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EP 0 120 665 B1 |
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EUROPEAN PATENT SPECIFICATION |
| (45) |
Mention of the grant of the patent: |
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13.05.1987 Bulletin 1987/20 |
| (22) |
Date of filing: 20.03.1984 |
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Soluble oil cutting fluid
Schneidflüssigkeit für lösliches Öl
Fluide de coupe d'huile soluble
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Designated Contracting States: |
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AT BE CH DE FR GB IT LI NL SE |
| (30) |
Priority: |
23.03.1983 GB 8307975
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| (43) |
Date of publication of application: |
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03.10.1984 Bulletin 1984/40 |
| (71) |
Applicant: The British Petroleum Company p.l.c. |
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London EC2Y 9BU (GB) |
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| (72) |
Inventors: |
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- Rawlinson, Anthony Paul
Sunbury-on-Thames
Middlesex, TW16 7LN (GB)
- White, James
Moor Lane
London, EC2Y 9BU (GB)
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| (74) |
Representative: Cohen, Alan Nicol (GB) et al |
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c/o The British Petroleum Company plc
Patents Division
Chertsey Road GB-Sunbury-on-Thames, Middlesex TW16 7LN GB-Sunbury-on-Thames, Middlesex TW16 7LN (GB) |
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| |
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| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
|
[0001] This invention relates to a soluble-oil and to an oil-in-water emulsion containing
the soluble-oil, which emulsion is suitable for use as a cutting fluid.
[0002] Soluble-oil emulsions are well known as cutting fluids. The term "soluble-oil" although
used throughout the industry is, in fact, a misnomer because the constituents are
not soluble in water. The soluble-oils are basically mineral oils blended with emulsifiers
and other additives which, when added to water and stirred, form an oil-in-water emulsion.
The emulsion allows the good cooling properties of water to be utilised in the metal
working process whilst the oil and additives provide lubrication and corrosion inhibiting
properties.
[0003] United States Patent US-A-2999064 discloses the use of a reaction product of boric
acid and an aliphatic amine and of the reaction product of an unsaturated fatty acid
and an aliphatic amine in an aqueous cutting fluid.
[0004] United States Patent US-A-4010107 discloses the addition of a chlorinated olefin
as a corrosion inhibitor to a lubricating oil composition comprising an oil of lubricating
viscosity and an effective amount of each of the following (i) an alkenyl succinimide,
(ii) a Group 11 metal salt of a hydrocarbyl dithiophosphoric acid, (iii) a friction
modifier for example fatty acid esters of polyhydric alcohols and (iv) a Group II
metal salt of a hydrocarbyl sulphonic acid.
[0005] The emulsifiers included in the soluble-oil may not readily form a stable blend with
the mineral oil and so a coupling agent is commonly required to bind the emulsifier
to the oil. Conventional coupling agents include, for example, volatile alcohols such
as sec. butanol, butyl oxitol or cyclohexanol. The volatility of these coupling agents
means that over a period of time coupling agent is lost from the soluble-oil by vaporisation.
This loss of coupling agent reduces the stability of the soluble-oil and is often
associated with an objectionable smell. Further, the coupling agents have relatively
low flash points which means that great care must be taken when they are blended or
otherwise handled.
[0006] The present invention relates to a soluble-oil which is relatively stable without
the need for a conventional coupling agent.
[0007] Thus according to the present invention a soluble-oil suitable, when diluted with
water, for use as a cutting fluid comprises an alkali or alkaline-earth metal alkyl
benzene sulphonate, a fatty acid diethanolamide, a mixed alkanolamine borate, a polyisobutenesuccinimide
and a major proportion of mineral oil.
[0008] Soluble-oil emulsions may become contaminated by bacteria, yeasts and moulds. The
growth of these micro-organisms may cause problems such as emulsion breakdown, the
production of slimes and fungal mats and the evolution of foul odours. Biocides are
often therefore included in soluble-oil formulations to control microbial growth.
