U.S. patent application number 11/547355 was filed with the patent office on 2008-01-31 for metal working fluid.
This patent application is currently assigned to NIPPON OIL CORPORATION. Invention is credited to Masanori Ibi, Satoshi Suda, Hideo Yokota.
Application Number | 20080026967 11/547355 |
Document ID | / |
Family ID | 35063760 |
Filed Date | 2008-01-31 |
United States Patent
Application |
20080026967 |
Kind Code |
A1 |
Suda; Satoshi ; et
al. |
January 31, 2008 |
Metal Working Fluid
Abstract
A first oil for metal working of the invention comprises an
ester oil and a hydrocarbon oil with a kinematic viscosity of 1-20
mm.sup.2/s at 40.degree. C. A second oil for metal working of the
invention employs an ester oil as the base oil and has a moisture
content of 200-20,000 ppm. The first and second oils for metal
working have excellent properties as water-insoluble oils for
non-ferrous metal working and as oils for cutting and grinding in a
minimum quantity lubrication system, and can therefore achieve
improved working efficiency and extended tool life.
Inventors: |
Suda; Satoshi; (Kanagawa,
JP) ; Yokota; Hideo; (Kanagawa, JP) ; Ibi;
Masanori; (Kanagawa, JP) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Assignee: |
NIPPON OIL CORPORATION
8, Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa
Yokohama-shi
JP
231-0815
|
Family ID: |
35063760 |
Appl. No.: |
11/547355 |
Filed: |
March 29, 2005 |
PCT Filed: |
March 29, 2005 |
PCT NO: |
PCT/JP05/05878 |
371 Date: |
September 29, 2006 |
Current U.S.
Class: |
508/459 |
Current CPC
Class: |
C10M 2207/2835 20130101;
C10M 2215/04 20130101; C10M 2207/401 20130101; C10N 2030/02
20130101; C10M 101/00 20130101; C10M 101/04 20130101; C10M
2203/0206 20130101; C10N 2030/40 20200501; C10N 2030/06 20130101;
C10N 2040/22 20130101; C10M 169/04 20130101; C10M 105/36 20130101;
C10M 2207/289 20130101; C10M 2207/126 20130101; C10M 2203/1006
20130101; C10N 2030/30 20200501; C10M 2223/041 20130101; C10M
2207/2825 20130101; C10M 105/38 20130101; C10M 111/02 20130101;
C10M 2219/024 20130101; C10M 2207/021 20130101; C10M 2203/003
20130101; C10M 2207/2835 20130101; C10M 2207/2835 20130101 |
Class at
Publication: |
508/459 |
International
Class: |
C10M 101/04 20060101
C10M101/04; C10M 101/00 20060101 C10M101/00; C10M 105/00 20060101
C10M105/00; C10M 105/32 20060101 C10M105/32; C10M 111/02 20060101
C10M111/02; C10N 30/00 20060101 C10N030/00; C10N 40/20 20060101
C10N040/20; C10N 50/04 20060101 C10N050/04; C10N 30/06 20060101
C10N030/06; C10M 111/04 20060101 C10M111/04; C10M 107/02 20060101
C10M107/02; C10M 105/02 20060101 C10M105/02; C10M 101/02 20060101
C10M101/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2004 |
JP |
2004-106112 |
Mar 31, 2004 |
JP |
2004-106128 |
Claims
1. An oil for metal working comprising an ester oil and a
hydrocarbon oil with a kinematic viscosity of 1-20 mm.sup.2/s at
40.degree. C.
2. The oil for metal working according to claim 1, wherein said
hydrocarbon oil is at least one selected from among white oils and
polyolefins or their hydrogenated forms.
3. The oil for metal working according to claim 1, wherein the
moisture content is 200-20,000 ppm.
4. The oil for metal working according to claim 1, further
comprising an oiliness agent and/or an extreme-pressure agent.
5. The oil for metal working according to claim 1, being used for
non-ferrous metal working.
6. The oil for metal working according to claim 1, being used for
cutting, grinding or rolling.
7. The oil for metal working according to claim 1, being used for
metal working in a minimum quantity lubrication system.
8. An oil for metal working comprising an ester oil as the base oil
and having a moisture content of 200-20,000 ppm.
9. The oil for metal working according to claim 8, further
comprising an oiliness agent and/or an extreme-pressure agent.
10. The oil for metal working according to claim 8, being used for
non-ferrous metal working.
11. The oil for metal working according to claim 8, being used for
cutting, grinding or rolling.
12. The oil for metal working according to claim 8, being used for
metal working in a minimum quantity lubrication system.
Description
TECHNICAL FIELD
[0001] The present invention relates to an oil for metal
working.
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, 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,
water-soluble cutting and grinding oils used by diluting
surfactants and lubricant components with water, and
water-insoluble cutting and grinding oils used directly as stock
solutions composed mainly of mineral oils. Generally speaking,
water-insoluble cutting and grinding oils exhibit superior
lubricating performance while water-soluble cutting and grinding
oils exhibit superior cooling performance.
