U.S. patent application number 13/064862 was filed with the patent office on 2011-08-18 for oil composition for use in trace oil supply cutting/grinding work.
This patent application is currently assigned to Nippon Oil Corporation. Invention is credited to Tomoyasu Kochu, Yoshiaki Matsuura, Satoshi Suda, Hideo Yokota.
Application Number | 20110201259 13/064862 |
Document ID | / |
Family ID | 36319192 |
Filed Date | 2011-08-18 |
United States Patent
Application |
20110201259 |
Kind Code |
A1 |
Suda; Satoshi ; et
al. |
August 18, 2011 |
Oil composition for use in trace oil supply cutting/grinding
work
Abstract
This invention provides an oil composition for cutting and
grinding by minimum quantity lubrication system, characterized by
comprising an ester oil with a kinematic viscosity of 0.5-20
mm.sup.2/s at 100.degree. C., and an ester-based polymer with a
kinematic viscosity exceeding 20 mm.sup.2/s at 100.degree. C. and
an average molecular weight of 5,000-10,000,000. The oil
composition for cutting and grinding by minimum quantity
lubrication system according to the invention can achieve an
excellent balance between misting property and inhibition of
floating mist and ensure that an adequate amount reaches the
working section, for cutting and grinding by minimum quantity
lubrication system.
Inventors: |
Suda; Satoshi;
(Yokohama-shi, JP) ; Yokota; Hideo; (Yokohama-shi,
JP) ; Kochu; Tomoyasu; (Toyota-shi, JP) ;
Matsuura; Yoshiaki; (Toyota-shi, JP) |
Assignee: |
Nippon Oil Corporation
|
Family ID: |
36319192 |
Appl. No.: |
13/064862 |
Filed: |
April 21, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11666829 |
Jul 2, 2008 |
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PCT/JP2005/020142 |
Nov 1, 2005 |
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13064862 |
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Current U.S.
Class: |
451/54 ;
451/64 |
Current CPC
Class: |
C10M 2207/2815 20130101;
C10M 2207/2835 20130101; C10M 2209/102 20130101; C10M 169/041
20130101; C10N 2030/30 20200501; C10M 2207/2825 20130101; C10N
2040/22 20130101; C10M 2209/084 20130101; C10M 2207/2805 20130101;
C10M 2207/401 20130101; C10M 2207/2805 20130101; C10N 2020/02
20130101; C10M 2209/084 20130101; C10N 2020/04 20130101; C10N
2020/02 20130101; C10M 2209/102 20130101; C10N 2020/04 20130101;
C10N 2020/02 20130101; C10M 2207/2805 20130101; C10N 2020/02
20130101; C10M 2209/084 20130101; C10N 2020/04 20130101; C10N
2020/02 20130101; C10M 2209/102 20130101; C10N 2020/04 20130101;
C10N 2020/02 20130101 |
Class at
Publication: |
451/54 ;
451/64 |
International
Class: |
B24B 1/00 20060101
B24B001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 1, 2004 |
JP |
P2004-318251 |
Claims
1. (canceled)
2. A process comprising the steps of: cutting and grinding a
workpiece by minimum quantity lubrication system with an oil
composition; wherein the oil composition comprises: an ester of a
polyhydric alcohol and a monobasic acid with a kinematic viscosity
of 0.2-12 mm.sup.2/s at 100.degree. C., and an ester-based polymer
with a kinematic viscosity exceeding 20 mm.sup.2/s to 2,500
mm.sup.2/s at 100.degree. C. and an average molecular weight of
10,000-300,000; wherein the content of the ester is 90.00 to 99.99%
by mass and the content of the ester-based polymer is 0.01 to
10.00% by mass based on a total amount of the composition.
3. A minimum quantity lubrication system, comprising: a cutting and
grinding apparatus cutting and grinding a workpiece; a lubrication
apparatus providing a lubricant oil composition to the cutting and
grinding apparatus; wherein the lubricant oil composition
comprises: an ester of a polyhydric alcohol and a monobasic acid
with a kinematic viscosity of 0.2-12 mm.sup.2/s at 100.degree. C.,
and an ester-based polymer with a kinematic viscosity exceeding 20
mm.sup.2/s to 2,500 mm.sup.2/s at 100.degree. C. and an average
molecular weight of 10,000-300,000; wherein the content of the
ester is 90.00 to 99.99% by mass and the content of the ester-based
polymer is 0.01 to 10.00% by mass based on a total amount of the
composition.
Description
TECHNICAL FIELD
[0001] The present invention relates to an oil composition for
cutting and grinding by minimum quantity lubrication (MQL) system,
and more specifically it relates to an oil composition for cutting
and grinding of a workpiece while supplying a minimum quantity of
oil to a working section together with a compressed fluid.
BACKGROUND ART
[0002] In cutting and grinding, it is common to employ cutting and
grinding oils for the purpose of extending the life of working
tools such as drills, end mills, cutting tools, grinding wheels and
the like, improving the surface roughness of working surfaces and
raising productivity in mechanical working by increasing machining
performance.
[0003] Cutting and grinding oils fall into two general categories,
namely water-soluble cutting and grinding oils used by diluting
surfactants and lubricant components with water, and
non-water-soluble cutting and grinding oils used directly as stock
solutions composed mainly of mineral oils. In conventional cutting
and grinding, a relatively large amount of cutting and grinding oil
is supplied to the working section regardless of the type of
oil.
[0004] The most basic and important functions of a cutting and
grinding oil are the lubricating function and cooling function.
Generally speaking non-water-soluble cutting and grinding oils
exhibit superior lubricating performance while water-soluble
cutting and grinding oils exhibit superior cooling performance.
Because the cooling effect of non-water-soluble oils is inferior to
that of water-soluble oils, there is usually required a large
amount of non-water-soluble cutting and grinding oil, from several
liters to in some cases several tens of liters per minute.
[0005] Cutting and grinding oils that are effective for improving
machining performance have drawbacks from other viewpoints,
typically their adverse effects on the environment. Whether
non-water-soluble or water-soluble, oils undergo gradual
degradation with use and eventually become unusable. In the case of
water-soluble oils, for example, solution stability is lost with
growth of microorganisms, resulting in separation of the
components, significant fouling of the environment and
unsuitability for use. In the case of non-water-soluble oils,
progressive oxidation produces acidic components that corrode metal
materials and produce significant changes in viscosity, also
resulting in unsuitability for use. The oils also adhere to shaved
chips and the like, becoming consumed and forming waste.
[0006] The degraded oils must therefore be disposed of and replaced
with new oils. Oils that have been discharged as waste must be
treated in some manner to avoid adversely affecting the
environment. For example, chlorine-based compounds that can
potentially generate harmful dioxin during thermal disposal are
often used in cutting and grinding oils developed for the principal
purpose of improving working efficiency, and such compounds must
therefore be removed. Cutting and grinding oils containing no
chlorine-based compounds have therefore been developed, but even
cutting and grinding oils free of such harmful components affect
the environment if their waste disposal volume is large.
Water-soluble oils can also contaminate environmental waters and
therefore require costly high-level treatment.
[0007] Research has been conducted recently with cooling of cutting
and grinding areas by cool air blowing, instead of using cutting
and grinding oils, as a means of dealing with these problems, but
the lubricating performance provided by cutting and grinding oils
cannot be achieved.
[0008] In light of this background, a cutting and grinding process
in minimum quantity lubrication system has been developed in which
a trace amount of oil at about 1/100,000-1/1,000,000 of the amount
of oil used for conventional cutting and grinding is supplied to
the working section together with a compressed fluid (for example,
compressed air) for cutting and grinding. In such systems, a
cooling effect is achieved due to the compressed air, and the trace
amount of oil used allows the amount of waste to be reduced,
thereby resulting in improvement in the effect on the environment
that is caused by large-scale emission of waste products (for
example, see Patent documents 1, 2). [0009] [Patent document 1]
WO02/083823 [0010] [Patent document 2] WO02/081605
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0011] The oil used in the aforementioned minimum quantity
lubrication system cutting and grinding process must have the
property of easily misting (hereinafter referred to as "misting
property"), because of the manner in which it is used. Using an oil
with a low misting property results in insufficient oil reaching
the working section, making it impossible to ensure adequate
machining performance.
[0012] However, investigation by the present inventors has shown
that simply using an oil with a high misting property produces a
mist that floats in the atmosphere as it forms and does not reach
the working section, or a mist that reaches the working section but
flies away without remaining on the working section (hereinafter,
this will be referred to as "floating mist"). This also reduces the
effective amount of oil functioning at the working section, making
it impossible to ensure adequate machining performance. Moreover,
generation of a floating mist is also undesirable from the
viewpoint of the working environment.
[0013] It is an object of the present invention, which has been
accomplished in light of the circumstances described above, to
provide an oil that can achieve an excellent balance between the
misting property and inhibition of floating mist when performing
cutting and grinding with minimum quantity lubrication system,
thereby ensuring that a sufficient amount reaches the working
section.
Means for Solving the Problems
[0014] In order to solve the problems described above, the oil
composition for cutting and grinding by minimum quantity
lubrication system according to the invention is characterized by
comprising an ester oil with a kinematic viscosity of 0.5-20
mm.sup.2/s at 100.degree. C. and an ester-based polymer with a
kinematic viscosity exceeding 20 mm.sup.2/s at 100.degree. C. and
an average molecular weight of 5,000-10,000,000.
[0015] Ester-based polymers with a kinematic viscosity exceeding 20
mm.sup.2/s at 100.degree. C. include those with a measured
kinematic viscosity of greater than at 100.degree. C., as well as
those whose kinematic viscosity at 100.degree. C. is too high to be
measured (semi-solids, solids and the like).
[0016] The oil composition for cutting and grinding by minimum
quantity lubrication system according to the invention (hereinafter
also referred to simply as "oil composition of the invention")
employs both an ester oil with a kinematic viscosity at 100.degree.
C. which satisfies the aforementioned conditions, and an
ester-based polymer whose kinematic viscosity at 100.degree. C. and
average molecular weight satisfy the aforementioned conditions,
thereby allowing an excellent balance to be achieved between the
misting property and inhibition of floating mist, in order to
ensure that an adequate amount reaches the working section.
Moreover, upon reaching the working section, the oil composition of
the invention can adequately enhance the machining performance for
cutting and grinding with the minimum quantity lubrication
system.
[0017] Although the reason for this effect of the invention is not
fully understood, the present inventors conjecture as follows. That
is, it is believed that the high affinity of the ester-based
polymer of the invention for the ester oil provides a function of
stably maintaining the ester oil in the oil composition of the
invention. Thus, while ester oils when used alone exhibit a very
high misting property but form minute oil droplets that can result
in floating mist, these are captured by the ester-based polymer and
prevented from forming a floating mist. On the other hand, ester
oil droplets of a size that can separate from the ester-based
polymer, as well as oil droplets composed of the ester oil and
ester-based polymer, have a high misting property and are resistant
to size increase by reaggregation, thus being able to reliably
reach the working section. The present inventors conjecture that
the ester oil droplet size-adjusting function of the ester-based
polymer is responsible for achieving both a misting property and
inhibition of floating mist.
Effect of the Invention
[0018] The cutting and grinding oil for minimum quantity
lubrication system according to the invention can achieve an
excellent balance between misting property and inhibition of
floating mist and ensure that an adequate amount reaches the
working section, when cutting and grinding is carried out with
minimum quantity lubrication system.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a side view of the essential parts of the test
apparatus used in the examples.
[0020] FIG. 2 is a top view of the essential parts of the test
apparatus used in the examples.
EXPLANATION OF SYMBOLS
[0021] 1: Table, 2: drill, 3: shank, 4: mist collector, 5: oil feed
line, 10: workpiece.
BEST MODE FOR CARRYING OUT THE INVENTION
[0022] Preferred modes of the invention will now be described in
detail.
[0023] The oil composition of the invention is an oil composition
to be used for cutting and grinding with minimum quantity
lubrication system, and it comprises (A) an ester oil with a
kinematic viscosity of 0.5-20 mm.sup.2/s at 100.degree. C.
(hereinafter also referred to as "component (A)"), and (B) an
ester-based polymer with a kinematic viscosity of 20 mm.sup.2/s at
100.degree. C. and an average molecular weight of 5,000-10,000,000
(hereinafter also referred to as "component (B)").
[0024] The term "cutting and grinding with minimum quantity
lubrication system" used here refers to cutting and grinding which
is carried out while supplying oil, in a trace amount of about
1/100,000-1/1,000,000 compared to the amount of oil used for
ordinary cutting and grinding, to a cutting and grinding area,
together with a compressed fluid (compressed air or the like). More
specifically, minimum quantity lubrication system is a system
wherein oil is supplied at 0.001-1 ml/min toward the cutting and
grinding area together with a compressed fluid (for example,
compressed air). A compressed fluid such as nitrogen, argon,
helium, carbon dioxide or water may also be used alone in addition
to compressed air, or such fluids may be used in combination.
[0025] The pressure of the compressed fluid for the cutting and
grinding with minimum quantity lubrication system is adjusted to a
pressure that does not cause fly-off of the oil and contamination
of the ambient area, but a pressure that allows the oil and gas, or
a fluid mixture thereof with a liquid, to sufficiently reach the
cutting and grinding point. From the standpoint of the cooling
property, the temperature of the compressed fluid will usually be
room temperature (about 25.degree. C.), or will be adjusted to
between room temperature and -50.degree. C.
[0026] Component (A) used for the invention is not particularly
restricted so long as it is an ester oil with a kinematic viscosity
of 0.5-20 mm.sup.2/s at 100.degree. C., and the ester may be either
a natural substance (usually one found in a natural fat or oil from
an animal or plant) or synthetic. According to the invention,
synthetic esters are preferred from the standpoint of stability of
the resulting oil composition and uniformity of the ester
component.
[0027] The alcohol in the ester oil used as component (A) may be a
monohydric alcohol or polyhydric alcohol, and the acid in the ester
oil may be a monobasic acid or polybasic acid.
[0028] As monohydric alcohols there may be used those with 1-24,
preferably 1-12, and more preferably 1-8 carbon atoms, and such
alcohols may be either straight-chain or branched, and either
saturated or unsaturated. As specific examples of C1-24 alcohols
there may be mentioned methanol, ethanol, straight-chain or
branched propanol, straight-chain or branched butanol,
straight-chain or branched pentanol, straight-chain or branched
hexanol, straight-chain or branched heptanol, straight-chain or
branched octanol, straight-chain or branched nonanol,
straight-chain or branched decanol, straight-chain or branched
undecanol, straight-chain or branched dodecanol, straight-chain or
branched tridecanol, straight-chain or branched tetradecanol,
straight-chain or branched pentadecanol, straight-chain or branched
hexadecanol, straight-chain or branched heptadecanol,
straight-chain or branched octadecanol, straight-chain or branched
nonadecanol, straight-chain or branched eicosanol, straight-chain
or branched heneicosanol, straight-chain or branched tricosanol,
straight-chain or branched tetracosanol, and mixtures of these.
