylic acids such as acids. Preferably, octanoic acid, nonanoic acid,
Decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid,
A linear or branched saturated carboxylic acid having 8 to 14 carbon atoms, such as tetradecanoic acid, or an unsaturated carboxylic acid having 16 to 22 carbon atoms, such as hexadecenoic acid, octadecenoic acid, eicosenoic acid, docosenoic acid, octadecadienoic acid, and octadecatrienoic acid. It is a saturated carboxylic acid. These may be used alone,
You may mix and use. When the compound of the formula (1) has two or more hydroxyl groups, not all of them need to be esterified with a carboxylic acid.

The polydispersity of the compound represented by the formula (1) is preferably 1.040 or less, more preferably 1.035 or less, and further preferably 1.030 or less. The polydispersity is an index indicating the molecular weight distribution, and the closer to 1, the narrower the molecular weight distribution and the more uniform the compound. It is preferable that the polydispersity is small because the hydrolysis stability, storage stability and lubricity are improved.

The polydispersity is generally obtained as an elution parameter of gel permeation chromatography (GPC), and is known to vary greatly depending on a measuring device, a column, a developing solvent and the like. The stated polydispersity is determined by dividing the weight average molecular weight (Mw) and number average molecular weight (Mn) and is expressed as Mw / Mn. Specifically, the GPC system SHODE
X GPC SYSTEM-11 (manufactured by Showa Denko KK)
Trademark), SHOdex RI-71 as a differential refractometer
(Showa Denko KK, trademark), SHO as GPC column
Three DEX KF804L (φ8 mm × 300 mm, trade name, manufactured by Showa Denko KK) are connected in series, the column constant temperature bath temperature is 40 ° C., and tetrahydrofuran (TH
F) at a flow rate of 1 ml / min.
0.1 ml of a weight% THF solution was injected, and the elution curve
RWIN GPC calculation program (manufactured by JASCO Corporation)
And the polydispersity can be obtained.

The compound represented by the formula (1) can be obtained by a general method. For example, a compound having one or more hydroxyl groups may be a catalyst such as an alkali hydroxide such as KOH or NaOH, or an alkali metal salt such as sodium methylate or sodium ethylate; preferably an alkali metal salt such as sodium methylate or sodium ethylate. A metal salt is added and dehydration or dealcoholation is performed sufficiently, and then the reaction temperature is 130 ° C. or lower, preferably 110 ° C. or lower, and the reaction pressure is 0.49 MPa (5 Kg / cm ² ) or lower, preferably 0.39 MPa (4 Kg / cm ^2). ) In the following, ethylene oxide or propylene oxide is added, followed by 1,
It can be obtained by adding 2-butylene oxide. In order to obtain a compound represented by the formula (1) having a small polydispersity, it is preferable to sufficiently perform dehydration or dealcoholation and lower the reaction temperature and reaction pressure. Further, the obtained compound represented by the formula (1) can be fractionated by a chromatogram to obtain a polyether derivative having a smaller polydispersity.

Next, the polyether derivative of the present invention can be obtained by esterifying the compound represented by the formula (1) with a carboxylic acid using an acid or alkali catalyst. Further, an alkali hydroxide is added to the carboxylic acid, and the mixture is sufficiently dehydrated.
Ethylene oxide or propylene oxide at a reaction pressure of 0.49 MPa (5 Kg / cm ² ) or lower, preferably 0.39 MPa (4 Kg / cm ² ) or lower,
It can also be obtained by adding 1,2-butylene oxide.

The concentration of the polyether derivative in the aqueous dispersion is preferably from 0.01% by weight to 80% by weight, more preferably from 0.01% by weight to 20% by weight. If it is less than 0.01% by weight, the performance cannot be sufficiently exhibited, and if it is more than 80% by weight, the viscosity of the aqueous solution becomes too high and there is a problem in work.

The aqueous dispersion according to the present invention can be used for lubricating, washing, dispersing,
It can be used for applications such as defoaming, oil-water separation, and gelling. Other compounds can be added within a range that does not impair the effects of the present invention depending on the use.