[0004] Cutting and grinding oils that are effective for improving
working efficiency have drawbacks from other viewpoints, typically
their adverse effects on the environment. Whether water-insoluble
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, a significantly fouled
environment and unsuitability for use. In the case of
water-insoluble 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 cutting chips and the like, becoming consumed
and forming waste.
[0005] The degraded oils must therefore be disposed of and replaced
with new oils. The 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 dioxins 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 compounds have therefore been developed, but even such
toxic substance-free cutting and grinding oils can adversely affect
the environment with large-scale emission of waste products.
Water-soluble oils can also contaminate environmental waters and
therefore require costly high-level treatment.
[0006] As examples of cases where it is difficult to achieve both
improved working efficiency and reduced environmental burden, there
may be mentioned the field of producing non-ferrous metal parts as
automobile parts or electronic appliance parts. More specifically,
while it has been common in the prior art to use water-soluble oils
for working of non-ferrous metal parts such as aluminum or aluminum
alloy parts, the metals generally tend to dissolve in the waste
liquid after the non-ferrous metals have been worked, thus vastly
increasing the cost for waste liquid treatment. Moreover, using
water-soluble oils results in decay or corrosion of parts unless
the working fluid is at the optimum pH, and therefore strict and
frequent management is essential during their use.
[0007] In order to solve these problems, the application of dry
working or water-insoluble working oils has been investigated in
the field of non-ferrous metal working.
[0008] Novel working methods are also being developed, such as
minimum quantity lubrication system cutting/grinding methods. In
such methods, 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 part together with a compressed gas (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. Such
methods, therefore, are promising not only for non-ferrous metal
working but also for ferrous metal working.
[0009] In the case of a minimum quantity lubrication system, higher
performance is demanded than for cutting/grinding oils in that,
preferably, it must be possible to obtain working pieces with
satisfactory surfaces even when only trace amounts of oil are
supplied, tool wear must be minimal, and cutting/grinding must be
efficiently achieved. Moreover, oils with excellent
biodegradability are preferred from the viewpoint of waste
treatment and working environment.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0010] However, dry working often leads to tool damage as a result
of adhesion of the metal from the workpieces or increased working
resistance in the case of non-ferrous metal (especially aluminum)
tools, such that it has not been possible to achieve adequate
working efficiency and tool life. Also, water-insoluble cutting
oils are associated with increased risk of fire and corrosion or
discoloration caused by additives, generally rendering them poor
substitutes for water-soluble cutting oils.
[0011] On the other hand, even when cutting and grinding is carried
out utilizing a minimum quantity lubrication system, it is very
difficult to achieve a satisfactory balance between all of the
required performance aspects if a conventional cutting/grinding oil
is used directly in the minimum quantity lubrication system.
Furthermore, even using a minimum quantity lubrication system with
a non-ferrous metal workpiece, it is not always a simple matter to
avoid damage to tools by adhesion of the metal from the workpieces
or increased working resistance of the non-ferrous metal.
[0012] It is an object of the present invention, which has been
accomplished in light of the circumstances described above, to
provide an oil for metal working with excellent properties as a
water-insoluble oil for non-ferrous metal working and excellent
properties as a cutting/grinding oil in a minimum quantity
lubrication system, and which can achieve improved working
efficiency and extended tool life.
Means for Solving the Problems
[0013] In order to achieve this object, the present invention
provides an oil for metal working characterized by comprising an
ester oil and a hydrocarbon oil with a kinematic viscosity of 1-20
mm.sup.2/s at 40.degree. C. (hereinafter referred to as "first oil
for metal working").
[0014] By thus using an ester oil together with a hydrocarbon oil
with a kinematic viscosity of 1-20 mm.sup.2/s at 40.degree. C., it
is possible to adequately control adhesion of the metal from the
workpieces or increased working resistance for non-ferrous metal
(especially aluminum) tools when using the aforementioned first oil
for metal working as a water-insoluble oil for non-ferrous metal
working, so that improved working efficiency and extended tool life
can be achieved. The first oil for metal working having the
composition described above can form a satisfactory oil mist when
used as a cutting/grinding oil in a minimum quantity lubrication
system, in order to achieve a high level of improved working
efficiency and extended tool life.
[0015] The hydrocarbon oil in the first oil for metal working is
preferably one or more types selected from among white oils and
polyolefins or their hydrogenated forms.
[0016] The moisture content of the first oil for metal working is
preferably 200-20,000 ppm.
[0017] The invention further provides an oil for metal working
comprising an ester oil as the base oil, characterized by having a
moisture content of 200-20,000 ppm (hereinafter referred to as
"second oil for metal working").