[0029] As polyhydric alcohols there may be used for most purposes
2-10 hydric alcohols, and preferably 2-6 hydric alcohols. As
specific examples of 2-10 hydric polyhydric alcohols there may be
mentioned polyhydric alcohols including ethylene glycol, diethylene
glycol and polyethylene glycol (3-15mers of ethylene glycol),
propylene glycol, dipropylene glycol and polypropylene glycol
(3-15mers of propylene glycol), dihydric alcohols such as
1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol,
2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol,
1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol
and neopentyl glycol; glycerin, polyglycerin (2-8mers of glycerin,
for example, diglycerin, triglycerin, tetraglycerin, etc.),
trimethylolalkanes (trimethylolethane, trimethylolpropane,
trimethylolbutane, etc.) and their 2-8mers, pentaerythritols and
their 2-4mers, 1,2,4-butanetriol, 1,3,5-pentanetriol,
1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan,
sorbitol-glycerin condensate, adonitol, arabitol, xylitol, mannitol
and the like; and sugars such as xylose, arabinose, ribose,
rhamnose, glucose, fructose, galactose, mannose, sorbose,
cellobiose, maltose, isomaltose, trehalose, sucrose and the like,
as well as their mixtures.
[0030] Preferred among these polyhydric alcohols are 2-6 hydric
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol (3-10mers of ethylene glycol), propylene
glycol, dipropylene glycol, polypropylene glycol (3-10mers of
propylene glycol), 1,3-propanediol, 2-methyl-1,2-propanediol,
2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin,
triglycerin, trimethylolalkanes (trimethylolethane,
trimethylolpropane, trimethylolbutane, etc.) and their 2-4mers,
pentaerythritol, dipentaerythritol, 1,2,4-butanetriol,
1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol,
sorbitol, sorbitan, sorbitol-glycerin condensate, adonitol,
arabitol, xylitol, mannitol and the like, as well as mixtures
thereof. More preferred are ethylene glycol, propylene glycol,
neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
pentaerythritol, sorbitan and mixtures thereof. Most preferred
among these are neopentyl glycol, trimethylolethane,
trimethylolpropane, pentaerythritol and mixtures thereof, since
these can provide higher oxidation stability.
[0031] The alcohol of the ester oil used as component (A) may be a
monohydric alcohol or polyhydric alcohol as mentioned above, but a
polyhydric alcohol is preferred from the viewpoint of obtaining
more excellent lubricity for cutting and grinding, improving the
finished surface precision of the workpiece and achieving a more
notable anti-wear effect at the tool blade edge, promoting a low
pour point and further improving the manageability during the
winter season or in cold climates.
[0032] In most cases a C2-24 fatty acid will be used as a monobasic
acid, among acids for the ester oil used as component (A), and such
fatty acids may be straight-chain or branched and either saturated
or unsaturated. As specific examples there may be mentioned
saturated fatty acids such as acetic acid, propionic acid,
straight-chain or branched butanoic acid, straight-chain or
branched pentanoic acid, straight-chain or branched hexanoic acid,
straight-chain or branched heptanoic acid, straight-chain or
branched octanoic acid, straight-chain or branched nonanoic acid,
straight-chain or branched decanoic acid, straight-chain or
branched undecenoic acid, straight-chain or branched dodecanoic
acid, straight-chain or branched tridecanoic acid, straight-chain
or branched tetradecanoic acid, straight-chain or branched
pentadecanoic acid, straight-chain or branched hexadecanoic acid,
straight-chain or branched heptadecanoic acid, straight-chain or
branched octadecanoic acid, straight-chain or branched
hydroxyoctadecanoic acid, straight-chain or branched nonadecanoic
acid, straight-chain or branched eicosanoic acid, straight-chain or
branched heneicosanoic acid, straight-chain or branched docosanoic
acid, straight-chain or branched tricosanoic acid and
straight-chain or branched tetracosanoic acid; and unsaturated
fatty acids such as acrylic acid, straight-chain or branched
butenoic acid, straight-chain or branched pentenoic acid,
straight-chain or branched hexenoic acid, straight-chain or
branched heptenoic acid, straight-chain or branched octenoic acid,
straight-chain or branched nonenoic acid, straight-chain or
branched decenoic acid, straight-chain or branched undecenoic acid,
straight-chain or branched dodecenoic acid, straight-chain or
branched tridecenoic acid, straight-chain or branched tetradecenoic
acid, straight-chain or branched pentadecenoic acid, straight-chain
or branched hexadecenoic acid, straight-chain or branched
heptadecenoic acid, straight-chain or branched octadecenoic acid,
straight-chain or branched hydroxyoctadecenoic acid, straight-chain
or branched nonadecenoic acid, straight-chain or branched
eicosenoic acid, straight-chain or branched heneicosenoic acid,
straight-chain or branched docosenoic acid, straight-chain or
branched tricosenoic acid and straight-chain or branched
tetracosenoic acid, as well as mixtures thereof. Among these, from
the viewpoint of obtaining more excellent lubricity for cutting and
grinding, improving precision of the finishing surface of the
workpiece and achieving an even greater anti-wear effect for the
tool blade edge, particularly C3-20 saturated fatty acids, C3-22
unsaturated fatty acids and mixtures thereof are preferred, C4-18
saturated fatty acids, C4-18 unsaturated fatty acids and their
mixtures are more preferred and C4-18 unsaturated fatty acids are
even more preferred, while from the viewpoint of preventing
sticking, C4-18 saturated fatty acids are especially preferred.
[0033] As polybasic acids there may be mentioned C2-16 dibasic
acids, trimellitic acid and the like. Such C2-16 dibasic acids may
be straight-chain or branched, and either saturated or unsaturated.
As specific examples there may be mentioned ethanedioic acid,
propanedioic acid, straight-chain or branched butanedioic acid,
straight-chain or branched pentanedioic acid, straight-chain or
branched hexanedioic acid, straight-chain or branched heptanedioic
acid, straight-chain or branched octanedioic acid, straight-chain
or branched nonanedioic acid, straight-chain or branched
decanedioic acid, straight-chain or branched undecanedioic acid,
straight-chain or branched dodecanedioic acid, straight-chain or
branched tridecanedioic acid, straight-chain or branched
tetradecanedioic acid, straight-chain or branched heptadecanedioic
acid, straight-chain or branched hexadecanedioic acid,
straight-chain or branched hexenedioic acid, straight-chain or
branched heptenedioic acid, straight-chain or branched octenedioic
acid, straight-chain or branched nonenedioic acid, straight-chain
or branched decenedioic acid, straight-chain or branched
undecenedioic acid, straight-chain or branched dodecenedioic acid,
straight-chain or branched tridecenedioic acid, straight-chain or
branched tetradecenedioic acid, straight-chain or branched
heptadecenedioic acid, straight-chain or branched hexadecenedioic
acid, and mixtures thereof.
[0034] The acid of the ester oil used as component (A) may be a
monobasic acid or polybasic acid as mentioned above, but it is
preferred to use a monobasic acid to more easily obtain an ester
contributing to an improved viscosity index and enhanced misting
and anti-sticking properties.
[0035] The combination of the alcohol and acid in the ester oil
used as component (A) may be any from among the following, for
example, so long as the kinematic viscosity of the ester oil is
0.5-20 mm.sup.2/s at 100.degree. C.
(i) Esters of monohydric alcohols and monobasic acids (ii) Esters
of polyhydric alcohols and monobasic acids (iii) Esters of
monohydric alcohols and polybasic acids (iv) Esters of polyhydric
alcohols and polybasic acids (v) Mixed esters of monohydric alcohol
and polyhydric alcohol mixtures and polybasic acids (vi) Mixed
esters of polyhydric alcohols and monobasic acid and polybasic acid
mixtures (vii) Mixed esters of monohydric alcohol and polyhydric
alcohol mixtures and monobasic acid and polybasic acid mixtures
[0036] Preferred among these are (ii) esters of polyhydric alcohols
and monobasic acids, from the standpoint of obtaining more
excellent lubricity during cutting and grinding, improving the
finished surface precision of the workpiece and achieving a more
notable anti-wear effect at the tool blade edge, promoting a low
pour point, further improving the manageability during the winter
season or in cold climates, more easily achieving a high viscosity
index and further improving the misting property.
[0037] As naturally-derived esters to be used as component (A)
there may be mentioned natural fats and oils including vegetable
oils such as palm oil, palm kernel oil, rapeseed oil, soybean oil,
sunflower oil, and high-oleic rapeseed oil or high-oleic sunflower
oil with increased oleic acid content among the glyceride fatty
acids achieved by cross-breeding or gene recombination, as well as
animal oils such as lard.
[0038] According to the invention, the ester oil obtained using a
polyhydric alcohol as the alcohol component may be a complete ester
obtained by esterification of all of the hydroxyl groups in the
polyhydric alcohol, or a partial ester wherein some of the hydroxyl
groups remain as hydroxyl groups without esterification. Likewise,
an organic acid ester obtained using a polybasic acid as the acid
component may be a complete ester obtained by esterification of all
of the carboxyl groups in the polybasic acid, or it may be a
partial ester wherein some of the carboxyl groups remain as
carboxyl groups without esterification. From the standpoint of
low-temperature manageability and misting property, component (A)
is preferably a complete ester.
[0039] As mentioned above, the kinematic viscosity of component (A)
at 100.degree. C. is no greater than 20 mm.sup.2/s, preferably no
greater than 17 mm.sup.2/s, more preferably no greater than 15
mm.sup.2/s and even more preferably no greater than 12 mm.sup.2/s.
If the kinematic viscosity of component (A) at 100.degree. C.
exceeds 20 mm.sup.2/s, the misting property will be inadequate and
it will be difficult to ensure that a sufficient amount of mist
reaches the working section. Also as mentioned above, the kinematic
viscosity of component (A) at 100.degree. C. is preferably at least
0.5 mm.sup.2/s, more preferably at least 0.7 mm.sup.2/s and even
more preferably at least 0.9 mm.sup.2/s. If the kinematic viscosity
of the ester oil at 100.degree. C. is less than 0.5 mm.sup.2/s, it
will not be possible to prevent generation of floating mist even by
using component (B), and the lubricity at the working section will
be inadequate.
[0040] The molecular weight of component (A) is not particularly
restricted so long as the kinematic viscosity at 100.degree. C. is
0.5-20 mm.sup.2/s, but it is preferably less than 5,000, more
preferably no greater than 3,000 and even more preferably no
greater than 2,000. If the molecular weight of component (A)
exceeds this upper limit, the misting property will tend to be
reduced. The molecular weight of component (A) is also preferably
at least 100, more preferably at least 150 and even more preferably
at least 200. If the molecular weight of component (A) is below
this lower limit, it will tend to be difficult to prevent
generation of floating mist even by using component (B). When
component (A) contains two or more ester oils with different
molecular weights, the "molecular weight of component (A)" is the
average molecular weight of the ester oils.
[0041] There are no particular restrictions on the pour point and
viscosity index of component (A), but the pour point is preferably
no higher than -10.degree. C. and more preferably no higher than
-20.degree. C. The viscosity index is preferably between 100 and
200.
[0042] The iodine value of component (A) is preferably 0-80, more
preferably 0-60, even more preferably 0-40, yet more preferably
0-20 and most preferably 0-10. The bromine value of the ester of
the invention is preferably 0-50 gBr.sub.2/100 g, more preferably
0-30 gBr.sub.2/100 g, even more preferably 0-20 gBr.sub.2/100 g and
most preferably 0-10 gBr.sub.2/100 g. If the iodine value and
bromine value of component (A) are within the respective ranges
specified above, the resulting oil composition will tend to have
further increased resistance to stickiness. The iodine value
referred to here is the value measured by the indicator titration
method described in "Test methods for acid value, saponification
value, ester value, iodine value, hydroxyl value and unsaponifiable
matter of chemical products" of JIS K 0070. The bromine value is
the value measured according to "Petroleum distillates and
commercial aliphatic olefins--Determination of bromine
number--Electric method" of JIS K 2605.
[0043] In order to impart more satisfactory lubricating performance
to the oil composition of the invention, the hydroxyl value of
component (A) is preferably 0.01-300 mgKOH/g and the saponification
value is preferably 100-500 mgKOH/g. To provide even higher
lubricity, the upper limit for the hydroxyl value of component (A)
according to the invention is more preferably 200 mgKOH/g and most
preferably 150 mgKOH/g, while the lower limit is more preferably
0.1 mgKOH/g, even more preferably 0.5 mgKOH/g, yet more preferably
1 mgKOH/g, even yet more preferably 3 mgKOH/g and most preferably 5
mgKOH/g. The upper limit for the saponification value of component
(A) is more preferably 400 mgKOH/g, and the lower limit is more
preferably 200 mgKOH/g. The hydroxyl value referred to here is the
value measured by the indicator titration method described in "Test
methods for acid value, saponification value, ester value, iodine
value, hydroxyl value and unsaponifiable matter of chemical
products" of JIS K 0070. The saponification value is the value
measured by the indicator titration method described in "Testing
method of lubricating oil for aircraft" of JIS K 2503.
[0044] Component (B) according to the invention is an ester-based
polymer with a kinematic viscosity of greater than 20 mm.sup.2/s at
100.degree. C. and an average molecular weight of 5,000-10,000,000.
The term "ester-based polymer" according to the invention includes
both (B-1) polymers having an ester bond in the main chain, and
(B-2) polymers having an ester bond in a side chain.
[0045] The (B-1) polymers having an ester bond in the main chain
are "polyesters", i.e. polymers containing a polybasic acid and
polyhydric alcohol as essential monomer components. Such polymers
may be straight-chain polyesters composed of dibasic acids and
dihydric alcohols, or they may be complex esters composed of
dibasic or greater polybasic acids and dihydric or greater
polyhydric alcohols, and containing a tribasic or greater polybasic
acid and/or a trihydric or greater polyhydric alcohol as an
essential monomer component. Either a straight-chain polyester or
complex polyester may further include a monobasic acid and/or a
monohydric alcohol. The polybasic acid and polyhydric alcohol as
essential monomer components and the monobasic acid and monohydric
alcohol as optional monomer components may be any of the polybasic
acids, polyhydric alcohols, monobasic acids and monohydric alcohols
mentioned in explaining the component (A) above, and appropriate
selection of the types and proportions of these constituent
monomers can yield an ester-based polymer as component (B).
[0046] The (B-2) polymers having an ester bond in a side chain may
be obtained, for example, using a polymerizable monomer with an
ethylenic unsaturated bond and an ester bond. As such polymerizable
monomers there are preferably used monomers represented by the
following general formula (B-2-1), (B-2-2) or (B-2-3).
##STR00001##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, R.sup.3 represents C1-18
alkylene, R.sup.4 represents a C1-24 hydrocarbon group and p
represents 0 or 1.]