When used as the water-based lubricant of the present invention,
Although the polyether derivative may be used alone, another compound may be appropriately compounded. Examples of such compounds include mineral oils, animal and vegetable oils, carboxylic esters, carboxylic acids and alkali metal or amine salts thereof, lubricants such as sulfurized oleic acid, chlorinated stearic acid, alkyl phosphate esters, monoethanolamine, triethanolamine, and the like. Examples include organic amines such as ethanolamine, N-dimethylaminoethanol, ethylenediamine, diethylenetriamine, cyclohexylamine, morpholine and their alkylene oxide adducts, corrosion inhibitors such as carboxylic acids and aromatic carboxylic acids, and silicone-based defoamers. Can be The hydrolysis rate of the polyether derivative is preferably 30% or less,
It is more preferably at most 20%. The hydrolysis rate described in the present invention is determined by the following method. 1 g of a sample is weighed correctly in a rubbed flask, and 0.1% KO is added thereto.
100 ml of H aqueous solution was added. Attach a condenser to the flask and leave at 40 ° C. for 2 hours. Thereafter, 25 ml of the liquid was withdrawn, and a phenolphthalene indicator was added thereto.
Titrate with 1 mol / L aqueous hydrochloric acid. A blank test is performed in parallel with this test, and the saponification value A is determined from the results. The hydrolysis rate of the sample is determined by the following equation. Hydrolysis rate (%) = A / SV × 100 SV is a saponification value of a sample obtained by heating at 85 ° C. for 6 hours in a 1N KOH aqueous solution.

[0016]

EXAMPLES The polyether derivatives used in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 1. The lubricity, rust prevention and hydrolysis rate were evaluated by the following methods, and the results are shown in Table 2. <Polydispersity> Weight average molecular weight (Mw) obtained from measurement of gel permeation chromatography (GPC)
The polydispersity (Mw / Mn) was determined from the above and the number average molecular weight (Mn). Specifically, the GPC system SHODE
X GPC SYSTEM-11 (manufactured by Showa Denko KK)
Trademark), SHOdex RI-71 as a differential refractometer
(Showa Denko KK, trademark), SHO as GPC column
Three DEX KF804L (φ8 mm × 300 mm, trade name, manufactured by Showa Denko KK) are connected in series, the column constant temperature bath temperature is 40 ° C., and tetrahydrofuran (TH
F) at a flow rate of 1 ml / min.
0.1 ml of a weight% THF solution was injected, and the elution curve
RWIN GPC calculation program (manufactured by JASCO Corporation)
And polydispersity was obtained.

<Hydrolysis Test> 1 g of a sample was weighed correctly in a rubbed flask, and 100 ml of a 0.1% KOH aqueous solution was added thereto. A condenser was attached to the flask and left at 40 ° C. for 2 hours. Thereafter, 25 ml of the liquid was withdrawn, a phenolphthalene indicator was added thereto, and 0.1 m
The solution was titrated with an ol / L aqueous hydrochloric acid solution. A blank test was performed in parallel with this test, and a saponification value A was determined from the results. The hydrolysis rate of the sample was determined by the following equation. Hydrolysis rate (%) = A / SV × 100 SV is a saponification value of a sample obtained by heating at 85 ° C. for 6 hours in a 1N KOH aqueous solution.

<Lubricity test> The polyether derivatives shown in Table 1 were prepared in a 1% by weight aqueous solution, and the friction coefficient of the test solution was measured using a Soda pendulum type friction tester at a liquid temperature of 2%.
It was measured at 5 ° C.

<Storage stability> A solution prepared by dissolving 10 g of the polyether derivative shown in Table 1 in 90 g of tap water was placed in a test tube with a lid, and allowed to stand at room temperature for 30 days. The state after the standing was indicated according to the following criteria. Judgment criteria ：: Accepted No change in appearance. ×: rejected cloudy, two-layer separation, sediment formation, etc.
Or it is viscous.

[0020]

[Table 1]

The symbols in the squares indicate random bonding.

[0022]

[Table 2]

Examples 1 to 6, which are the aqueous dispersions of the present invention,
Not only has a low hydrolysis rate and excellent storage stability,
Excellent lubricity. Comparative Example 1 having no ester bond in the molecule has insufficient lubricity, and Comparative Examples 2 to 4 comprising a polyether and a fatty acid ester having structures different from those of the present invention have high hydrolysis rates and storage stability. Is bad.

[0024]

The aqueous dispersion of the present invention has hydrolytic stability,
It has excellent storage stability, and particularly when used as an aqueous lubricant, has excellent lubricity.

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Claims (4)

[Claims] 1. A compound represented by the formula (1):
24. A water dispersion of a polyether derivative derived from 24 carboxylic acids. R [-O- (BO) _h- (AO) _l- (BO) _m -H] _n . . . (1) (R is a residue or a hydrogen atom of a compound having a hydroxyl group having 1 to 24 carbon atoms, AO is an oxyethylene group or an oxypropylene group, BO is an oxybutylene group, and h, l and m are average addition moles. Represents a number, h is 0 to 30, l is 1
~ 200, m is 1-30, n is 1-6, hn + mn = 1
６０60, ln = 1１〜200. ) 2. The aqueous dispersion according to claim 1, wherein the polydispersity of the compound represented by the formula (1) is 1.040 or less. 3. An aqueous lubricant comprising the aqueous dispersion according to claim 1 or 2. 4. A polyether derivative having a hydrolysis rate of 30.
%.