It has surprisingly been found that at least some of the soluble-oils according to
the present invention are bio-static even though conventional biocides are not included
in the formulation. Suitably, the soluble-oil according to the present invention comprises
the following amounts of the components:

[0009] The alkali metal or alkaline-earth metal of the alkyl benzene sulphonate is preferably
potassium or calcium or more preferably sodium. The alkyl group is preferably derived
from polypropylene. The alkali or alkaline-earth metal alkyl benzene sulphonate may
be produced by known methods from synthetic sulphonic acids. Preferably the molecular
weight of the compound is from 400 to 520. A high molecular weight improves the corrosion
inhibiting properties of the soluble oil whereas a low molecular weight improves emulsion
stability and so the choice of molecular weight involves a compromise. Mixtures of
alkyl benzene sulphonates may be used.
[0010] The fatty acid diethanolamides are preferably formed by the reaction of diethanolamine
with naturally occurring fatty acids having from 12 to 20 carbon atoms. The fatty
acids may be saturated or unsaturated but are preferably unsaturated.
[0011] The mixed alkanolamine borate comprises the reaction products of more than one alkanolamine
with boric acid. The alkanolamines may be selected from monoethanolamine, diethanolamine,
triethanolamine, N,N dimethyl ethanolamine. A preferred combination of alkanolamines
is mono- and di-ethanolamine.
[0012] The polyisobutene succinimide is preferably overbased with excess amine and preferably
has a molecular weight of from 1000 to 3000.
[0013] The soluble-oil formulation also preferably contains a small amount of distilled
water e.g. from 0 to 2% by weight of the total weight of the soluble-oil. The distilled
water improves the stability of the blend.
[0014] A defoaming agent such as a Friedel Krafts wax may also be included in the soluble
oil. A suitable wax is SASOL wax SH 105 supplied by Weber. The amount of defoaming
agent is preferably in the range 0-0.05% by weight of the total weight of the soluble-oil.
[0015] The soluble-oils according to the present invention may also contain other conventional
additives for soluble-oils such as for example corrosion inhibiting additives. A suitable
commercially available corrosion inhibitor comprises a solution of benzene sulphonamido
hexyl carboxylic acid in water and N,N-dimethyl amino propyl amine. This commercially
available corrosion inhibitor is particularly effective when supplemented with triethanolamine.
Alternatively, a mixture of triethanolamine and other carboxylic acids such as, for
example, caprylic acid or capric acid may be used to inhibit corrosion. Typically,
the corrosion inhibitor is used up to an amount of 2% by weight of the total weight
of the soluble-oil. If the corrosion inhibitor comprises a mixture of triethanolamine
and a carboxylic acid then the two compounds may be present in equal weights up to
a combined weight of 2% of the total weight of the soluble-oil.
[0016] If a biocidal soluble-oil is required, a conventional biocide may be included in
the formulation.
[0017] It is to be understood that the optional components of the soluble-oil are included
in the composition in place of some of the mineral oil.
[0018] Although a wide range of mineral oils may be used in the soluble-oil formulations
according to the present invention, base oils designated 100 to 500 solvent neutral
have been found to be particularly suitable, i.e. paraffinic oils typically having
kinematic viscosities at 40°C in the range 12 to 100 cSt.
[0019] The soluble-oil according to the present invention is relatively stable and when
mixed with water readily forms an emulsion which may be used in a number of metal
working operations e.g. cutting, drilling and grinding. Preferably, the emulsion has
a water to soluble-oil ratio of from 10:1 1 to 40: although higher and lower dilutions
may be useful in certain applications.
[0020] The invention is illustrated with reference to the following example.
Example 1
[0021] Two soluble-oil formulations were prepared by mixing the following components:-

[0022] The sodium alkyl benzene sulphonate had an average molecular weight of 440 and was
used as a 60% by weight solution in a paraffinic mineral oil. The fatty acid diethanolamine
was oleic acid diethanolamide and was approximately 25% overbased with excess diethanolamine.