##STR00002##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, R.sup.3 represents C1-18
alkylene, R.sup.4 represents a C1-24 hydrocarbon group and p
represents 0 or 1.]
##STR00003##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, R.sup.3 and R.sup.5 may be the
same or different and each represents C1-18 alkylene, R.sup.4 and
R.sup.6 may be the same or different and each represents a C1-24
hydrocarbon group, and p and q may be the same or different and
each represents 0 or 1.]
[0047] R.sup.1 and R.sup.2 in general formulas (B-2-1)-(B-2-3)
above represent hydrogen or C1-4 alkyl. As C1-4 alkyl groups
represented by R.sup.1 and R.sup.2 there may be mentioned methyl,
ethyl, straight-chain or branched propyl and straight-chain or
branched butyl. Preferred as R.sup.1 and R.sup.2 are hydrogen,
methyl or ethyl, with hydrogen or methyl being more preferred. For
the compounds represented by general formulas (B-2-1) and (B-2-3),
both R.sup.1 and R.sup.2 are most preferably hydrogen. For the
monomer represented by general formula (B-2-2), most preferably
R.sup.1 is hydrogen and R.sup.2 is methyl.
[0048] As C1-18 alkylene groups represented by R.sup.3 and R.sup.5
there may be mentioned specifically, methylene, ethylene,
straight-chain or branched propylene, straight-chain or branched
butylene, straight-chain or branched pentyl, straight-chain or
branched hexylene, straight-chain or branched heptylene,
straight-chain or branched octylene, straight-chain or branched
nonylene, straight-chain or branched decylene, straight-chain or
branched undecylene, straight-chain or branched dodecylene,
straight-chain or branched tridecylene, straight-chain or branched
tetradecylene, straight-chain or branched pentadecylene,
straight-chain or branched hexadecylene, straight-chain or branched
heptadecylene and straight-chain or branched octadecylene.
[0049] Also, p in general formulas (B-2-1)-(B-2-3) and p and q in
general formula (B-2-3) are each 0 or 1. When p and q are 0, the
structure has a double bonded carbon atom and an ester group carbon
atom directly bonded together.
[0050] In the monomers represented by general formulas
(B-2-1)-(B-2-3), preferably p and q are 0 or p and q are 1 and
R.sup.3 and R.sup.5 are C1-10 alkylene groups, more preferably p
and q are 0 or p and q are 1 and R.sup.3 and R.sup.5 are C1-4
alkylene groups, even more preferably p and q are 0 or p and q are
1 and R.sup.3 and R.sup.5 are methylene or ethylene, even yet more
preferably p and q are 0 or p and q are 1 and R.sup.3 and R.sup.5
are methylene, and most preferably p and q are 0.
[0051] As specific examples of C1-24 hydrocarbon groups represented
by R.sup.4 and R.sup.6 there may be mentioned alkyl, cycloalkyl,
alkenyl, alkylcycloalkyl, aryl, alkylaryl and arylalkyl.
[0052] As examples of alkyl groups there may be mentioned alkyl
groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl and octadecyl (where the alkyl
groups may be straight-chain or branched).
[0053] As examples of cycloalkyl groups there may be mentioned C5-7
cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl.
As examples of the aforementioned alkylcycloalkyl groups there may
be mentioned C6-11 alkylcycloalkyl groups such as
methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl,
diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl,
methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl,
dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl
(with any positions of substitution of the alkyl groups on the
cycloalkyl groups).
[0054] As examples of the aforementioned alkenyl groups there may
be mentioned alkenyl groups such as butenyl, pentenyl, hexenyl,
heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl
and octadecenyl (where the alkenyl groups may be straight-chain or
branched, and the double bonds may be at any positions).
[0055] As examples of the aforementioned aryl groups there may be
mentioned aryl groups such as phenyl and naphthyl. As examples of
the aforementioned alkylaryl groups there may be mentioned C7-18
alkylaryl groups such as tolyl, xylyl, ethylphenyl, propylphenyl,
butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl,
nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl (where
the alkyl groups may be straight-chain or branched and substituted
at any positions on the aryl groups).
[0056] As examples of the aforementioned arylalkyl groups there may
be mentioned C7-12 arylalkyl groups such as benzyl, phenylethyl,
phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl (where the
alkyl groups may be straight-chain or branched).
[0057] The hydrocarbon groups represented by R.sup.4 and R.sup.6
are preferably C1-22 hydrocarbon groups, more preferably C1-20
hydrocarbon groups and even more preferably C1-18 hydrocarbon
groups.
[0058] The monomer represented by general formula (B-2-1) above is
preferably an ester of a monobasic fatty acid and a vinyl alcohol,
wherein R.sup.4 is a C1-22 (preferably C1-20, and more preferably
C1-18) hydrocarbon group.
[0059] The monomer represented by general formula (B-2-2) above is
preferably an acrylic acid ester wherein R.sup.4 is a C1-22
(preferably C1-20, and more preferably C1-18) hydrocarbon group or
a methacrylic acid ester wherein R.sup.4 is a C1-22 (preferably
C1-20, and more preferably C1-18) hydrocarbon group, and more
preferably it is a methacrylic acid ester wherein R.sup.4 is a
C1-22 (preferably C1-20, and more preferably C1-18) hydrocarbon
group.
[0060] The monomer represented by general formula (B-2-3) is
preferably a maleic acid diester or fumaric acid diester wherein
R.sup.4 and R.sup.6 are both C1-22 (preferably C1-20, and more
preferably C1-18) hydrocarbon groups, and more preferably it is
dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl
maleate or the like.
[0061] Of the monomers represented by general formulas
(B-2-1)-(B-2-3) above, monomers represented by general formula
(B-2-2) are preferred from the standpoint of stability and floating
mist inhibition.
[0062] Component (B) may be a homopolymer consisting of a single
type of monomer represented by general formulas (B-2-1)-(B-2-3)
above, or it may be a copolymer consisting of two or more thereof.
In addition to the monomers represented by general formulas
(B-2-1)-(B-2-3) above, there may be further included monomers
represented by the following general formulas (B-2-4)-(B-2-7).
##STR00004##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, and R.sup.7 represents hydrogen
or a C1-24 hydrocarbon group.]
##STR00005##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, and X.sup.1 and X.sup.2 may be
the same or different and each represents hydrogen or C1-18
monoalkylamino.]
##STR00006##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, R.sup.8 represents C2-18
alkylene, r represents 0 or 1 and X.sup.3 represents a C1-30
organic group containing a nitrogen atom.]
##STR00007##
[wherein R.sup.1 and R.sup.2 may be the same or different and each
represents hydrogen or C1-4 alkyl, and X.sup.3 represents a C1-30
organic group containing a nitrogen atom.]
[0063] R.sup.1 and R.sup.2 in general formulas (B-2-4)-(B-2-7) each
represent hydrogen or C1-4 alkyl. When R.sup.1 and R.sup.2 are C1-4
alkyl groups, the alkyl groups may be any of the C1-4 alkyl groups
mentioned in explaining R.sup.1 and R.sup.2 for (B-2-1)-(B-2-3)
above.
[0064] Also, R.sup.7 in general formula (B-2-4) is hydrogen or a
C1-24 hydrocarbon group. When R.sup.7 is a C1-24 hydrocarbon group,
the hydrocarbon group may be any of the C1-24 hydrocarbon groups
mentioned in explaining R.sup.4 and R.sup.6 above. R.sup.7 is
preferably hydrogen or a C1-20 hydrocarbon group, more preferably
hydrogen or a C1-15 hydrocarbon group, even more preferably
hydrogen or a C1-10 hydrocarbon group and most preferably hydrogen
or a C1-6 hydrocarbon group.
[0065] Also, X.sup.1 and X.sup.2 in general formula (B-2-5) each
represent hydrogen or C1-18 monoalkylamino. The C1-18
monoalkylamino groups represented by X.sup.1 and X.sup.2 are
residues resulting from removal of hydrogen from the amino group of
a C1-18 monoalkylamine group (--NHR.sup.8; where R.sup.8 is C1-18
alkyl). As C1-18 alkyl groups represented by R.sup.8 there may be
mentioned alkyl groups such as methyl, ethyl, propyl, butyl,
pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and
octadecyl (where the alkyl groups may be straight-chain or
branched).
[0066] As C2-18 alkylene groups represented by R.sup.8 in general
formula (B-2-6) there may be mentioned, specifically, alkylene
groups such as ethylene, propylene, butylene, pentylene, hexylene,
heptylene, octylene, nonylene, decylene, undecylene, dodecylene,
tridecylene, tetradecylene, pentadecylene, hexadecylene,
heptadecylene and octadecylene (where the alkylene groups may be
straight-chain or branched).
[0067] Also in (B-2-6), r represents 0 or 1. When r is 0, the
structure contains O (an oxygen atom) directly bonded to
X.sup.3.
[0068] X.sup.3 in general formulas (B-2-6) and (B-2-7) is a C1-30
organic group containing a nitrogen atom. The number of nitrogen
atoms in the organic group represented by X.sup.3 is not
particularly restricted but is preferably one. As mentioned above,
the number of carbon atoms in the organic group represented by
X.sup.3 is 1-30, preferably 1-20, and more preferably 1-16.
[0069] The organic group represented by X.sup.3 is preferably a
group containing an oxygen atom, and it also preferably contains a
ring. Particularly from the viewpoint of stability and machining
performance, the organic group represented by X.sup.3 preferably
has an oxygen-containing ring. When the organic group represented
by X.sup.3 is a group containing a ring, the ring may be an
aliphatic ring or aromatic ring, but it is preferably an aliphatic
ring. The ring of the organic group represented by X.sup.3 is
preferably a 6-membered ring from the standpoint of stability and
machining performance.
[0070] As organic groups represented by X.sup.3 there may be
mentioned, specifically, dimethylamino, diethylamino,
dipropylamino, dibutylamino, anilino, toluidino, xylidino,
acetylamino, benzoylamino, morpholino, pyrolyl, pyrrolino, pyridyl,
methylpyridyl, pyrrolidinyl, piperidinyl, quinonyl, pyrrolidonyl,
pyrrolidono, imidazolino and pyrazino, among which morpholino is
particularly preferred.
[0071] As preferred examples of monomers represented by general
formula (B-2-4) there may be mentioned ethylene, propylene,
1-butene, 2-butene, isobutene and styrene.
[0072] As preferred examples of monomers represented by general
formula (B-2-5) there may be mentioned maleic acid, fumaric acid,
maleic acid amide, fumaric acid amide and mixtures thereof.
[0073] As preferred examples of monomers represented by general
formula (B-2-6) or (B-2-7) there may be mentioned
dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
2-methyl-5-vinylpyridine, morpholinomethyl methacrylate,
morpholinoethyl methacrylate, N-vinylpyrrolidone and mixtures
thereof.
[0074] Preferred among the monomers represented by general formulas
(B-2-4)-(B-2-7) from the standpoint of stability and machining
performance are monomers represented by general formulas (B-2-4),
(B-2-6) and (B-2-7). Monomers represented by general formulas
(B-2-6) and (B-2-7) are more preferred, especially for combination
with monomers represented by general formula (B-2-2). Monomers
represented by general formulas (B-2-4) are more preferred for
combination with monomers represented by general formula
(B-2-3).
[0075] When component (B) of the invention is a copolymer
comprising a monomer represented by general formulas
(B-2-1)-(B-2-3) above or two or more monomers represented by
general formulas (B-2-4)-(B-2-7) above, there are no particular
restrictions on the polymerization form and it may be a block
copolymer or random copolymer, although random copolymers are
preferred from the standpoint of stability and machining
performance.
[0076] As preferred examples of (B-2) polymers having an ester bond
in a side chain there may be mentioned, specifically,
polymethacrylates, polyacrylates, polyvinyl esters,
isobutylene-fumaric acid diester copolymers, styrene-fumaric acid
diester copolymers and vinyl acetate-fumaric acid diester
copolymers.
[0077] An ester-based polymer as component (B) is one having a
kinematic viscosity of greater than 20 mm.sup.2/s at 100.degree. C.
Ester-based polymers with a kinematic viscosity of up to 20
mm.sup.2/s at 100.degree. C. are within the definition of component
(A) according to the invention, and if such an ester-based polymer
is used instead of component (B), it will not be possible to
achieve both a misting property and inhibition of floating
mist.
[0078] The average molecular weight of component (B) must be at
least 5,000 as mentioned above, and it is preferably at least 7,000
and more preferably at least 10,000. If the average molecular
weight of the ester-based polymer is less than 5,000, inhibition of
floating mist will be insufficient. The average molecular weight of
component (B) must also be no greater than 10,000,000 as mentioned
above, and it is preferably no greater than 1,000,000, more
preferably no greater than 500,000, even more preferably no greater
than 300,000 and most preferably no greater than 150,000. If the
average molecular weight of the ester-based polymer is greater than
10,000,000 the misting property will be insufficient.
[0079] There are no particular restrictions on the content of
component (B), but it is preferably at least 0.001% by mass, more
preferably at least 0.005% by mass and even more preferably at
least 0.01% by mass based on the total weight of the composition.
If the content of component (B) is less than 0.001% by mass, the
inhibiting effect against floating mist by using component (B) may
not be adequately exhibited. The content of component (B) is also
preferably no greater than 20% by mass, more preferably no greater
than 10% by mass and even more preferably no greater than 8% by
mass based on the total weight of the composition. If the content
of component (B) exceeds 20% by mass, the misting property and
biodegradability will tend to be reduced.
[0080] The oil composition of the invention may consist entirely of
components (A) and (B) described above, but if necessary it may
further contain the following base oils and additives.
[0081] As base oils in addition to components (A) and (B) there may
be mentioned mineral-based oils such as paraffin-based mineral oils
and naphthene-based mineral oils; polyolefins such as propylene
oligomers, polybutene, polyisobutylene, C5-20 .alpha.-olefin
oligomers and co-oligomers of ethylene and C5-20 .alpha.-olefins,
or their hydrogenated forms; alkylbenzenes such as
monoalkylbenzenes, dialkylbenzenes and polyalkylbenzenes;
alkylnaphthalenes such as monoalkylnaphthalenes,
dialkylnaphthalenes and polyalkylnaphthalenes; polyglycols such as
polyethylene glycol, polypropylene glycol,
polyoxyethylenepolyoxypropyleneglycol, polyethylene
glycolmonoether, polypropyleneglycolmonoether,
polyoxyethylenepolyoxypropyleneglycolmonoether, polyethyleneglycol
diether, polypropyleneglycol diether and
polyoxyethylenepolyoxypropyleneglycol diether; phenyl ethers such
as monoalkyldiphenyl ethers, dialkyldiphenyl ethers,
monoalkyltriphenyl ethers, dialkyltriphenyl ethers, tetraphenyl
ethers, monoalkyltetraphenyl ethers, dialkyltetraphenyl ethers and
pentaphenyl ethers, silicone oils; fluoroethers such as
perfluoroether, and the like.