[0018] If the moisture content of the oil for metal working
comprising an ester oil as the base oil is 200-20,000 ppm, as the
second oil for metal working which is to be used as a
water-insoluble oil for non-ferrous metal working, it is possible
to sufficiently prevent adhesion of the metal from the workpieces
or working resistance increase for non-ferrous metal (especially
aluminum) tools, in order to achieve improved working efficiency
and extended tool life. The second oil for metal working having the
composition described above can form a satisfactory oil mist when
used as a cutting/grinding oil in a minimum quantity lubrication
system, in order to achieve a high level of improved working
efficiency and extended tool life. Moreover, since the second oil
for metal working comprises an ester oil with higher
biodegradability than mineral oils and water, which does not
adversely affect the environment, it is also useful from the
standpoint of alleviating the burden on the environment.
[0019] These effects of the second oil for metal working are based
on knowledge of the present inventors that a moisture content
within the aforementioned range allows sufficient control of
phenomena such as water separation or ester oil hydrolysis, while
effectively taking advantage of the excellent properties of water
as an additive. This is an unexpected effect considering the
technical knowledge of the prior art that the moisture content
should be minimized when using an ester oil from the viewpoint of
preventing hydrolysis of the ester oil.
[0020] The first and second oils for metal working preferably
further comprise an oiliness agent and/or an extreme-pressure
agent.
[0021] The first and second oils for metal working of the invention
may be suitably used for non-ferrous metal working. In addition,
the first and second oils for metal working may also be suitably
used for cutting, grinding or rolling, as well as for minimum
quantity lubrication system metal working.
[0022] Here, minimum quantity lubrication system metal working is
metal working carried out while supplying to the cutting/grinding
site a trace amount of oil at about 1/100,000- 1/1,000,000 of the
amount of oil used for conventional metal working, together with a
compressed gas. More specifically, a minimum quantity lubrication
system is a system wherein a trace amount of oil, usually at no
more than 1 milliliter/min, is supplied toward the working site
(for example, the cutting/grinding site) together with a compressed
gas (for example, compressed air). Instead of compressed air,
compressed gass such as nitrogen, argon, helium, carbon dioxide or
water may be used alone or any of these may be used in
admixture.
[0023] In the case of a minimum quantity lubrication system, it is
of utmost importance to generate a satisfactory oil mist. If the
oil mist condition is poor, the pipes may become clogged and
prevent a sufficient amount of oil from reaching the working point,
thereby reducing the working efficiency and shortening the tool
life. On the other hand, if the oil forms a mist too readily, the
discharged oil mist will fly out and contaminate the working
environment. In this case as well, the oil mist tends to fly out
and result in loss of oil such that the amount of oil reaching the
working point becomes insufficient, and the working efficiency is
reduced and tool life is shortened.
[0024] Moreover, because the oil is supplied as an oil mist in a
minimum quantity lubrication system, using an oil with poor
stability can result in adhesion to the machine tool interior,
workpiece, tool, mist collector interior, etc. producing a sticking
phenomenon, and can thereby impair the handleability and lower
working efficiency. Thus, the oil used in a minimum quantity
lubrication system is preferably one which is resistant to
sticking.
[0025] Although both the first and second oils for metal working of
the invention may be suitably used for metal working in a minimum
quantity lubrication system, the first oil for metal working of the
invention is particularly preferred from the standpoint of mist
properties and sticking resistance.
EFFECT OF THE INVENTION
[0026] According to the invention, there is provided an oil for
metal working that exhibits excellent properties as a
water-insoluble oil for non-ferrous metal working and excellent
properties as a cutting/grinding oil for a minimum quantity
lubrication system, and that therefore allows improved working
efficiency and extended tool life to be achieved.
BRIEF EXPLANATION OF THE DRAWINGS
[0027] FIG. 1 is a schematic diagram showing an example of a
machine tool suitable for use in a cutting/grinding method with a
minimum quantity lubrication system.
EXPLANATION OF SYMBOLS
[0028] 1: Bed, 2: table, 3: workpiece, 11: tool, 12: oil feeding
tank, 13: working oil feeding section, 14: sliding surface oil
feeding section, 15: bearing oil feeding section, 16: sliding
surface, 17: bearing section, 18: compressed air injection
port.
BEST MODE FOR CARRYING OUT THE INVENTION
[0029] Preferred embodiments of the invention will now be described
in detail.
[0030] The first oil for metal working of the invention comprises
(A) an ester oil and (B) a hydrocarbon oil with a kinematic
viscosity of 1-20 mm.sup.2/s at 40.degree. C. (hereinafter referred
to simply as "(B) hydrocarbon oil").
[0031] The (A) ester oil may be a natural substance (which
generally includes any natural fat or oil such as an animal or
vegetable oil) or a synthetic substance. According to the
invention, a synthetic ester is preferred from the viewpoint of
stability of the obtained lubricating oil and uniformity of the
ester component. However, a natural ester is preferred from the
standpoint of effects on the environment.
[0032] The alcohol in the (A) ester oil may be a monohydric alcohol
or polyhydric alcohol, and the acid of the (A) ester oil may be a
monobasic acid or polybasic acid.
[0033] As monohydric alcohols there may be used C1-24, preferably
C1-12 and even more preferably C1-8 alcohols, which may be
straight-chain or branched and may be 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 thereof.