The mixed alkanolamine borate was a mixture of boric acid, monoethanolamine and diethanolamine
in the approximate weight ratio 30:33:35. The polyisobutene succinimide was formed
by the reaction between a polyisobutene having a molecular weight of approximately
1000, succinic acid anhydride and diethanolamine and was overbased with a small excess
of N,N dimethyl ethanolamine.
[0023] The thermal stability of each formulation was tested after 14 days at temperatures
in the range -5°C to 50°C using a method based on the Institute of Petroleum test
method IP 311, Thermal Stability of Emulsifiable Cutting Oil. Both formulations were
very viscous at temperatures of 0°C and below but were stable on warming. Formulation
B was also stable at temperatures up to 50°C. Formulation A became unstable at temperatures
above 40°C. However, in the presence of 0.5% wt of water, Formulation A was also stable
up to 50°C.
[0024] Samples of the two formulations were mixed with mains tap water at ratios of water
to oil of from 10:1 to 25:1. The oil readily emulsified in the water at each dilution
and each emulsion was subjected to the Institute of Petroleum standard test method
IP 125 Aqueous Cutting Fluid Corrosion of Cast Iron. There was no visible staining
or pitting at the lower dilutions and the corrosion at the highest dilutions was hardly
perceptible.
[0025] The propensity to foam of Formulation B was less than that of Formulation A as determined
by the Institute of Petroleum standard test method IP 312, Frothing Characteristics
of Emulsifiable Cutting Oil. This is presumably due to the inclusion in Formulation
B of Sasol wax, a known defoaming agent.
[0026] A test rig was used to evaluate the microbial degradation of the soluble-oil emulsions
in a simulated workshop operation. The rig comprised a reservoir for the cutting fluid
and an air lift pump to transfer the fluid from the reservoir to a funnel containing
metal cuttings, the funnel being mounted over the reservoir so that the fluid drained
back into the reservoir. Duplicate samples of Formulation A diluted with mains tap
water in the ratio of water to oil of 20:1 were tested in the test rig. An inoculum
prepared from a mixed culture of fungi and bacteria originating from a spoiled cutting
oil emulsion was added to the test samples so that an initial total viable count of
approximately 10
6 micro-organisms per millilitre of emulsion was obtained. Air was passed through the
rig to circulate and aerate the fluid during normal working hours from Monday to Friday
each week. Each Monday morning, viable counts of aerobic bacteria, yeasts and moulds
were prepared and the presence of sulphide producing bacteria, evolution of H
2S, pH and emulsion stability were determined.
[0027] Up to the end of 14 weeks, the emulsion had not evolved H
2S or encouraged yeast, mould or fungal growth. The total viable bacteria count remained
at approximately 10
6 organisms per millilitre of emulsion throughout the test. The strength of the emulsion
was relatively constant throughout the test and the pH which was initially 9.5 fell
to around 8.5 after 12 days and then remained at this value for the remainder of the
test period.
[0028] The results show that Formulation A, which contains no conventional biocide or coupling
agent, forms a stable emulsion which has biostatic properties and does not evolve
H
2S.
Example 2
[0029] Two soluble-oil formulations were prepared by mixing the following components:-
[0030]

[0031] Formulation D is similar to Formulation C except that it contains a corrosion inhibiting
mixture comprising triethanolamine and Hostacor H. Hostacor H is a commercially available
corrosion inhibitor comprising a solution of benzene sulphonamido hexyl carboxylic
acid in water and N,N-dimethyl amino propyl amine.
[0032] The thermal stability of each formulation was tested after 14 days at temperatures
in the range 0 to 60°C using a method based on the Institute of Petroleum test method
IP311, Thermal Stability of Emulsifiable Cutting Oil. Both formulations were stable
throughout the temperature range.