[0082] The content of such base oils is not particularly restricted
so long as they do not impair the performance of the oil
composition of the invention, but it is preferably no greater than
90% by mass, more preferably no greater than 80% by mass, even more
preferably no greater than 70% by mass, yet more preferably no
greater than 50% by mass and even yet more preferably no greater
than 30% by mass, although most preferably no base oils are added
in addition to components (A) and (B).
[0083] The oil composition of the invention preferably contains (C)
an oil agent (preferably an oil agent with a molecular weight of
less than 5,000) from the viewpoint of further increasing the
machining efficiency and tool life.
[0084] As (C) oil agents there may be mentioned alcohol oil agents,
carboxylic acid oil agents, unsaturated carboxylic acid sulfides,
compounds represented by the following general formula (C-1),
compounds represented by the following general formula (C-2),
polyoxyalkylene compounds, ester oil agents, polyhydric alcohol
hydrocarbyl ethers, amine oil agents and the like.
##STR00008##
[wherein R.sup.9 represents a C1-30 hydrocarbon group, a represents
an integer of 1-6 and b represents an integer of 0-5.]
##STR00009##
[wherein R.sup.10 represents a C1-30 hydrocarbon group, C
represents an integer of 1-6 and D represents an integer of
0-5.]
[0085] An alcohol oil agent may be a monohydric alcohol or a
polyhydric alcohol. From the standpoint of achieving even better
machining efficiency and tool life, C1-40 monohydric alcohols are
preferred, C1-25 alcohols are more preferred and C8-18 alcohols are
most preferred. Specifically, there may be mentioned the examples
of cited as alcohols for the base oil ester. These alcohols may be
straight-chain or branched and either saturated or unsaturated, but
from the standpoint of preventing sticking, they are preferably
saturated.
[0086] A carboxylic acid oil agent may be a monobasic acid or a
polybasic acid. From the standpoint of achieving even higher
machining efficiency and tool life, C1-40 monobasic carboxylic
acids are preferred, C5-25 carboxylic acids are more preferred and
C5-20 carboxylic acids are most preferred. Specifically, there may
be mentioned the examples of carboxylic acids cited for the base
oil ester. These carboxylic acids may be straight-chain or branched
and either saturated or unsaturated, but from the standpoint of
preventing sticking, saturated carboxylic acids are preferred.
[0087] As examples of unsaturated carboxylic acid sulfides there
may be mentioned sulfides of unsaturated carboxylic acid oil agents
among those cited above. More specifically, there may be mentioned
sulfides of oleic acid.
[0088] As examples of C1-30 hydrocarbon groups represented by
R.sup.9 in compounds represented by general formula (C-1) above,
there may be mentioned C1-30 straight-chain or branched alkyl, C5-7
cycloalkyl, C6-30 alkylcycloalkyl, C2-30 straight-chain or branched
alkenyl, C6-10 aryl, C7-30 alkylaryl and C7-30 arylalkyl. Among
these, C1-30 straight-chain or branched alkyl groups are preferred,
C1-20 straight-chain or branched alkyl groups are more preferred,
C1-10 straight-chain or branched alkyl groups are even more
preferred, and C1-4 straight-chain or branched alkyl groups are
most preferred. As examples of C1-4 straight-chain or branched
alkyl groups there may be mentioned methyl, ethyl, straight-chain
or branched propyl and straight-chain or branched butyl.
[0089] A hydroxyl group may be substituted at any position, but in
the case of two or more hydroxyl groups they are preferably
substituted at adjacent carbon atoms. The symbol a is preferably an
integer of 1-3 and more preferably 2. The symbol b is preferably an
integer of 0-3 and more preferably 1 or 2. As an example of a
compound represented by general formula (1) there may be mentioned
p-tert-butylcatechol.
[0090] As examples of C1-30 hydrocarbon groups represented by
R.sup.10 in compounds represented by general formula (C-2) above,
there may be mentioned the same ones as cited for the C1-30
hydrocarbon group represented by R.sup.9 in general formula (C-1),
and the preferred ones are also the same. A hydroxyl group may be
substituted at any position, but in the case of two or more
hydroxyl groups they are preferably substituted at adjacent carbon
atoms. The symbol c is preferably an integer of 1-3 and more
preferably 2. The symbol d is preferably an integer of 0-3 and more
preferably 1 or 2. As examples of compounds represented by general
formula (2) there may be mentioned 2,2-dihydroxynaphthalene and
2,3-dihydroxynaphthalene.
[0091] As examples of polyoxyalkylene compounds there may be
mentioned compounds represented by the following general formula
(C-3) or (C-4).
R.sup.11O--(R.sup.12O).sub.e--R.sup.13 (C-3)
[wherein R.sup.11 and R.sup.13 may be the same or different and
each represents hydrogen or a C1-30 hydrocarbon group, R.sup.12
represents C2-4 alkylene and e represents an integer such that the
number-average molecular weight is 100-3500.]
A-[(R.sup.14O).sub.f--R.sup.15].sub.g (C-4)
[wherein A represents the residue of a polyhydric alcohol having
3-10 hydroxyl groups of which all or a portion of the hydrogens of
the hydroxyl groups have been removed, R.sup.14 represents C2-4
alkylene, R.sup.15 represents hydrogen or a C1-30 hydrocarbon
group, f represents an integer such that the number-average
molecular weight is 100-3500, and g represents the same number as
the number of hydrogens removed from the hydroxyl groups of A.]
[0092] In general formula (C-3), preferably either or both R.sup.11
and R.sup.13 are hydrogen. As examples of C1-30 hydrocarbon groups
represented by R.sup.11 and R.sup.13 there may be mentioned the
examples of C1-30 hydrocarbon groups represented by R.sup.9 in
general formula (C-1), and their preferred examples are also the
same. As specific examples of C2-4 alkylene groups represented by
R.sup.12 there may be mentioned ethylene, propylene
(methylethylene) and butylene (ethylethylene). The symbol e is
preferably a integer such that the number-average molecular weight
is 300-2000, and more preferably an integer such that the
number-average molecular weight is 500-1500.
[0093] As specific examples of polyhydric alcohols having 3-10
hydroxyl groups for A in general formula (C-4) above, there may be
mentioned polyhydric alcohols such as glycerin, polyglycerin
(2-4mers of glycerin including diglycerin, triglycerin and
tetraglycerin), trimethylolalkanes (trimethylolethane,
trimethylolpropane, trimethylolbutane) and their 2-4mers,
pentaerythritol, dipentaerythritol, 1,2,4-butanetriol,
1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol,
sorbitol, sorbitan, sorbitol-glycerin condensate, adonitol,
arabitol, xylitol, mannitol, iditol, tallitol, dulcitol, allitol
and the like; and sugars such as xylose, arabinose, ribose,
rhamnose, glucose, fructose, galactose, mannose, sorbose,
cellobiose, maltose, isomaltose, trehalose and sucrose. Preferred
among these are glycerin, polyglycerin, trimethylolalkanes and
their 2-4mers, pentaerythritol, dipentaerythritol, sorbitol and
sorbitan.
[0094] As examples of C2-4 alkylene groups represented by R.sup.14
there may be mentioned the same examples of C2-4 alkylene groups
represented by R.sup.12 in general formula (C-3). As examples of
C1-30 hydrocarbon groups represented by R.sup.15 there may be
mentioned the same examples of C1-30 hydrocarbon groups represented
by R.sup.9 in general formula (C-1), and their preferred examples
are also the same. At least one of the g R.sup.15 groups is
preferably hydrogen, and more preferably all of them are hydrogen.
The symbol f is preferably an integer such that the number-average
molecular weight is 300-2000, and more preferably an integer such
that the number-average molecular weight is 500-1500.
[0095] The alcohol in an ester oil agent may be a monohydric
alcohol or polyhydric alcohol, and the carboxylic acid may be a
monobasic acid or polybasic acid.
[0096] Examples of monohydric alcohols and polyhydric alcohols in
the ester oil include any monohydric alcohols and polyhydric
alcohols, while the acid of the ester oil agent may be a monobasic
acid or polybasic acid.
[0097] As monohydric alcohols there may be used those with 1-24,
preferably 1-12, and more preferably 1-8 carbon atoms, and such
alcohols may be either straight-chain or branched, and either
saturated or unsaturated. As specific examples of C1-24 alcohols
there may be mentioned methanol, ethanol, straight-chain or
branched propanol, straight-chain or branched butanol,
straight-chain or branched pentanol, straight-chain or branched
hexanol, straight-chain or branched heptanol, straight-chain or
branched octanol, straight-chain or branched nonanol,
straight-chain or branched decanol, straight-chain or branched
undecanol, straight-chain or branched dodecanol, straight-chain or
branched tridecanol, straight-chain or branched tetradecanol,
straight-chain or branched pentadecanol, straight-chain or branched
hexadecanol, straight-chain or branched heptadecanol,
straight-chain or branched octadecanol, straight-chain or branched
nonadecanol, straight-chain or branched eicosanol, straight-chain
or branched heneicosanol, straight-chain or branched tricosanol,
straight-chain or branched tetracosanol, and mixtures of these.
[0098] As polyhydric alcohols there may usually be used 2-10 hydric
alcohols, and preferably 2-6 hydric alcohols. As specific examples
of 2-10 hydric polyhydric alcohols there may be mentioned ethylene
glycol, diethylene glycol, polyethylene glycol (3-15mers of
ethylene glycol), propylene glycol, dipropylene glycol,
polypropylene glycol (3-15mers of propylene glycol), dihydric
alcohols such as 1,3-propanediol, 1,2-propanediol, 1,3-butanediol,
1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol,
1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol,
neopentyl glycol and the like; other polyhydric alcohols such as
glycerin, polyglycerin (2-8mers of glycerin including diglycerin,
triglycerin and tetraglycerin), trimethylolalkanes
(trimethylolethane, trimethylolpropane and trimethylolbutane) and
their 2-8mers, pentaerythritols and their 2-4mers,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensate, adonitol, arabitol, xylitol, mannitol and the like; and
sugars such as xylose, arabinose, ribose, rhamnose, glucose,
fructose, galactose, mannose, sorbose, cellobiose, maltose,
isomaltose, trehalose and sucrose, and mixtures thereof.
[0099] Preferred among these polyhydric alcohols are 2-6 hydric
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol (3-10mers of ethylene glycol), propyleneglycol,
dipropyleneglycol, polypropyleneglycol (3-10mers of
propyleneglycol), 1,3-propanediol, 2-methyl-1,2-propanediol,
2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin,
triglycerin, trimethylolalkanes (trimethylolethane,
trimethylolpropane, trimethylolbutane, and the like) and their
2-4mers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol,
1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol,
sorbitol, sorbitan, sorbitol-glycerin condensate, adonitol,
arabitol, xylitol, mannitol and the like, as well as mixtures
thereof. More preferred are ethylene glycol, propylene glycol,
neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
pentaerythritol, sorbitan and mixtures thereof. Most preferred
among these are neopentyl glycol, trimethylolethane,
trimethylolpropane, pentaerythritol and mixtures thereof, since
these can yield higher heat and oxidation stability.
[0100] The alcohol of the ester oil agent may be a monohydric
alcohol or polyhydric alcohol as mentioned above, but it is
preferably a polyhydric alcohol from the standpoint of achieving
machining efficiency and tool life, and of more easily lowering the
pour point and further improving manageability in winter season and
cold climates. Using a polyhydric alcohol ester will increase the
effect of improving the finished surface precision of the workpiece
and preventing wear of the tool blade edge during cutting and
grinding.
[0101] In most cases a C2-24 fatty acid will be used as the
monobasic acid among acids for the ester oil agent, and such fatty
acids may be straight-chain or branched and either saturated or
unsaturated. As specific examples there may be mentioned saturated
fatty acids such as acetic acid, propionic acid, straight-chain or
branched butanoic acid, straight-chain or branched pentanoic acid,
straight-chain or branched hexanoic acid, straight-chain or
branched heptanoic acid, straight-chain or branched octanoic acid,
straight-chain or branched nonanoic acid, straight-chain or
branched decanoic acid, straight-chain or branched undecanoic acid,
straight-chain or branched dodecanoic acid, straight-chain or
branched tridecanoic acid, straight-chain or branched tetradecanoic
acid, straight-chain or branched pentadecanoic acid, straight-chain
or branched hexadecanoic acid, straight-chain or branched
heptadecanoic acid, straight-chain or branched octadecanoic acid,
straight-chain or branched hydroxyoctadecanoic acid, straight-chain
or branched nonadecanoic acid, straight-chain or branched
eicosanoic acid, straight-chain or branched heneicosanoic acid,
straight-chain or branched docosanoic acid, straight-chain or
branched tricosanoic acid and straight-chain or branched
tetracosanoic acid; and unsaturated fatty acids such as acrylic
acid, straight-chain or branched butenoic acid, straight-chain or
branched pentanoic acid, straight-chain or branched hexenoic acid,
straight-chain or branched heptenoic acid, straight-chain or
branched octenoic acid, straight-chain or branched nonenoic acid,
straight-chain or branched decenoic acid, straight-chain or
branched undecenoic acid, straight-chain or branched dodecenoic
acid, straight-chain or branched tridecenoic acid, straight-chain
or branched tetradecenoic acid, straight-chain or branched
pentadecenoic acid, straight-chain or branched hexadecenoic acid,
straight-chain or branched heptadecenoic acid, straight-chain or
branched octadecenoic acid, straight-chain or branched
hydroxyoctadecenoic acid, straight-chain or branched nonadecenoic
acid, straight-chain or branched eicosenoic acid, straight-chain or
branched heneicosenoic acid, straight-chain or branched docosenoic
acid, straight-chain or branched tricosenoic acid and
straight-chain or branched tetracosenoic acid, as well as mixtures
thereof. From the viewpoint of achieving superior working
efficiency and tool life, as well as manageability, C3-20 saturated
fatty acids, C3-22 unsaturated fatty acids and their mixtures are
preferred, C4-18 saturated fatty acids, C4-18 unsaturated fatty
acids and their mixtures are more preferred and C4-18 unsaturated
fatty acids are even more preferred, and from the viewpoint of
sticking prevention, C4-18 saturated fatty acids are preferred.
[0102] As polybasic acids there may be mentioned C2-16 dibasic
acids, trimellitic acid and the like. Such C2-16 dibasic acids may
be straight-chain or branched, and either saturated or unsaturated.