[0034] As polyhydric alcohols there may be used C2-10 and
preferably C2-6 alcohols. As specific examples of C2-10 polyhydric
alcohols there may be mentioned dihydric alcohols such as ethylene
glycol, diethylene glycol, polyethylene glycol (trimer to
pentadecamer of ethylene glycol), propylene glycol, dipropylene
glycol, polypropylene glycol (trimer to pentadecamer of propylene
glycol), 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; polyhydric alcohols such as glycerin,
polyglycerin (dimer to octamer of glycerin, such as diglycerin,
triglycerin, tetraglycerin and the like), trimethylolalkanes
(trimethylolethane, trimethylolpropane, trimethylolbutane) and
their dimer to octamer, pentaerythritol and its dimer to tetramer,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensation product, adonitol, arabitol, xylitol and mannitol;
sugars such as xylose, arabinose, ribose, rhamnose, glucose,
fructose, galactose, mannose, sorbose, cellobiose, maltose,
isomaltose, trehalose and sucrose; and mixtures thereof.
[0035] Preferred among these polyhydric alcohols are C2-6
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol (trimer to decamer of ethylene glycol),
propylene glycol, dipropylene glycol, polypropylene glycol (trimer
to decamer 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) and
their dimer to tetramer, pentaerythritol, dipentaerythritol,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensation product, adonitol, arabitol, xylitol and mannitol, and
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.
[0036] The alcohol composing the ester oil may be a monohydric
alcohol or a polyhydric alcohol as mentioned above, but it is
preferably a polyhydric alcohol from the viewpoint of achieving
superior lubricity, more easily obtaining a low pour point and
improving the handleability in winter season and cold climates.
Using a polyhydric alcohol ester oil will result in improved
precision of the finishing surface of the workpiece and an even
greater anti-abrasive effect for tool blades during cutting and
grinding.
[0037] In most cases a C2-24 fatty acid will be used as the
monobasic acid among acids for the ester oil, 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; 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; and mixtures
thereof. Particularly preferred among these, from the Standpoint of
improving the lubricity and handleability, are C3-20 saturated
fatty acids, C3-22 unsaturated fatty acids and mixtures thereof,
among which C4-18 saturated fatty acids, C4-18 unsaturated fatty
acids and mixtures thereof 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 yet more
preferred.
[0038] 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.
[0039] The acid of the (A) ester oil may be a monobasic acid or
polybasic acid as mentioned above, but using a monobasic acid is
preferred to obtain an ester for an improved viscosity index and
improved sticking resistance.
[0040] The combination of the alcohol and acid in the (A) ester may
be as desired and is not particularly restricted, but the following
esters may be mentioned as examples of ester oils to be used for
the invention.
[0041] (i) Esters of monohydric alcohols and monobasic acids [0042]
(ii) Esters of polyhydric alcohols and monobasic acids [0043] (iii)
Esters of monohydric alcohols and polybasic acids [0044] (iv)
Esters of polyhydric alcohols and polybasic acids [0045] (v) Mixed
esters of monohydric alcohol and polyhydric alcohol mixtures with
polybasic acids [0046] (vi) Mixed esters of polyhydric alcohols
with monobasic acid and polybasic acid mixtures [0047] (vii) Mixed
esters of monohydric alcohol and polyhydric alcohol mixtures with
monobasic acids and polybasic acids
[0048] Preferred among these are (ii) esters of polyhydric alcohols
and monobasic acids, from the viewpoint of achieving superior
lubricity, more easily obtaining a low pour point, improving the
handleability in winter season and cold climates, and more easily
obtaining a high viscosity index.
[0049] As naturally-derived esters to be used for the invention
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 obtained by increasing the oleic acid content of the fatty
acids in glycerides by cross-breeding or gene recombinant
techniques, and animal oils such as lard.
[0050] Among these naturally-derived esters, there are preferred
high-oleic natural fats and oils with increased oleic acid contents
from the viewpoint of lubricant stability, and there are
particularly preferred fatty acid and glycerin triesters
(hereinafter referred to simply as "triesters") with 40-98% by mass
oleic acid in the fatty acid portion. By using such triesters it is
possible to achieve a satisfactory high-level balance between
lubricity and heat/oxidation stability. The oleic acid content of
the fatty acid composing the triester is preferably not less than
50% by mass, more preferably not less than 60% by mass, even more
preferably not less than 70% by mass, and preferably not greater
than 95% by mass and more preferably not greater than 90% by mass,
from the standpoint of achieving a satisfactory high-level balance
between lubricity and heat/oxidation stability.
[0051] The proportions of oleic acid, and of linoleic acid, etc.
described hereunder in the fatty acid of the aforementioned
triester (hereinafter referred to as "constituent fatty acid") are
measured in a manner based on the Standard Fat and Oil Analysis
Methods 2.4.2, "Fatty Acid Composition", established by the Japan
Oil Chemists' Society.