[0033] Each of the formulations were mixed with mains tap water at ratios of water to soluble-oil
of from 10:1 to 40:1. The soluble-oils readily emulsified in the water at each dilution.
Each of the emulsions was subjected to the Institute of petroleum standard test method
IP125, Aqueous Cutting Fluid Corrosion of Cast Iron. Formulation C showed no pitting
or staining up to dilutions of 20:1 and Formulation D showed no pitting or staining
up to dilutions of 40:1.
[0034] The results show that both formulations, which contain no conventioned coupling agent,
form relatively stable emulsions with water and that the inclusion of the triethanolamine
and Hostacor H improve the corrosion inhibiting properties of the soluble-oil.
1. A soluble-oil suitable, when diluted with water, for use as a cutting fluid comprises
minor proportions of an alkali or alkaline-earth metal alkyl benzene sulphonate, a
fatty acid diethanolamide, a mixed alkanolamine borate, and a polyisobutenesuccinimide
and a major proportion of mineral oil.
2. A soluble-oil as claimed in claim 1 comprising the following proportion of the
components as percentages of the total weight of the soluble oil:-
3. A soluble-oil as claimed in either claim 1 or claim 2 in which the alkali or alkaline-earth
metal alkyl benzene sulphonate has a molecular weight of from 400 to 520, the alkali
metal or alkaline-earth metal is selected from the group comprising sodium, potassium
and calcium and the alkyl group is derived from polypropylene.
4. A soluble-oil as claimed in any of claims 1 to 3 in which the fatty acid diethanolamide
is the reaction product of diethanolamine with a naturally occurring fatty acid having
from 12 to 20 carbon atoms.
5. A soluble-oil as claimed in any of claims 1 to 4 in which the mixed alkanolamine
borate is the reaction product of boric acid and at least two alkanolamines selected
from the group comprising monoethanolamine, diethanolamine, triethanolamine and N,N
dimethyl ethanolamine.
6. A soluble-oil as claimed in claim 5 in which the alkanolamines are mono- and di-ethanolamine.
7. A soluble-oil as claimed in any of claims 1 to 6 in which the polyisobutenesuccinimide
is overbased with excess amine and has a molecular weight of from 1000 to 3000.
8. A soluble-oil as claimed in any of claims 1 to 7 which contains up to 2% of distilled
water by weight of the total weight of the soluble-oil.
9. A soluble-oil as claimed in any of claims 1 to 8 which contains up to 0.05% of
a defoaming agent by weight of the total weight of the soluble oil.
10. An emulsion, suitable for use as a cutting fluid comprising water and a soluble-oil
as claimed in any of the preceding claims in a volumetric ratio of 10:1 to 40:1.
1. Lösliches Öl, das nach Verdünnen mit Wasser zur Verwendung als Schneidflüssigkeit
geeignet ist, enthaltend kleinere Anteile eines Alkali- oder Erdalkalimetallalkylbenzolsulfonats,
eines Fettsäurediethanolamids, eines gemischten Alkanolaminborats und eines Polyisobutensuccinimids
und einen Hauptanteil Mineralöl.
2. Lösliches Öl nach Anspruch 1, umfassend die nachstehenden Anteile der Komponenten
als Prozentsätze des Gesamtgewichts des löslichen Öls:
3. Lösliches Öl nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß das Alkali-
oder Erdalkalimetallalkylbenzolsulfonat ein Molekulargewicht von 400 bis 520 hat,
das Alkali- oder Erdalkalimetall aus der Natrium, Kalium und Calcium umfassend Gruppe
ausgewählt ist und die Alkyl-Gruppe von Polypropylen abgeleitet ist.
4. Lösliches Öl nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß
das 1 Fettsäurediethanoiamid das Reaktionsprodukt von Diethanolamin mit einer natürlich
vorkommenden Fettsäure mit 12 bis 20 Kohlenstoff-Atomen ist.