As specific examples there may be mentioned ethanedioic acid,
propanedioic acid, straight-chain or branched butanedioic acid,
straight-chain or branched pentanedioic acid, straight-chain or
branched hexanedioic acid, straight-chain or branched heptanedioic
acid, straight-chain or branched octanedioic acid, straight-chain
or branched nonanedioic acid, straight-chain or branched
decanedioic acid, straight-chain or branched undecenedioic acid,
straight-chain or branched dodecanedioic acid, straight-chain or
branched tridecanedioic acid, straight-chain or branched
tetradecanedioic acid, straight-chain or branched heptadecanedioic
acid, straight-chain or branched hexadecanedioic acid,
straight-chain or branched hexenedioic acid, straight-chain or
branched heptenedioic acid, straight-chain or branched octenedioic
acid, straight-chain or branched nonenedioic acid, straight-chain
or branched decenedioic acid, straight-chain or branched
undecenedioic acid, straight-chain or branched dodecenedioic acid,
straight-chain or branched tridecenedioic acid, straight-chain or
branched tetradecenedioic acid, straight-chain or branched
heptadecenedioic acid, straight-chain or branched hexadecenedioic
acid, and mixtures thereof.
[0103] The combination of alcohol and acid in the ester oil agent
may be as desired without any particular restrictions, but the
following esters may be mentioned as preferred examples for ester
oil agents to be used for the invention.
(i) Esters of monohydric alcohols and monobasic acids (ii) Esters
of polyhydric alcohols and monobasic acids (iii) Esters of
monohydric alcohols and polybasic acids (iv) Esters of polyhydric
alcohols and polybasic acids (v) Mixed esters of monohydric alcohol
and polyhydric alcohol mixtures and polybasic acids (vi) Mixed
esters of polyhydric alcohols and monobasic acid and polybasic acid
mixtures (vii) Mixed esters of monohydric alcohol and polyhydric
alcohol mixtures and monobasic acid and polybasic acid mixtures
[0104] When a polyhydric alcohol is used as the alcohol component,
the ester may be a complete ester obtained by esterification of all
of the hydroxyl groups in the polyhydric alcohol, or a partial
ester wherein some of the hydroxyl groups remain as hydroxyl groups
without esterification. When a polybasic acid is used as the
carboxylic acid component, the ester may be a complete ester
obtained by esterification of all of the carboxyl groups in the
polybasic acid, or a partial ester wherein some of the carboxyl
groups remain as carboxyl groups without esterification. From the
standpoint of machining performance, the ester oil agent is
preferably a partial ester.
[0105] There are no particular restrictions on the total number of
carbon atoms in the ester oil agent, but from the standpoint of
achieving superior machining efficiency and tool life, the ester
preferably has a total of at least 7 carbon atoms, more preferably
at least 9 carbon atoms and most preferably at least 11 carbon
atoms. From the standpoint of avoiding increased staining and
corrosion, and of compatibility with organic materials, the ester
preferably has a total of no greater than 60 carbon atoms, more
preferably no greater than 45 carbon atoms, even more preferably no
greater than 26 carbon atoms, yet more preferably no greater than
24 carbon atoms and most preferably no greater than 22 carbon
atoms.
[0106] The polyhydric alcohol in the polyhydric alcohol hydrocarbyl
ether will usually be a 2-10 hydric and preferably 2-6 hydric
compound. As specific examples of 2-10 hydric polyhydric alcohols
there may be mentioned ethylene glycol, diethylene glycol,
polyethylene glycol (3-15mers of ethylene glycol), propylene
glycol, dipropylene glycol, polypropylene glycol (3-15mers of
propylene glycol), dihydric alcohols such as 1,3-propanediol,
1,2-propanediol, 1,3-butanediol, 1,4-butanediol,
2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol,
1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol,
neopentyl glycol and the like; polyhydric alcohols such as
glycerin, polyglycerin (2-8mers of glycerin including diglycerin,
triglycerin and tetraglycerin), trimethylolalkanes
(trimethylolethane, trimethylolpropane and trimethylolbutane) and
their 2-8mers, pentaerythritols and their 2-4mers,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensate, adonitol, arabitol, xylitol, mannitol and the like; and
sugars such as xylose, arabinose, ribose, rhamnose, glucose,
fructose, galactose, mannose, sorbose, cellobiose, maltose,
isomaltose, trehalose and sucrose, and mixtures thereof.
[0107] Preferred among these polyhydric alcohols are 2-6 hydric
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol (3-10mers of ethylene glycol), propyleneglycol,
dipropyleneglycol, polypropyleneglycol (3-10mers of
propyleneglycol), 1,3-propanediol, 2-methyl-1,2-propanediol,
2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin,
triglycerin, trimethylolalkanes (trimethylolethane,
trimethylolpropane, trimethylolbutane, and the like) and their
2-4mers pentaerythritol, dipentaerythritol, 1,2,4-butanetriol,
1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol,
sorbitol, sorbitan, sorbitol-glycerin condensate, adonitol,
arabitol, xylitol, mannitol and the like, as well as mixtures
thereof. More preferred are ethylene glycol, propylene glycol,
neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane,
pentaerythritol, sorbitan and mixtures thereof. Among these,
glycerin is most preferred from the standpoint of achieving
superior machining efficiency and tool life.
[0108] The polyhydric alcohol hydrocarbyl ether used may be one
having all or only a portion of the hydroxyl groups of the
polyhydric alcohol converted by hydrocarbyl etherification. From
the standpoint of achieving superior machining efficiency and tool
life, preferably only a portion of the hydroxyl groups of the
polyhydric alcohol are converted by hydrocarbyl etherification
(partial etherified product). The hydrocarbyl group referred to
here is a C1-24 hydrocarbon group such as C1-24 alkyl, C2-24
alkenyl, C5-7 cycloalkyl, C6-11 alkylcycloalkyl, C6-10 aryl, C7-18
alkylaryl or C7-18 arylalkyl.
[0109] As C1-24 alkyl groups there may be mentioned methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
straight-chain or branched pentyl, straight-chain or branched
hexyl, straight-chain or branched heptyl, straight-chain or
branched octyl, straight-chain or branched nonyl, straight-chain or
branched decyl, straight-chain or branched undecyl, straight-chain
or branched dodecyl, straight-chain or branched tridecyl,
straight-chain or branched tetradecyl, straight-chain or branched
pentadecyl, straight-chain or branched hexadecyl, straight-chain or
branched heptadecyl, straight-chain or branched octadecyl,
straight-chain or branched nonadecyl, straight-chain or branched
eicosyl, straight-chain or branched heneicosyl, straight-chain or
branched docosyl, straight-chain or branched tricosyl and
straight-chain or branched tetracosyl.
[0110] As C2-24 alkenyl groups there may be mentioned vinyl,
straight-chain or branched propenyl, straight-chain or branched
butenyl, straight-chain or branched pentenyl, straight-chain or
branched hexenyl, straight-chain or branched heptenyl,
straight-chain or branched octenyl, straight-chain or branched
nonenyl, straight-chain or branched decenyl, straight-chain or
branched undecenyl, straight-chain or branched dodecenyl,
straight-chain or branched tridecenyl, straight-chain or branched
tetradecenyl, straight-chain or branched pentadecenyl,
straight-chain or branched hexadecenyl, straight-chain or branched
heptadecenyl, straight-chain or branched octadecenyl,
straight-chain or branched nonadecenyl, straight-chain or branched
eicosenyl, straight-chain or branched heneicosenyl, straight-chain
or branched docosenyl, straight-chain or branched tricosenyl and
straight-chain or branched tetracosenyl.
[0111] As C5-7 cycloalkyl groups there may be mentioned
cyclopentyl, cyclohexyl and cycloheptyl. As C6-11 alkylcycloalkyl
groups there may be mentioned methylcyclopentyl,
dimethylcyclopentyl (including all structural isomers),
methylethylcyclopentyl (including all structural isomers),
diethylcyclopentyl (including all structural isomers),
methylcyclohexyl, dimethylcyclohexyl (including all structural
isomers), methylethylcyclohexyl (including all structural isomers),
diethylcyclohexyl (including all structural isomers),
methylcycloheptyl, dimethylcycloheptyl (including all structural
isomers), methylethylcycloheptyl (including all structural isomers)
and diethylcycloheptyl (including all structural isomers).
[0112] As C6-10 aryl groups there may be mentioned phenyl and
naphthyl. As C7-18 alkylaryl groups there may be mentioned tolyl
(including all structural isomers), xylyl (including all structural
isomers), ethylphenyl (including all structural isomers),
straight-chain or branched propylphenyl (including all structural
isomers), straight-chain or branched butylphenyl (including all
structural isomers), straight-chain or branched pentylphenyl
(including all structural isomers), straight-chain or branched
hexylphenyl (including all structural isomers), straight-chain or
branched heptylphenyl (including all structural isomers),
straight-chain or branched octylphenyl (including all structural
isomers), straight-chin or branched nonylphenyl (including all
structural isomers), straight-chain or branched decylphenyl
(including all structural isomers), straight-chain or branched
undecylphenyl (including all structural isomers) and straight-chain
or branched dodecylphenyl (including all structural isomers).
[0113] As C7-12 arylalkyl groups there may be mentioned benzyl,
phenylethyl, phenylpropyl (including propyl isomers), phenylbutyl
(including butyl isomers), phenylpentyl (including pentyl isomers)
and phenylhexyl (including hexyl isomers).
[0114] Preferred among these from the standpoint of achieving
superior machining efficiency and tool life are C2-18
straight-chain or branched alkyl groups and C2-18 straight-chain or
branched alkenyl groups, among which C3-12 straight-chain or
branched alkyl and oleyl (residue obtained by removing hydroxyl
from oleyl alcohol) are more preferred.
[0115] A monoamine is preferred for use as an amine oil agent. The
number of carbon atoms of the monoamine is preferably 6-24 and more
preferably 12-24. Here, the number of carbon atoms is the total
number of carbon atoms of the monoamine, and when the monoamine has
two or more hydrocarbon groups it is the total number of their
carbon atoms.
[0116] Monoamines to be used for the invention include primary
monoamines, secondary monoamines and tertiary monoamines, although
primary monoamines are preferred from the standpoint of increasing
working efficiency and extending tool life.
[0117] As hydrocarbon groups bonded to the nitrogen atom of the
monoamine there may be used alkyl, alkenyl, cycloalkyl,
alkylcycloalkyl, aryl, alkylaryl, arylalkyl and the like, although
alkyl and alkenyl groups are preferred from the standpoint of
achieving superior machining efficiency and tool life. The alkyl
and alkenyl groups may be straight-chain or branched, but are
preferably straight-chain from the standpoint of achieving superior
machining efficiency and tool life.
[0118] As specific examples of preferred monoamines to be used for
the invention there may be mentioned hexylamine (including all
isomers), heptylamine (including all isomers), octylamine
(including all isomers), nonylamine (including all isomers),
decylamine (including all isomers), undecylamine (including all
isomers), dodecylamine (including all isomers), tridecylamine
(including all isomers), tetradecylamine (including all isomers),
pentadecylamine (including all isomers), hexadecylamine (including
all isomers), heptadecylamine (including all isomers),
octadecylamine (including all isomers), nonadecylamine (including
all isomers), eicosylamine (including all isomers), heneicosylamine
(including all isomers), docosylamine (including all isomers),
tricosylamine (including all isomers), tetracosylamine (including
all isomers), octadecenylamine (including all isomers) (including
oleylamine and the like), and mixtures of two or more thereof.
Among these, C12-24 primary monoamines are preferred, C14-20
primary monoamines are more preferred and C16-18 primary monoamines
are even more preferred, from the standpoint of achieving superior
machining efficiency and tool life.
[0119] According to the invention, only one selected from among the
aforementioned oil agents may be used, or a mixture of two or more
thereof may be used. Preferred among these, from the standpoint of
achieving superior machining efficiency and tool life, are one or a
mixture of two or more selected from carboxylic acid oil agents and
amine oil agents.
[0120] The content of the (C) oil agent is not particularly
restricted, but from the standpoint of achieving superior machining
efficiency and tool life, it is preferably at least 0.01% by mass,
more preferably at least 0.05% by mass and even more preferably at
least 0.1% by mass based on the total weight of the composition.
From the standpoint of stability, the oil agent content is
preferably no greater than 15% by mass, more preferably no greater
than 10% by mass and even more preferably no greater than 5% by
mass based on the total weight of the composition.
[0121] The oil composition of the invention preferably also further
contains (D) an extreme-pressure agent, from the viewpoint of
achieving superior machining efficiency and tool life. Particularly
when the (D) extreme-pressure agent is used together with the (C)
oil agent described above, the components work synergistically to
allow even greater superiority to be achieved in machining
efficiency and tool life. As described hereunder, the oil
composition of the invention may be used as a lubricating oil for
sections other than machine tool working sections, in which case
they preferably contain the (C) oil agent.
[0122] As preferred extreme pressure agents there may be mentioned
the sulfur compounds and phosphorus compounds mentioned below.
[0123] There are no particular restrictions on sulfur compounds to
be used so long as the properties of the oil composition of the
invention are not impaired, but preferred for use are dihydrocarbyl
polysulfide, sulfidized esters, sulfide mineral oils, zinc
dithiophosphate compounds, zinc dithiocarbaminate compounds,
molybdenum dithiophosphate compounds and molybdenum
dithiocarbaminate.
[0124] Dihydrocarbyl polysulfides are sulfur-based compounds
commonly known as polysulfides or olefin sulfides, and specifically
they are represented by the following general formula (D-1).
R.sup.16--S.sub.h--R.sup.17 (D-1)
[wherein R.sup.16 and R.sup.17 may be the same or different and
each represents C3-20 straight chain or branched alkyl, C6-20 aryl,
C6-20 alkylaryl or C6-20 arylalkyl, and h represents an integer of
2-6 and preferably 2-5.]