[0052] There are no particular restrictions on fatty acids other
than oleic acid for the constituent fatty acid of the triester so
long as the lubricity and heat/oxidation stability are not
impaired, but preferably they are C6-24 fatty acids. The C6-24
fatty acids may be saturated fatty acids, or they may be
unsaturated fatty acids with 1-5 unsaturated bonds. The fatty acids
may also be either straight-chain or branched. They may also
contain 1-3 hydroxyl groups (--OH) in the molecule in addition to
carboxyl groups (--COOH). As such fatty acids there may be
mentioned, specifically, caproic acid, caprylic acid, capric acid,
lauric acid, myristic acid, palmitic acid, stearic acid, arachidic
acid, behenic acid, lignoceric acid, lauroleic acid, myristoleic
acid, palmitoleic acid, gadoleic acid, erudic acid, ricinolic acid,
linoleic acid, linolenic acid, oleostearic acid, licanic acid,
arachidonic acid and clupanodoic acid. Linoleic acid is preferred
among these fatty acids from the viewpoint of achieving both
lubricity and heat/oxidation stability, and more preferably
linoleic acid constitutes 1-60% by mass (more preferably 2-50% by
mass, and even more preferably 4-40% by mass) of the constituent
fatty acids of the triester.
[0053] Also from the viewpoint of achieving both lubricity and
heat/oxidation stability, C6-16 fatty acids preferably constitute
0.1-30% by mass (more preferably 0.5-20% by mass and even more
preferably 1-10% by mass) of the constituent fatty acids in the
triester. If the proportion of C6-16 fatty acids is less than 0.1%
by mass the heat/oxidation stability will tend to be reduced, while
if it is greater than 30% by mass the lubricity will tend to be
reduced.
[0054] The total degree of unsaturation of the triester is
preferably not greater than 0.3, and more preferably not greater
than 0.2. If the total degree of unsaturation of the triester is
greater than 0.3, the heat/oxidation stability of the lubricating
oil of the invention will tend to be impaired. The total degree of
unsaturation according to the invention is the total degree of
unsaturation measured by the "Testing method of polyether for
polyurethane" (JIS K1557-1970), using the same apparatus and
procedure, except that a triester was used instead of a polyether
for polyurethane.
[0055] The triester of the invention may be a synthetically
obtained oil or a natural oil such as a triester-containing
vegetable oil, so long as the proportion of oleic acid of the
constituent fatty acid satisfies the conditions specified above,
but from the standpoint of human safety it is preferred to use a
natural oil such as a vegetable oil. Preferred vegetable oils
include rapeseed oil, sunflower oil, soybean oil, corn oil and
canola oil, among which sunflower oil, rapeseed oil and soybean oil
are particularly preferred.
[0056] Although most natural vegetable oils have a total degree of
unsaturation exceeding 0.3, their total degree of unsaturation can
be reduced by treatment such as hydrogenation in a refining step.
In addition, vegetable oils with low total degrees of unsaturation
can be easily produced by gene recombinant techniques. Examples of
vegetable oils with a degree of unsaturation of not greater than
0.3 and an oleic acid content of 70% by mass or greater include
high-oleic-acid canola oil, and examples of vegetable oils having
contents of 80% by mass and greater include high-oleic-acid soybean
oil, high-oleic-acid sunflower oil and high-oleic-acid rapeseed
oil.
[0057] According to the invention, when a polyhydric alcohol is
used as the alcohol component, the ester may be a total ester
wherein all of the hydroxyl groups of the polyhydric alcohol are
esterified, or it may be a partial ester wherein a portion of the
hydroxyl groups remain as hydroxyl groups without esterification.
Also, when a polybasic acid is used as the acid component, the
organic acid ester may be a total ester wherein all of the carboxyl
groups of the polybasic acid are esterified, or it may be a partial
ester wherein a portion of the carboxyl groups remain as carboxyl
groups without esterification.
[0058] The iodine value of the (A) ester oil 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 g Br.sub.2/100 g, more
preferably 0-30 g Br.sub.2/100 g, even more preferably 0-20 g
Br.sub.2/100 g and most preferably 0-10 g Br.sub.2/100 g. If the
iodine value or bromine value of the ester are within the
aforementioned ranges, the obtained lubricating oil will tend to
have higher sticking resistance. Here, the "iodine value" is the
value measured by the indicator titration method defined by JIS K
0070 "Method of measuring acid value, saponification value, ester
value, iodine value, hydroxyl value and unsaponifiable matter of
chemical products". The bromine value is the value measured by JIS
K 2605 "Chemical Products--Test method for bromine
value--electometric titration".