5. Lösliches Öl nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß
das gemischte Alkanolaminborat das Reaktionsprodukt von Borsäure und wenigstens zwei
aus der Monoethanolamin, Diethanolamin, Triethanolamin und N,N-Dimethylethanolamin
umfassenden Gruppe ausgewählten Alkanolaminen ist.
6. Lösliches Öl nach Anspruch 5, dadurch gekennzeichnet, daß die Alkanolamine Mono-
und Diethanolamin sind.
7. Lösliches Öl nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß
das Polyisobutensuccinimid mit überschüssigem Amin überbasifiziert ist und ein Molekulargewicht
von 1 000 bis 3 000 hat.
8. Lösliches Öl nach irgendeinem der Ansprüche 1 bis 7, enthaltend bis zu 2 Gew.-%
destilliertes Wasser, bezogen auf das Gesamtgewicht des löslichen Öls.
9. Lösliches Öl nach irgendeinem der Ansprüche 1 bis 8, enthaltend bis zu 0,05 Gew.-%
eines Entschäumungsmittels, bezogen auf das Gesamtgewicht des löslichen Öls.
10. Emulsion, geeignet zur Verwendung als Schneidflüssigkeit, umfassend Wasser und
ein lösliches Öl nach irgendeinem der vorhergehenden Ansprüche in einem Volumenverhältnis
10:1 bis 40:1.
1. Une huile soluble convenant lorsqu'elle est diluée avec de l'eau, pour l'utilisation
comme fluide de coupe, comprend des proportions mineures d'un alkyle benzène sulphonate
de métal alcalin ou alcalino-terreux, un diéthanolamide d'acide gras, un borate d'alcanolamines
mélangées et un polyisobutène succinimide et une proportion prédominante d'huiles
minérales.
2. Une huile soluble suivant la revendication 1, comprenant les proportions suivantes
des constituants en pourcentages du poids total de l'huile soluble:
3. Une huile soluble suivant l'une des revendications 1 ou 2, dans laquelle l'alkyle
benzène sulphonate de métal alcalin ou alcalino-terreux a un poids moléculaire de
400 à 520, le métal alcalin ou le métal alcalino-terreux est choisi dans le groupe
comprenant le sodium, le potassium et le calcium et le groupe alkyle dérive du propylène.
4. Une huile soluble suivant l'une quelconque des revendications 1 à 3, dans laquelle
le diéthanolamide d'acide gras est le produit de la réaction de la diéthanolamine
avec un acide gras naturel ayant de 12 à 20 atomes de carbone.
5. Une huile soluble suivant l'une quelconque des revendications 1 à 4, dans laquelle
le borate d'alcanolamine mélangée est le produit de la réaction de l'acide borique
et d'au moins deux alcanolamines choisies dans le groupe constitué de la monoéthanolamine,
de la diéthanolamine, de la triéthanolamine, et de la N,N-diméthyl éthanolamine.
6. Une huile soluble suivant la revendication 5, dans laquelle les alcanolamines sont
la mono- et la diéthanolamine.
7. Une huile soluble suivant l'une quelconque des revendications 1 à 6, dans laquelle
le polyisobutène succinimide est suralcanalisé par un excès d'amine qui a une masse
moléculaire de 1000 à 3000.
8. Une huile soluble suivant l'une quelconque des revendications 1 à 7, qui contient
jusqu'à 2% d'eau distillée en poids du poids total d'huile soluble.
9. Une huile soluble suivant l'une quelconque des revendications 1 à 8, qui contient
jusqu'à 0,05% d'un agent anti-mousse en poids du poids total de l'huile soluble.
10. Une émulsion convenant pour l'utilisation comme fluide de coupe, comprenant de
l'eau et une huile soluble suivant l'une quelconque des revendications précédentes
dans un rapport volumique de 10:1 à 40:1.