[0125] As specific examples of R.sup.16 and R.sup.17 in general
formula (D-1) there may be mentioned straight chain or branched
alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, straight-chain or branched pentyl,
straight-chain or branched hexyl, straight-chain or branched
heptyl, straight-chain or branched octyl, straight-chain or
branched nonyl, straight-chain or branched decyl, straight-chain or
branched undecyl, straight-chain or branched dodecyl,
straight-chain or branched tridecyl, straight-chain or branched
tetradecyl, straight-chain or branched pentadecyl, straight-chain
or branched hexadecyl, straight-chain or branched heptadecyl,
straight-chain or branched octadecyl, straight-chain or branched
nonadecyl and straight-chain or branched eicosyl; aryl groups such
as phenyl and naphthyl; alkylaryl groups such as tolyl (including
all structural isomers), ethylphenyl (including all structural
isomers), straight-chain or branched propylphenyl (including all
structural isomers), straight-chain or branched butylphenyl
(including all structural isomers), straight-chain or branched
pentylphenyl (including all structural isomers), straight-chain or
branched hexylphenyl (including all structural isomers),
straight-chain or branched heptylphenyl (including all structural
isomers), straight-chain or branched octylphenyl (including all
structural isomers), straight-chain or branched nonylphenyl
(including all structural isomers), straight-chain or branched
decylphenyl (including all structural isomers), straight-chain or
branched undecylphenyl (including all structural isomers),
straight-chain or branched dodecylphenyl (including all structural
isomers), xylyl (including all structural isomers),
ethylmethylphenyl (including all structural isomers), diethylphenyl
(including all structural isomers), di(straight-chain or
branched)propylphenyl (including all structural isomers),
di(straight-chain or branched)butylphenyl (including all structural
isomers), methylnaphthyl (including all structural isomers),
ethylnaphthyl (including all structural isomers), straight-chain or
branched propylnaphthyl (including all structural isomers),
straight-chain or branched butylnaphthyl (including all structural
isomers), dimethylnaphthyl (including all structural isomers),
ethylmethylnaphthyl (including all structural isomers),
diethylnaphthyl (including all structural isomers),
di(straight-chain or branched)propylnaphthyl (including all
structural isomers) and di(straight-chain or branched)butylnaphthyl
(including all structural isomers); and arylalkyl groups such as
benzyl, phenylethyl (including all isomers) and phenylpropyl
(including all isomers). Among these there are preferred compounds
wherein R.sup.16 and R.sup.17 in general formula (D-1) are C3-18
alkyl groups derived from propylene, 1-butene or isobutylene, or
C6-8 aryl, alkylaryl or arylalkyl groups, and as examples of such
groups there may be mentioned alkyl groups such as isopropyl,
branched hexyl derived from propylene dimer (including all branched
isomers), branched nonyl derived from propylene trimer (including
all branched isomers), branched dodecyl derived from propylene
tetramer (including all branched isomers), branched pentadecyl
derived from propylene pentamer (including all branched isomers),
branched octadecyl derived from propylene hexamer (including all
branched isomers), sec-butyl, tert-butyl, branched octyl derived
from 1-butene dimer (including all branched isomers), branched
octyl derived from isobutylene dimer (including all branched
isomers), branched dodecyl derived from 1-butene trimer (including
all branched isomers), branched dodecyl derived from isobutylene
trimer (including all branched isomers), branched hexadecyl derived
from 1-butene tetramer (including all branched isomers) and
branched hexadecyl derived from isobutylene tetramer (including all
branched isomers); alkylaryl groups such as phenyl, tolyl
(including all structural isomers), ethylphenyl (including all
structural isomers) and xylyl (including all structural isomers);
and arylalkyl groups such as benzyl and phenylethyl (including all
isomers).
[0126] From the standpoint of achieving superior machining
efficiency and tool life, R.sup.16 and R.sup.17 in general formula
(D-1) above are more preferably each separately a C3-18 branched
alkyl group derived from ethylene or propylene and most preferably
a C6-15 branched alkyl group derived from ethylene or
propylene.
[0127] As specific examples of sulfidized esters there may be
mentioned those prepared by sulfidizing of vegetable oils and fats
such as beef tallow, lard, fish oil, rapeseed oil and soybean oil;
unsaturated fatty acid esters obtained by reacting unsaturated
fatty acids (including oleic acid, linoleic acid and fatty acids
extracted from the aforementioned animal and vegetable oils and
fats) and various alcohols; as well as mixtures thereof, by any
desired methods.
[0128] A sulfide mineral oil is a mineral oil in which simple
sulfur is dissolved. The mineral oil used for the sulfide mineral
oil of the invention is not particularly restricted, and
specifically there may be mentioned paraffin-based mineral oils,
naphthene-based mineral oils and the like obtained by refining
lube-oil distillates, in turn obtained by atmospheric distillation
and vacuum distillation of stock oil, by an appropriate combination
of refining treatments such as solvent deasphalting, solvent
extraction, hydrotreatment, solvent dewaxing, catalytic dewaxing,
hydrorefining, sulfuric acid cleaning, white clay treatment or the
like. The simple sulfur may be in the form of a mass, powder,
molten liquid or the like, but simple sulfur in powder or molten
liquid form is preferred for use because it allows efficient
dissolution in base oils. Simple sulfur in molten liquid form is
miscible with other liquids and therefore has the advantage of
allowing the solution operation to be accomplished in a very brief
period, but the handling temperature must be above the melting
point of simple sulfur, requiring special apparatuses such as
heating equipment, and because it must be handled in a high
temperature atmosphere the handling is often associated with
danger. Simple sulfur in powder form, however, is inexpensive and
easy to handle and has a sufficiently short dissolution time, and
is therefore particularly preferred. There are no particular
restrictions on the sulfur content of a sulfide mineral oil for the
invention, but in most cases it is preferably 0.05-1.0% by mass and
more preferably 0.1-0.5% by mass based on the total weight of the
sulfide mineral oil.
[0129] The zinc dithiophosphate compounds, zinc dithiocarbaminate
compounds, molybdenum dithiophosphate compounds and molybdenum
dithiocarbaminate compounds referred to here are compounds
represented by the following general formulas (D-2)-(D-5).
##STR00010##
[wherein R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22,
R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28,
R.sup.29, R.sup.30, R.sup.31, R.sup.32 and R.sup.33 may be the same
or different and each represents a C1 or greater hydrocarbon group,
and Y.sup.1 and Y.sup.2 each represent an oxygen or sulfur
atom.]
[0130] As specific examples of hydrocarbon groups represented by
R.sup.18-R.sup.33 there may be mentioned alkyl groups such as
methyl, ethyl, propyl (including all branched isomers), butyl
(including all branched isomers), pentyl (including all branched
isomers), hexyl (including all branched isomers), heptyl (including
all branched isomers), octyl (including all branched isomers),
nonyl (including all branched isomers), decyl (including all
branched isomers), undecyl (including all branched isomers),
dodecyl (including all branched isomers), tridecyl (including all
branched isomers), tetradecyl (including all branched isomers),
pentadecyl (including all branched isomers), hexadecyl (including
all branched isomers), heptadecyl (including all branched isomers),
octadecyl (including all branched isomers), nonadecyl (including
all branched isomers), eicosyl (including all branched isomers),
heneicosyl (including all branched isomers), docosyl (including all
branched isomers), tricosyl (including all branched isomers) and
tetracosyl (including all branched isomers); cycloalkyl groups such
as cyclopentyl, cyclohexyl and cycloheptyl; alkylcycloalkyl groups
such as methylcyclopentyl (including all substituted isomers),
ethylcyclopentyl (including all substituted isomers),
dimethylcyclopentyl (including all substituted isomers),
propylcyclopentyl (including all branched isomers and substituted
isomers), methyl ethylcyclopentyl (including all substituted
isomers), trimethylcyclopentyl (including all substituted isomers),
butylcyclopentyl (including all branched isomers and substituted
isomers), methylpropylcyclopentyl (including all branched isomers
and substituted isomers), diethylcyclopentyl (including all
substituted isomers), dimethyl ethylcyclopentyl (including all
substituted isomers), methylcyclohexyl (including all substituted
isomers), ethylcyclohexyl (including all substituted isomers),
dimethylcyclohexyl (including all substituted isomers),
propylcyclohexyl (including all branched isomers and substituted
isomers), methylethylcyclohexyl (including all substituted
isomers), trimethylcyclohexyl (including all substituted isomers),
butylcyclohexyl (including all branched isomers and substituted
isomers), methylpropylcyclohexyl (including all branched isomers
and substituted isomers), diethylcyclohexyl (including all
substituted isomers), dimethylethylcyclohexyl (including all
substituted isomers), methylcycloheptyl (including all substituted
isomers), ethylcycloheptyl (including all substituted isomers),
dimethylcycloheptyl (including all substituted isomers),
propylcycloheptyl (including all branched isomers and substituted
isomers), methylethylcycloheptyl (including all substituted
isomers), trimethylcycloheptyl (including all substituted isomers),
butylcycloheptyl (including all branched isomers and substituted
isomers), methylpropylcycloheptyl (including all branched isomers
and substituted isomers), diethylcycloheptyl (including all
substituted isomers) and dimethylethylcycloheptyl (including all
substituted isomers); aryl groups such as phenyl and naphthyl;
alkylaryl groups such as tolyl (including all substituted isomers),
xylyl (including all substituted isomers), ethylphenyl (including
all substituted isomers), propylphenyl (including all branched
isomers and substituted isomers), methylethylphenyl (including all
substituted isomers), trimethylphenyl (including all substituted
isomers), butylphenyl (including all branched isomers and
substituted isomers), methylpropylphenyl (including all branched
isomers and substituted isomers), diethylphenyl (including all
substituted isomers), dimethylethylphenyl (including all
substituted isomers), pentylphenyl (including all branched isomers
and substituted isomers), hexylphenyl (including all branched
isomers and substituted isomers), heptylphenyl (including all
branched isomers and substituted isomers), octylphenyl (including
all branched isomers and substituted isomers), nonylphenyl
(including all branched isomers and substituted isomers),
decylphenyl (including all branched isomers and substituted
isomers), undecylphenyl (including all branched isomers and
substituted isomers), dodecylphenyl (including all branched isomers
and substituted isomers), tridecylphenyl (including all branched
isomers and substituted isomers), tetradecylphenyl (including all
branched isomers and substituted isomers), pentadecylphenyl
(including all branched isomers and substituted isomers),
hexadecylphenyl (including all branched isomers and substituted
isomers), heptadecylphenyl (including all branched isomers and
substituted isomers) and octadecylphenyl (including all branched
isomers and substituted isomers); and arylalkyl groups such as
benzyl, phenethyl, phenylpropyl (including all branched isomers)
and phenylbutyl (including all branched isomers).
[0131] According to the invention, using at least one compound
selected from the group consisting of dihydrocarbyl polysulfides
and sulfidized esters among the aforementioned sulfur compounds is
preferred since it will allow an even higher level of machining
efficiency and tool life to be achieved.
[0132] As specific examples of phosphorus compounds there may be
mentioned phosphoric acid esters, acidic phosphoric acid esters,
acidic phosphoric acid ester amine salts, chlorinated phosphoric
acid esters, phosphorous acid esters and phosphorothionates, as
well as metal salts of phosphorus compounds represented by the
following general formula (D-6) or (D-7). These phosphorus
compounds may also be esters of phosphoric acid, phosphorous acid
or thiophosphoric acid with alkanols or polyether alcohols, or
derivatives thereof.
##STR00011##
[wherein Y.sup.3, Y.sup.4 and Y.sup.5 may be the same or different
and each represents an oxygen or sulfur atom, with the proviso that
at least two of Y.sup.3, Y.sup.4 and Y.sup.5 are oxygen atoms,
while R.sup.34, R.sup.35 and R.sup.36 may be the same or different
and each represents hydrogen or a C1-30 hydrocarbon group.]
##STR00012##
[wherein Y.sup.6, Y.sup.7, Y.sup.8 and Y.sup.9 may be the same or
different and each represents an oxygen atom or sulfur atom, with
the proviso that at least three among Y.sup.6, Y.sup.7, Y.sup.8 and
Y.sup.9 are oxygen atoms, while R.sup.37, R.sup.38 and R.sup.39 may
be the same or different and each represents hydrogen or a C1-30
hydrocarbon group.]
[0133] More specifically, as phosphoric acid esters there may be
mentioned tributyl phosphate, tripentyl phosphate, trihexyl
phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl
phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl
phosphate, tritridecyl phosphate, tritetradecyl phosphate,
tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl
phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl
phosphate, tricresyl phosphate, trixylenyl phosphate,
cresyldiphenyl phosphate, xylenyldiphenyl phosphate and the
like;
as acidic phosphoric acid esters there may be mentioned monobutyl
acid phosphate, monopentyl acid phosphate, monohexyl acid
phosphate, monoheptyl acid phosphate, monooctyl acid phosphate,
monononyl acid phosphate, monodecyl acid phosphate, monoundecyl
acid phosphate, monododecyl acid phosphate, monotridecyl acid
phosphate, monotetradecyl acid phosphate, monopentadecyl acid
phosphate, monohexadecyl acid phosphate, monoheptadecyl acid
phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate,
dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid
phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl
acid phosphate, didecyl acid phosphate, diundecyl acid phosphate,
didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl
acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid
phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate,
dioleyl acid phosphate and the like; as acidic phosphoric acid
ester amine salts there may be mentioned salts of amines such as
methylamines, ethylamines, propylamines, butylamines, pentylamines,
hexylamines, heptylamines, octylamines, dimethylamines,
diethylamines, dipropylamines, dibutylamines, dipentylamines,
dihexylamines, diheptylamines, dioctylamines, trimethylamines,
triethylamines, tripropylamines, tributylamines, tripentylamines,
trihexylamines, triheptylamine and trioctylamines of the
aforementioned acidic phosphoric acid esters; as chlorinated
phosphoric acid esters there may be mentioned tris.dichloropropyl
phosphate, tris.chloroethyl phosphate, tris.chlorophenyl phosphate,
polyoxyalkylene.bis[di(chloroalkyl)]phosphate and the like; as
phosphorous acid esters there may be mentioned dibutyl phosphite,
dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl
phosphite, dinonyl phosphite, didecyl phosphite, diundecyl
phosphite, didodecyl phosphite, dioleyl phosphite, diphenyl
phosphite, dicresyl phosphite, tributyl phosphite, tripentyl
phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl
phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl
phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl
phosphite, tricresyl phosphite and the like; and as
phosphorothionates there may be mentioned tributyl
phosphorothionate, tripentyl phosphorothionate, trihexyl
phosphorothionate, triheptyl phosphorothionate, trioctyl
phosphorothionate, trinonyl phosphorothionate, tridecyl
phosphorothionate, triundecyl phosphorothionate, tridodecyl
phosphorothionate, tritridecyl phosphorothionate, tritetradecyl
phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl
phosphorothionate, triheptadecyl phosphorothionate, trioctadecyl
phosphorothionate, trioleyl phosphorothionate, triphenyl
phosphorothionate, tricresyl phosphorothionate, trixylenyl
phosphorothionate, cresyldiphenyl phosphorothionate,
xylenyldiphenyl phosphorothionate,
tris(n-propylphenyl)phosphorothionate,
tris(isopropylphenyl)phosphorothionate, tris(n-butylphenyl)
phosphorothionate, tris(isobutylphenyl)phosphorothionate,
tris(s-butylphenyl)phosphorothionate and tris(t-butylphenyl)
phosphorothionate.
[0134] For metal salts of the phosphorus compounds represented by
general formulas (D-6) and (D-7) above, alkyl, cycloalkyl, alkenyl,
alkylcycloalkyl, aryl, alkylaryl and arylalkyl groups may be
mentioned as specific examples of C1-30 hydrocarbon groups
represented by R.sup.34-R.sup.39 in the formulas.
[0135] As examples of the aforementioned alkyl groups there may be
mentioned alkyl groups such as methyl, ethyl, propyl, butyl,
pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and
octadecyl (where the alkyl groups may be straight-chain or
branched).
[0136] As the aforementioned cycloalkyl groups there may be
mentioned C5-7 cycloalkyl groups such as cyclopentyl, cyclohexyl
and cycloheptyl. As examples of the aforementioned alkylcycloalkyl
groups there may be mentioned C6-11 alkylcycloalkyl groups such as
methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl,
diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methyl
ethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl,
dimethylcycloheptyl, methyl ethylcycloheptyl and diethylcycloheptyl
(with any positions of substitution of the alkyl groups on the
cycloalkyl groups).