[0059] In order to impart more satisfactory lubricating performance
to the oil for metal working of the invention, preferably the
hydroxyl value of the (A) ester oil is 0.01-300 mgKOH/g and the
saponification degree is 100-500 mgKOH/g. In order to obtain even
further increased lubricity according to the invention, the upper
limit for the hydroxyl value of the ester 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
degree of the (A) ester oil is more preferably 400 mgKOH/g, while
the lower limit is more preferably 200 mgKOH/g. Here, the "hydroxyl
value" is the value measured by the indicator titration method
defined by JIS K 0070 "Method of measuring acid value,
saponification value, ester value, iodine value, hydroxyl value and
unsaponifiable matter of chemical products". The saponification
value is the value measured by the indicator titration method of
JIS K 2503 "Testing method of lubricating oil for aircraft".
[0060] There are no particular restrictions on the kinematic
viscosity of the (A) ester oil, but the kinematic viscosity at
40.degree. C. is preferably not greater than 300 mm.sup.2/s, more
preferably not greater than 200 mm.sup.2/s, even more preferably
not greater than 100 mm.sup.2/s and most preferably not greater
than 75 mM.sup.2/s. The kinematic viscosity of the ester is also
preferably not less than 1 mm.sup.2/s, more preferably not less
than 3 mm.sup.2/s and even more preferably not less than 5
mm.sup.2/s.
[0061] There are no particular restrictions on the pour point and
viscosity index of the (A) ester oil, 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.
[0062] The (B) hydrocarbon oil in the first oil for metal working
is not particularly restricted so long as it has a kinematic
viscosity of 1-20 mm.sup.2/s at 40.degree. C., and it may be a
mineral oil or synthetic oil, or a mixture of two or more different
types.
[0063] As examples of mineral oils there may be mentioned
paraffin-based mineral oils or naphthene-based mineral oils which
are lube-oil distillates obtained by atmospheric distillation and
vacuum distillation of crude oil, with refinement by appropriate
combinations of refining treatments such as solvent deasphalting,
solvent extraction, hydrocracking, solvent dewaxing, catalytic
dewaxing, hydrotreating, sulfuric acid treating and clay
treatment.
[0064] As synthetic oils there may be mentioned, specifically,
polyolefins such as propylene oligomer, polybutene,
polyisobutylene, C5-20 .alpha.-olefin oligomers and ethylene and
C5-20 .alpha.-olefin co-oligomers, or their hydrogenated products;
alkylbenzenes such as monoalkylbenzenes, dialkylbenzenes and
polyalkylbenzenes; and alkylnaphthalenes such as
monoalkylnaphthalenes, dialkylnaphthalenes and
polyalkylnaphthalenes. These may be used alone or in combinations
of two or more.
[0065] When the polyolefin is a copolymer of olefin monomers with
different structures, there are no particular restrictions on the
monomer ratio and monomer arrangement of the copolymer, and it may
be a random copolymer, an alternating copolymer or a block
copolymer. An olefin monomer may be an .alpha.-olefin, internal
olefin, straight-chain olefin or branched olefin.
[0066] Among these, white oils and polyolefins or their
hydrogenated forms are preferred from the viewpoint of oil mist
properties and biodegradability.
[0067] White oil is also known as liquid paraffin, and it is highly
refined by sulfuric acid treatment or hydrogenation treatment of
mineral oil. More specifically, white oil is a substance that
matches the specification of "liquid paraffin" of JIS K 2231, i.e.
has an evaluation score of not greater than 1 in the corrosion test
(100.degree. C., 3 hrs), has a color (Saybolt) of +30 or greater,
exhibits the same or a lighter color than standard color solution
in the readily carbonizable substances test, and does not produce a
residue of yellow crystals (nitronaphthalene) in a nitronaphthalene
test.
[0068] Among polyolefins and their hydrogenated products, there are
preferred C5-20 .alpha.-olefin oligomers and their hydrogenated
products, among which hydrogenated 1-octene oligomers, hydrogenated
1-decene oligomers and hydrogenated 1-dodecene oligomers are
particularly preferred.
[0069] The polyolefin used for the invention may be produced by a
process known in the prior art. Specifically, a target polyolefin
may be produced, for example, by heated reaction in the absence of
a catalyst, or it may be produced by homopolymerization or
copolymerization of the aforementioned olefins using a publicly
known catalyst, for example, an organic peroxide catalyst such as
benzoyl peroxide; a Friedel-Crafts catalyst such as aluminum
chloride, aluminum chloride-polyhydric alcohol, aluminum
chloride-titanium tetrachloride, aluminum chloride-alkyl tin halide
or boron fluoride; a Ziegler catalyst such as organic aluminum
chloride-titanium tetrachloride or organic aluminum-titanium
tetrachloride; a metallocene catalyst such as
aluminoxane-zirconocene or ionic compound-zirconocene; or a Lewis
acid complex catalyst such as aluminum chloride-base or boron
fluoride-base.
[0070] The polyolefin obtained by this process usually has a double
bond, but as mentioned above, the first oil for metal working
preferably uses a polyolefin having the double bonded carbons
hydrogenated, i.e. a hydrogenated polyolefin, as the base oil.