[0137] As examples of the aforementioned alkenyl groups there may
be mentioned alkenyl groups such as butenyl, pentenyl, hexenyl,
heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl
and octadecenyl (where the alkenyl groups may be straight-chain or
branched, and the double bonds may be at any positions).
[0138] As examples of the aforementioned aryl groups there may be
mentioned aryl groups such as phenyl and naphthyl. As examples of
the aforementioned alkylaryl groups there may be mentioned C7-18
alkylaryl groups such as tolyl, xylyl, ethylphenyl, propylphenyl,
butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl,
nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl (where
the alkyl groups may be straight-chain or branched and substituted
at any positions on the aryl groups).
[0139] As examples of the aforementioned arylalkyl groups there may
be mentioned C7-12 arylalkyl groups such as benzyl, phenylethyl,
phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl (where the
alkyl groups may be straight-chain or branched).
[0140] The C1-30 hydrocarbon groups represented by
R.sup.34-R.sup.39 are preferably C1-30 alkyl or C6-24 aryl groups,
more preferably C3-18 alkyl groups and even more preferably C4-12
alkyl groups.
[0141] Here, R.sup.34, R.sup.35 and R.sup.36 may be the same or
different and each represents hydrogen or one of the aforementioned
hydrocarbon groups, where preferably 1-3 from among R.sup.34,
R.sup.35 and R.sup.36 are the aforementioned hydrocarbon groups,
more preferably 1-2 are the aforementioned hydrocarbon groups and
even more preferably two are the aforementioned hydrocarbon
groups.]
[0142] Also, R.sup.37, R.sup.38 and R.sup.39 may be the same or
different and each represents hydrogen or one of the aforementioned
hydrocarbon groups, where preferably 1-3 from among R.sup.37,
R.sup.38 and R.sup.39 are the aforementioned hydrocarbon groups,
more preferably 1-2 are the aforementioned hydrocarbon groups and
even more preferably two are the aforementioned hydrocarbon
groups.]
[0143] For the phosphorus compound represented by general formula
(D-6), at least two among Y.sup.3-Y.sup.5 must be oxygen atoms, but
preferably all of Y.sup.3-Y.sup.5 are oxygen atoms.
[0144] For the phosphorus compound represented by general formula
(D-7), at least two among Y.sup.6-Y.sup.9 must be oxygen atoms, but
preferably all of Y.sup.6-Y.sup.9 are oxygen atoms.
[0145] As examples of phosphorus compounds represented by general
formula (D-6) there may be mentioned phosphorous acid and
monothiophosphorous acid; phosphorous acid monoesters and
monothiophosphorous acid monoesters containing one of the
aforementioned C1-30 hydrocarbon groups, phosphorous acid diesters
and monothiophosphorous acid diesters containing two of the
aforementioned C1-30 hydrocarbon groups; phosphorous acid triesters
and monothiophosphorous acid triesters containing three of the
aforementioned C1-30 hydrocarbon groups; and mixtures thereof.
Preferred among these are phosphorous acid monoesters and
phosphorous acid diesters, with phosphorous acid diesters being
more preferred.
[0146] As examples of phosphorus compounds represented by general
formula (D-7) there may be mentioned phosphoric acid and
monothiophosphoric acid; phosphoric acid monoesters and
monothiophosphoric acid monoesters containing one of the
aforementioned C1-30 hydrocarbon groups, phosphoric acid diesters
and monothiophosphoric acid diesters containing two of the
aforementioned C1-30 hydrocarbon groups; phosphoric acid triesters
and monothiophosphoric acid triesters containing three of the
aforementioned C1-30 hydrocarbon groups; and mixtures thereof.
Preferred among these are phosphoric acid monoesters and phosphoric
acid diesters, with phosphoric acid diesters being more
preferred.
[0147] As metal salts of phosphorus compounds represented by
general formulas (D-6) and (D-7) there may be mentioned salts
obtained by neutralization of all or a portion of the acidic
hydrogens of the phosphorus compounds using metal bases. As such
metal bases there may be mentioned metal oxides, metal hydroxides,
metal carbonates, metal chlorides and the like, where specific
examples of metals include alkali metals such as lithium, sodium,
potassium and cesium, alkaline earth metals such as calcium,
magnesium and barium and heavy metals such as zinc, copper, iron,
lead, nickel, silver, manganese and the like. Preferred among these
are alkaline earth metals such as calcium and magnesium, and
zinc.
[0148] These phosphorus compound metal salts will differ in
structure depending on the valence of the metal and the number of
OH groups or SH groups in the phosphorus compound, and therefore no
limitations are placed on the structure; however, when 1 mole of
zinc oxide is reacted with 2 moles of a phosphoric acid diester
(with one OH group), for example, a compound having the structure
represented by formula (D-8) below may be obtained as the major
component, although polymerized molecules may also be present.
##STR00013##
[0149] Also, when 1 mole of zinc oxide is reacted with 1 mole of a
phosphoric acid monoester (with two OH groups), for example, a
compound having the structure represented by (D-9) below may be
obtained as the major component, although polymerized molecules may
also be present.
##STR00014##
[0150] Two or more of these may also be used in admixture.
[0151] According to the invention, phosphoric acid esters, acidic
phosphoric acid esters and acidic phosphoric acid ester amines are
preferred among these phosphorus compounds from the standpoint of
achieving superior machining efficiency and tool life.
[0152] As described hereunder, the oil composition of the invention
may be applied for purposes other than metal working, and when the
oil composition of the invention is used as an oil for machine tool
sliding surfaces, it preferably comprises an acidic phosphoric acid
ester or an acidic phosphoric acid ester amine salt. Also, when the
oil composition of the invention is used as a hydraulic oil, a
phosphoric acid ester is preferred. When it is used as both a
sliding surface oil and a hydraulic oil, it is preferred to use a
combination of a phosphoric acid ester with at least one selected
from among acidic phosphoric acid esters and acidic phosphoric acid
ester amine salts.
[0153] The oil composition of the invention may contain either a
sulfur compound or phosphorus compound, or it may contain both.
From the standpoint of achieving superior machining efficiency and
tool life, it preferably contains a phosphorus compound or both a
sulfur compound and phosphorus compound, and more preferably it
contains both a sulfur compound and phosphorus compound.
[0154] The content of the (D) extreme pressure agent may be as
desired, but from the standpoint of achieving superior machining
efficiency and tool life, it is preferably at least 0.005% by mass,
more preferably at least 0.01% by mass and even more preferably at
least 0.05% by mass, based on the total weight of the composition.
From the viewpoint of preventing abnormal abrasion, the extreme
pressure agent content is preferably no greater than 20% by mass,
more preferably no greater than 15% by mass and even more
preferably no greater than 12% by mass, based on the total weight
of the composition.
[0155] According to the invention, the aforementioned (C) oil agent
or (D) extreme pressure agent may be used alone, but from the
viewpoint of achieving superior machining efficiency and tool life,
the (C) oil agent and (D) extreme pressure agent are preferably
used in combination.
[0156] The oil composition of the invention preferably also further
contains (E) an organic acid salt, from the viewpoint of achieving
superior machining efficiency and tool life. As organic acid salts
there are preferably used sulfonates, phenates, salicylates and
mixtures thereof. As cationic components for these organic acid
salts there may be mentioned alkali metals such as sodium and
potassium; alkaline earth metals such as magnesium, calcium and
barium; ammonia, amines such as C1-3 alkyl group-containing
alkylamines (monomethylamine, dimethylamine, trimethylamine,
monoethylamine, diethylamine, triethylamine, monopropylamine,
dipropylamine, tripropylamine and the like), C1-3 alkanol
group-containing alkanolamines (monomethanolamine, dimethanolamine,
trimethanolamine, monoethanolamine, diethanolamine,
triethanolamine, monopropanolamine, dipropanolamine,
tripropanolamine and the like), and zinc, but alkali metals and
alkaline earth metals are preferred among these, and calcium is
particularly preferred. Using an alkali metal or alkaline earth
metal as the cationic component of the organic acid salt will tend
to produce even higher lubricity.
[0157] The sulfonate used may be one produced by any desired
process. For example, there may be used alkali metal salts,
alkaline earth metal salts and amine salts of alkylaromatic
sulfonic acids obtained by sulfonation of alkylaromatic compounds
with molecular weights of 100-1500 and preferably 200-700, as well
as mixtures thereof. As the alkylaromatic sulfonic acids referred
to here there may be mentioned synthetic sulfonic acids including
sulfonated alkylaromatic compounds of lube-oil distillates of
common mineral oils, petroleum sulfonic acids such as "mahogany
acid" yielded as a by-product of white oil production, sulfonated
products of alkylbenzenes with straight-chain or branched alkyl
groups, which are by-products in production plants for
alkylbenzenes used as starting materials for detergents or are
obtained by alkylation of benzene with polyolefins, and sulfonated
alkylnaphthalenes such as dinonylnaphthalene. There may also be
mentioned neutral (normal) sulfonates obtained by reacting the
aforementioned alkylaromatic sulfonic acids with alkali metal bases
(alkali metal oxides, hydroxides and the like), alkaline earth
metal bases (alkaline earth metal oxides, hydroxides and the like)
or the aforementioned amines (ammonia, alkylamines, alkanolamines,
etc.); basic sulfonates obtained by heating neutral (normal)
sulfonates with an excess of an alkali metal base, alkaline earth
metal base or amine in the presence of water; "carbonated overbased
sulfonates" obtained by reacting neutral (normal) sulfonates with
alkali metal bases, alkaline earth metal bases or amines in the
presence of carbon dioxide gas; "borated overbased sulfonates"
produced by reacting neutral (normal) sulfonates with alkali metal
bases, alkaline earth metal bases or amines and boric acid
compounds such as boric acid and boric anhydride, or by reacting
carbonated overbased sulfonates with boric acid compounds such as
boric acid and boric anhydride; as well as mixtures of the
above-mentioned compounds.
[0158] As phenates there may be mentioned, specifically, neutral
phenates obtained by reacting alkylphenols having one or two C4-20
alkyl groups with alkali metal bases (alkali metal oxides,
hydroxides and the like), alkaline earth metal bases (alkaline
earth metal oxides, hydroxides and the like) or the aforementioned
amines (ammonia, alkylamines, alkanolamines, etc.) in the presence
or in the absence of elemental sulfur; basic phenates obtained by
heating neutral phenates with an excess of an alkali metal base,
alkaline earth metal base or amine in the presence of water;
"carbonated overbased phenates" obtained by reacting neutral
phenates with alkali metal bases, alkaline earth metal bases or
amines in the presence of carbon dioxide gas; "borated overbased
phenates" produced by reacting neutral phenates with alkali metal
bases, alkaline earth metal bases or amines and boric acid
compounds such as boric acid and boric anhydride, or by reacting
carbonated overbased phenates with boric acid compounds such as
boric acid and boric anhydride; as well as mixtures of the
above-mentioned compounds.
[0159] As salicylates there may be mentioned, specifically, neutral
salicylates obtained by reacting alkylsalicylic acids having one or
two C4-20 alkyl groups with alkali metal bases (alkali metal
oxides, hydroxides and the like), alkaline earth metal bases
(alkaline earth metal oxides, hydroxides and the like) or the
aforementioned amines (ammonia, alkylamines, alkanolamines, etc.)
in the presence or in the absence of elemental sulfur; basic
salicylates obtained by heating neutral salicylates with an excess
of an alkali metal base, alkaline earth metal base or amine in the
presence of water; "carbonated overbased salicylates" obtained by
reacting neutral salicylates with alkali metal bases, alkaline
earth metal bases or amines in the presence of carbon dioxide gas;
"borated overbased salicylates" produced by reacting neutral
salicylates with alkali metal bases, alkaline earth metal bases or
amines and boric acid compounds such as boric acid and boric
anhydride, or by reacting carbonated overbased salicylates with
boric acid compounds such as boric acid and boric anhydride; as
well as mixtures of the above-mentioned compounds.
[0160] The base value of the (E) organic acid salt is preferably
50-500 mgKOH/g and more preferably 100-450 mgKOH/g. If the total
base value of the organic acid salt is less than 100 mgKOH/g the
lubricity-enhancing effect of the organic acid salt addition will
tend to be unsatisfactory, while organic acid salts with a total
base value of greater than 500 mgKOH/g are also not preferred
because they are generally very difficult to produce and obtain.
The base value referred to here is the base value [mgKOH/g]
measured by a perchloric acid method based on section 7 of
"Petroleum product and lubricating oils--Neutralization value test
methods" of JIS K 2501.
[0161] The content of the (E) organic acid salt is preferably
0.1-30% by mass, more preferably 0.5-25% by mass and even more
preferably 1-20% by mass based on the total weight of the
composition. If the content of the (E) organic acid salt is below
this lower limit, the improving effect of the addition on the
machining efficiency and tool life will tend to be unsatisfactory,
while if it is above the aforementioned upper limit the stability
of the oil composition will be reduced and deposits will tend to
form.
[0162] According to the invention, the (E) organic acid salt may be
used alone or the organic acid salt may be used in combination with
other additives. From the standpoint of achieving superior
machining efficiency and tool life, it is preferred to use a
combination of an organic acid salt with the aforementioned
extreme-pressure agent, and it is particularly preferred to use a
combination of three components, a sulfur compound, a phosphorus
compound and an organic acid salt.
[0163] The oil composition of the invention preferably further
contains (F) an antioxidant. Addition of an antioxidant can prevent
sticking caused by degradation of the constituent components, while
further enhancing the heat and oxidation stability.
[0164] As (F) antioxidants there may be mentioned phenol-based
antioxidants, amine-based antioxidants, zinc dithiophosphate-based
antioxidants, and antioxidants used as food additives.
[0165] As phenol-based antioxidants there may be used any
phenol-based compounds that are employed as antioxidants for
lubricating oils, with no particular restrictions, and as preferred
examples there may be mentioned one or more alkylphenol compounds
selected from among compounds represented by the following general
formulas (F-1) and (F-2).
##STR00015##
[wherein R.sup.40 represents a C1-4 alkyl group, R.sup.41
represents hydrogen or a C1-4 alkyl group, and R.sup.42 represents
hydrogen, a C1-4 alkyl group, or a group represented by the
following general formula (i) or (ii):
##STR00016##
(where R.sup.43 represents C1-6 alkylene and R.sup.44 represents a
C1-24 alkyl or alkenyl group)
##STR00017##
(where R.sup.45 represents a C1-6 alkylene group, R.sup.46
represents a C1-4 alkyl group, R.sup.47 represents hydrogen or a
C1-4 alkyl group and k represents 0 or 1).]