Using a hydrogenated polyolefin will tend to improve the
heat/oxidation stability of the oil for metal working. A
hydrogenated polyolefin can be obtained, for example, by
hydrogenating a polyolefin with hydrogen in the presence of a
publicly known hydrogenation catalyst, for saturation of the double
bonds in the polyolefin. Selection of the catalyst used for
polymerization of the olefin will allow polymerization of the
olefin and hydrogenation of the double bonds in the polymer to be
accomplished in a single step without requiring two separate steps
for polymerization of the olefin and hydrogenation of the
polymer.
[0071] As mentioned above, the kinematic viscosity of the (B)
hydrocarbon oil at 40.degree. C. is not greater than 20 mm.sup.2/s,
preferably not greater than 15 mm.sup.2/s, more preferably not
greater than 10 mm.sup.2/s and even more preferably not greater
than 5 mm.sup.2/s. If the kinematic viscosity is greater than 20
mm.sup.2/s, the oil mist property will be reduced, resulting in an
insufficient working efficiency and tool life with minimum quantity
lubrication systems, as well as unsatisfactory biodegradability.
Also as mentioned above, the kinematic viscosity of the (B)
hydrocarbon oil at 40.degree. C. is not less than 1 mm.sup.2/s,
preferably not less than 2 mm.sup.2/s and even more preferably not
less than 3 mm.sup.2/s. If the kinematic viscosity is 1 mm.sup.2/s,
the oil will form a mist too readily, causing more mist to fly out
into the working environment and preventing a sufficient amount of
oil from being supplied in the minimum quantity lubrication system,
or it may become impossible to avoid adhesion of the metal from the
workpieces or increased working resistance for non-ferrous metal
working, resulting in insufficient working efficiency and tool life
in either case.
[0072] The content of the (B) hydrocarbon oil in the first oil for
metal working is preferably not greater than 70% by mass, more
preferably not greater than 60% by mass and even more preferably
not greater than 50% by mass based on the total amount of the oil
for metal working. If the content exceeds 70% by mass the oil mist
property will be reduced, and the working efficiency and tool life
will tend to be poor when it is used for cutting and grinding in a
minimum quantity lubrication system. The content of the (B)
hydrocarbon oil is preferably not less than 1% by mass, more
preferably not less than 5% by mass, even more preferably not less
than 10% by mass and most preferably not less than 20% by mass
based on the total amount of the oil for metal working. If the
content is less than 1% by mass, it may become impossible to avoid
adhesion of the metal from the workpieces or increased working
resistance for non-ferrous metal working, and the working
efficiency and tool life will tend to be reduced.
[0073] The first oil for metal working of the invention may be
composed entirely of the (A) ester oil and (B) hydrocarbon oil, but
it may also contain other base oils as well. As other base oils
there may be mentioned, specifically, polyglycols such as
polyethylene glycol, polypropylene glycol,
polyoxyethylenepolyoxypropylene glycol, polyethyleneglycol
monoether, polypropyleneglycol monoether,
Polyoxyethylenepolyoxypropyleneglycol monoether, Polyethyleneglycol
diether, polypropyleneglycol diether and
Polyoxyethylenepolyoxypropyleneglycol diether; phenyl ethers such
as monoalkyldiphenyl ethers, dialkyldiphenyl ether,
monoalkyltriphenyl ethers, dialkyltriphenyl ethers, tetraphenyl
ether, monoalkyl tetraphenyl ethers, dialkyltetraphenyl ethers and
pentaphenyl ether; silicone oil; and fluoroethers such as
perfluoroether. These may be used alone or in combinations of two
or more.
[0074] The content of base oils other than components (A) and (B)
in the first oil for metal working of the invention is preferably
not greater than 65% by mass, more preferably not greater than 50%
by mass, even more preferably not greater than 30% by mass, yet
more preferably not greater than 20% by mass and most preferably
not greater than 10% by mass based on the total amount of the oil
for metal working.
[0075] The moisture content of the first oil for metal working is
not particularly restricted, but from the viewpoint of storage
stability and rust inhibition, it is preferably not greater than
20,000 ppm, more preferably not greater than 10,000 ppm and even
more preferably not greater than 5000 ppm. From the viewpoint of
preventing adhesion of the metal from the workpieces and increase
in working resistance to achieve an excellent working efficiency
and tool life, the moisture content is preferably not less than 200
ppm, more preferably not less than 300 ppm, even more preferably
not less than 400 ppm and yet more preferably not less than 500
ppm. The moisture content according to the invention is the
moisture content as measured by Karl Fischer coulometric titration
based on JIS K 2275.
[0076] When the moisture content is adjusted by addition of water
to the first oil for metal working, the added water may be hard
water or soft water, and any desired source such as city water,
industrial water, ion-exchanged water, distilled water or alkali
ion water may be used.
[0077] The second oil for metal working of the invention employs
the (A) ester oil as the base oil and has a moisture content of
200-20,000 ppm. Specific examples and preferred modes of the (A)
ester oil in the second oil for metal working are the same as for
the (A) ester oil of the first oil for metal working, and their
explanation will not be repeated.