##STR00018##
[wherein R.sup.48 and R.sup.50 may be the same or different and
each represents C1-4 alkyl, R.sup.49 and R.sup.51 may be the same
or different and each represents hydrogen or C1-4 alkyl, R.sup.52
and R.sup.53 may be the same or different and each represents C1-6
alkylene, and B represents C1-18 alkylene or a group represented by
the following general formula (iii):
--R.sup.55--S--R.sup.56-- (iii)
(where R.sup.55 and R.sup.56 may be the same or different and each
represents a C1-6 alkylene group).]
[0166] As amine-based antioxidants for the invention there may be
used any amine-based compounds that are employed as antioxidants
for lubricating oils, with no particular restrictions, and as
preferred examples there may be mentioned one or more aromatic
amines selected from among phenyl-.alpha.-naphthylamine or
N-p-alkylphenyl-.alpha.-naphthylamines represented by the following
general formula (F-3), and p,p'-dialkyldiphenylamines represented
by the following general formula (F-4).
##STR00019##
[wherein R.sup.57 represents hydrogen or an alkyl group.]
##STR00020##
[wherein R.sup.58 and R.sup.59 may be the same or different and
each represents an alkyl group.]
[0167] As specific examples of amine-based antioxidants there may
be mentioned 4-butyl-4'-octyldiphenylamine,
phenyl-.alpha.-naphthylamine, octylphenyl-.alpha.-naphthylamine,
dodecylphenyl-.alpha.-naphthylamine, and mixtures thereof.
[0168] As dithiozinc phosphate-based antioxidants there may be
mentioned zinc dithiophosphate compounds represented by general
formula (D-2) above.
[0169] Antioxidants employed as food additives may also be used,
although these partially overlap with the aforementioned
phenol-based antioxidants, and there may be mentioned as examples
2,6-di-tert-butyl-p-cresol (DBPC),
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-bis(2,6-di-tert-butylphenol),
4,4'-thiobis(6-tert-butyl-o-cresol), ascorbic acid (vitamin C),
ascorbic acid fatty acid esters, tocopherol (vitamin E),
3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole,
3-tert-butyl-4-hydroxyanisole,
1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin),
2-(1,1-dimethyl)-1,4-benzenediol (TBHQ) and
2,4,5-trihydroxybutyrophenone (THBP).
[0170] Preferred among these antioxidants are phenol-based
antioxidants, amine-based antioxidants and antioxidants that are
employed as food additives. The use of food additive antioxidants
is especially preferred when biodegradability is a primary concern,
and of these, ascorbic acid (vitamin C), ascorbic acid fatty acid
esters, tocopherol (vitamin E), 2,6-di-tert-butyl-p-cresol (DBPC),
3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole,
3-tert-butyl-4-hydroxyanisole,
1,2-dihydro-6-ethoxy-2,2,4-trimethylquinoline (ethoxyquin),
2-(1,1-dimethyl)-1,4-benzenediol (TBHQ) and
2,4,5-trihydroxybutyrophenone (THBP) are preferred, among which
ascorbic acid (vitamin C), ascorbic acid fatty acid esters,
tocopherol (vitamin E), 2,6-di-tert-butyl-p-cresol (DBPC) and
3,5-di-tert-butyl-4-hydroxyanisole are more preferred.
[0171] There are no particular restrictions on the (F) antioxidant
content, but for maintenance of satisfactory heat and oxidation
stability the content is preferably 0.01% by mass or greater, more
preferably 0.05% by mass or greater and most preferably 0.1% by
mass or greater based on the total weight of the composition. Since
no corresponding effect can be expected with larger amounts of
addition, the content is preferably no greater than 10% by mass,
more preferably no greater than 5% by mass and most preferably no
greater than 3% by mass.
[0172] The oil composition of the invention may contain various
additives known in the prior art in addition to those mentioned
above. As examples of such additives there may be mentioned extreme
pressure agents (including chlorine-based extreme pressure agents)
other than the aforementioned phosphorus compounds and sulfur
compounds; moistening agents such as diethyleneglycol
monoalkylethers; film-forming agents such as acrylic polymers,
paraffin wax, microwax, slack wax and polyolefin wax; water
displacement agents such as fatty acid amine salts; solid
lubricants such as graphite, fluorinated graphite, molybdenum
disulfide, boron nitride and polyethylene powder; corrosion
inhibitors such as amines, alkanolamines, amides, carboxylic acids,
carboxylic acid salts, sulfonic acid salts, phosphoric acid,
phosphoric acid salts and polyhydric alcohol partial esters; metal
inactivators such as benzotriazole and thiadiazole; antifoaming
agents such as methylsilicone, fluorosilicone and polyacrylate; and
non-ash dispersants such as alkenylsuccinic imides, benzylamine and
polyalkenylamineaminoamides. The contents of such known additives
when used in combination are not particularly restricted, but they
are generally added in amounts so that the total content of the
known additives is 0.1-10% by mass based on the total weight of the
composition.
[0173] The oil composition of the invention may also contain
chlorine-based additives such as the aforementioned chlorine-based
extreme-pressure agents, but they preferably contain no
chlorine-based additives from the viewpoint of improving stability
and reducing the burden on the environment. The chlorine
concentration is preferably no greater than 1000 ppm by mass, more
preferably no greater than 500 ppm by mass, even more preferably no
greater than 200 ppm by mass and most preferably no greater than
100 ppm by mass, based on the total weight of the composition.
[0174] There are no particular restrictions on the kinematic
viscosity of the oil composition of the invention, but from the
standpoint of facilitating supply to the working section, the
kinematic viscosity at 100.degree. C. is preferably no greater than
20 mm.sup.2/s, more preferably no greater than 17 mm.sup.2/s, even
more preferably no greater than 15 mm.sup.2/s and most preferably
no greater than 12 mm.sup.2/s. On the other hand, the kinematic
viscosity of the oil composition of the invention at 100.degree. C.
is preferably at least 0.5 mm.sup.2/s, more preferably at least 0.7
mm.sup.2/s and most preferably at least 0.9 mm.sup.2/s.
[0175] From the standpoint of storage stability and rust
prevention, the moisture content of the oil composition of the
invention is preferably no greater than 20,000 ppm, more preferably
no greater than 10,000 ppm and even more preferably no greater than
5000 ppm. From the viewpoint of achieving superior machining
efficiency and tool life, the moisture content is preferably at
least 200 ppm, more preferably at least 300 ppm, even more
preferably at least 400 ppm and yet more preferably at least 500
ppm.
[0176] The moisture content according to the invention is the
moisture content as measured by Karl Fischer coulometric titration
based on JIS K 2275.
[0177] When the moisture content of the oil composition of the
invention is adjusted by addition of water, the added water may be
hard water or soft water, and the source of water used may be tap
water, industrial water, ion-exchanged water, distilled water,
alkali ion water or the like.
[0178] The oil composition of the invention having the construction
described above can achieve both misting and floating mist
properties that have been difficult to achieve by the prior art
with cutting and grinding in minimum quantity lubrication systems.
The oil composition of the invention is therefore highly useful for
enhancing machining performance and improving working
environments.
EXAMPLES
[0179] The present invention will now be explained in greater
detail based on examples and comparative examples, with the
understanding that these examples are in no way limitative on the
invention.
Examples 1-14
Comparative Example 1
[0180] For Examples 1-14 and Comparative Example 1, the ester oils
and ester-based polymers listed below were used to prepare the oil
compositions shown in Tables 1 to 3.
[0181] (Ester Oils)
A1: Methyl oleate (kinematic viscosity at 100.degree. C.: 1.8
mm.sup.2/s) A2: Diisodecyl adipate (kinematic viscosity at
100.degree. C.: 3.7 mm.sup.2/s) A3: Triester of trimethylolpropane
and n-octanoic acid/n-decanoic acid mixed acid (kinematic viscosity
at 100.degree. C.: 4.4 mm.sup.2/s) A4: Diester of neopentyl glycol
and oleic acid (kinematic viscosity at 100.degree. C.: 5.8
mm.sup.2/s) A5: High-oleic rapeseed oil (kinematic viscosity at
100.degree. C.: 8.5 mm.sup.2/s) A6: Triester of trimethylolpropane
and oleic acid (kinematic viscosity at 100.degree. C.: 9.8
mm.sup.2/s)
(Ester-Based Polymers)
[0182] B1: Polymethacrylate (polymer comprising monomer mixture
represented by general formula (B-2-2) wherein R.sup.1 is hydrogen,
R.sup.2 is methyl, R.sup.3 is C1-18 alkyl; kinematic viscosity at
100.degree. C.: 400 mm.sup.2/s, average molecular weight: 10,000)
B2: Polymethacrylate (polymer comprising monomer mixture
represented by general formula (B-2-2) wherein R.sup.1 is hydrogen,
R.sup.2 is methyl, R.sup.3 is C1-18 alkyl; kinematic viscosity at
100.degree. C.: 1200 mm.sup.2/s, average molecular weight: 50,000)
B3: Polymethacrylate (polymer comprising monomer mixture
represented by general formula (B-2-2) wherein R.sup.1 is hydrogen,
R.sup.2 is methyl, R.sup.3 is C1-18 alkyl; kinematic viscosity at
100.degree. C.: 1700 mm.sup.2/s, average molecular weight: 150,000)
B4: Polymethacrylate (polymer comprising monomer mixture
represented by general formula (B-2-2) wherein R.sup.1 is hydrogen,
R.sup.2 is methyl, R.sup.3 is C1-18 alkyl; kinematic viscosity at
100.degree. C.: 2,500 mm.sup.2/s, average molecular weight:
500,000) B5: Complex ester of neopentyl glycol and dimer acid
(kinematic viscosity at 100.degree. C.: 2,000 mm.sup.2/s, average
molecular weight: 100,000)
[0183] The oil compositions of Examples 1-14 and Comparative
Example 1 were then subjected to the following tests.
[0184] [Floating Mist Measurement Test]
FIG. 1 and FIG. 2 are, respectively, a side view and top view of
the essential parts of a test apparatus used for the floating mist
measurement test. The test apparatus shown in FIG. 1 and FIG. 2 has
an MQL device (EB-3, product of Fuji BC Engineering Co., Ltd.) and
a mist counter installed on a machining center (MB-46V, product of
Okuma Machine Tools, Inc.), for cutting and grinding in minimum
quantity lubrication system. Specifically, the test apparatus shown
in FIG. 1 and FIG. 2 is equipped with a table 1 supporting a
workpiece 10, a tool 2 situated opposite the top of the table 1
(NACHI straight drill SGOH3D (5.0 mm.times.82 mm.times.28 mm),
hereinafter referred to as "drill 2"), a shank 3 supported in a
rotatable manner around its rotation axis as the center, and a mist
counter 5 (P-5L Portable Dust Monitor, product of Sibata Scientific
Technology, Ltd.) situated around the edge of the top of the table
1.
[0185] While not shown in detail here, the drill 2 has a helical
groove, and two discharge holes (oil holes, .phi.1.0 mm) are
provided at prescribed locations on the cutting blade flank of the
groove. Inside the drill 2 and shank 3 there are provided channels
connecting with the discharge holes of the drill 2, and an oil feed
line 5 is connected to the opening at the side of the channel of
the shank 3 opposite the drill 2 side. Thus, the oil composition
fed from the oil feed line 5 together with compressed air can be
converted to a mist from the discharge holes of the drill 2,
through the channels formed by the drill 2 and shank 3, toward the
workpiece 10.
[0186] In the test apparatus having this construction, cutting and
grinding was performed with minimum quantity lubrication system at
a drill rotation rate of 1,000 rpm, a misting pressure difference
of 0.12 MPa (injection pressure: 0.38 MPa, discharge pressure: 0.26
MPa), a discharge pressure from the misting apparatus of 0.26 MPa
and blowing toward the workpiece at 180 shots/min. The amount of
floating mist produced during one minute, from 3 minutes to 4
minutes after the start of machining, was measured using the mist
counter 5. The results are shown in Tables 1 to 3.
[0187] [Test for Measurement of Amount of Tapped Oil Reaching
Cutting Point]
A glass dish (inner diameter: 95 mm) was placed in the test
apparatus shown in FIG. 1 and FIG. 2 instead of the workpiece 10,
and the drill 2 and shank 3 were situated so that the distance
between the bottom of the dish and the tip of the drill 2 was 50
mm. The misted oil composition was blown in from the discharge hole
of the drill 2 toward the dish under the same conditions as for the
floating mist measurement test, and the amount of oil composition
collected in the dish (amount delivered per unit time) was
measured. The results are shown in Tables 1 to 3.
[0188] [Lubricity Performance Test (Tapping Test)]
Each oil composition was subjected to a tapping test under the
following conditions. Supply of the oil composition to the working
section was accomplished by using an MQL apparatus (MCA by TACO)
for blowing toward the working section at 2 cm.sup.2/min, with a
misting pressure difference of 0.20 MPa (injection pressure: 0.42
MPa, discharge pressure: 0.22 MPa) and a discharge pressure of 0.22
MPa from the misting apparatus. The test was carried out 9 times
for each oil composition, and the average value for the tapping
energy was calculated. The results are shown in Tables 1 to 3.
[0189] (Tapping Conditions)
Tool: Nut tap M8 (P=1.25 mm)
[0190] Lower hole diameter: .phi.6.8 mm Workpiece: S25C (t=10 mm)
Cutting speed: 9.0 m/min
TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Composition A1 99.00 -- -- -- -- -- [% by mass]
A2 -- 99.00 -- -- -- -- A3 -- -- 99.00 -- -- -- A4 -- -- -- 99.00
-- -- A5 -- -- -- -- 99.00 -- A6 -- -- -- -- -- 99.00 B2 1.00 1.00
1.00 1.00 1.00 1.00 Floating mist 2.01 0.95 1.09 0.89 0.81 0.77
[mg/m.sup.3] Amount of tapped 7.01 8.12 7.22 7.98 7.11 6.99 oil
reaching cutting point [g/h] Tapping energy 368 360 358 350 362 347
(mean) [N m]
TABLE-US-00002 TABLE 2 Example 7 Example 8 Example 9 Example 10
Example 11 Composition A4 99.99 99.90 95.00 90.00 99.00 [% by mass]
B1 -- -- -- 10.00 1.00 B2 -- 0.10 5.00 -- -- B3 -- -- -- -- -- B4
0.01 -- -- -- -- B5 -- -- -- -- -- Floating mist 2.07 1.88 0.77
0.69 1.18 [mg/m.sup.3] Amount of tapped 7.88 8.11 6.99 6.89 7.71
oil reaching cutting point [g/h] Tapping energy 362 367 360 368 361
(mean) [N m]
TABLE-US-00003 TABLE 3 Example Example Example Comp. 12 13 14 Ex. 1
Composition A4 99.00 99.00 95.00 100.00 [% by mass] B3 1.00 -- --
-- B4 -- 1.00 -- -- B5 -- -- 1.00 -- Floating mist 0.78 0.74 1.78
19.1 [mg/m.sup.3] Amount of tapped oil 8.43 7.05 7.51 5.81 reaching
cutting point [g/h] Tapping energy (mean) 355 361 365 379 [N m]
* * * * *