[0078] The moisture content of the second oil for metal working of
the invention is 200-20,000 ppm. Specifically, the moisture content
of the second oil for metal working must be not greater than 20,000
ppm, preferably not greater than 10,000 ppm and more preferably not
greater than 5000 ppm from the standpoint of storage stability and
rust inhibition. From the viewpoint of preventing adhesion of the
metal from the workpieces and increased working resistance to
achieve an excellent working efficiency and tool life, the moisture
content is preferably not less than 200 ppm, more preferably not
less than 300 ppm, even more preferably not less than 400 ppm and
yet more preferably not less than 500 ppm. The moisture content
according to the invention is the moisture content as measured by
Karl Fischer coulometric titration based on JIS K 2275.
[0079] When the moisture content is adjusted by addition of water
to the second oil for metal working, the added water may be hard
water or soft water, and any desired source such as city water,
industrial water, ion-exchanged water, distilled water or alkali
ion water may be used.
[0080] So long as the second oil for metal working of the invention
has a moisture content in the range of 200-20,000 ppm, it may
consist entirely of the (A) ester oil or it may further contain
other base oils and additives described hereunder. When the second
oil for metal working contains components other than the (A) ester
oil, the content of the (A) ester oil is preferably not less than
30% by mass, more preferably not less than 50% by mass, even more
preferably not less than 70% by mass and most preferably not less
than 80% by mass based on the total amount of the oil for metal
working. If the content is less than 30% by mass, the oil mist
property will be reduced, leading to adhesion of the metal from the
workpieces or increased working resistance when used for cutting
and grinding in a minimum quantity lubrication system, and tending
to result in insufficient working efficiency and tool life, as well
as reduced biodegradability.
[0081] When the second oil for metal working also contains a base
oil other than the (A) ester oil, the additional base oil may be a
mineral oil or synthetic oil, or it may be a mixture of two or more
thereof.
[0082] As examples of mineral oils there may be mentioned
paraffin-based mineral oils or naphthene-based mineral oils which
are lube-oil distillates obtained by atmospheric distillation and
vacuum distillation of crude oil, with refinement by appropriate
combinations of refining treatments such as solvent deasphalting,
solvent extraction, hydrocracking, solvent dewaxing, catalytic
dewaxing, hydrotreating, sulfuric acid treating and clay
treatment.
[0083] As synthetic oils there may be mentioned, specifically,
polyolefins such as propylene oligomer, polybutene,
polyisobutylene, C5-20 .alpha.-olefin oligomers and ethylene and
C5-20 .alpha.-olefin co-oligomers, or their hydrogenated products;
alkylbenzenes such as monoalkylbenzenes, dialkylbenzenes and
polyalkylbenzenes; alkylnaphthalenes such as monoalkylnaphthalenes,
dialkylnaphthalenes and polyalkylnaphthalenes, polyglycols such as
polyethylene glycol, polypropylene glycol,
polyoxyethylenepolyoxypropylene glycol, Polyethyleneglycol
monoether, polypropyleneglycol monoether,
Polyoxyethylenepolyoxypropyleneglycol monoether, polyethylene
glycol diether, polypropylene glycol diether and
Polyoxyethylenepolyoxypropylene glycol diether; phenyl ethers such
as monoalkyldiphenyl ethers, dialkyldiphenyl ethers,
monoalkyltriphenyl ethers, dialkyltriphenyl ethers,
tetraphenylether, monoalkyltetraphenyl ethers, dialkyltetraphenyl
ethers and pentaphenyl ether; silicone oil; fluoroethers such as
perfluoroether, and the like. These may be used alone or in
combinations of two or more.
[0084] The content of the other base oils in the second oil for
metal working is preferably not greater than 70% by mass, more
preferably not greater than 50% by mass, even more preferably not
greater than 30% by mass, yet more preferably not greater than 20%
by mass and most preferably not greater than 10% by mass based on
the total amount of the oil for metal working.
[0085] The first and second oils for metal working according to the
invention preferably also contain (C) an oiliness agent from the
viewpoint of preventing adhesion of the metal from the workpieces
and increased working resistance to achieve superior working
efficiency and tool life. As oiliness agents there may be mentioned
(C-1) alcohol oiliness agents, (C-2) carboxylic acid oiliness
agents, (C-3) unsaturated carboxylic acid sulfides, (C-4) compounds
represented by general formula (1) below, (C-S) compounds
represented by general formula (2) below, (C-6) polyoxyalkylene
compounds, (C-7) ester oiliness agents, (C-8) polyhydric alcohol
hydrocarbylethers and (C-9) amine oiliness agents. ##STR1##
[wherein R.sup.1 represents a C1-30 hydrocarbon group, a represents
an integer of 1-6 and b represents an integer of 0-5.] ##STR2##
[wherein R.sup.2 represents a C1-30 hydrocarbon group, c represents
an integer of 1-6 and d represents an integer of 0-5.]
[0086] The (C-1) alcohol oiliness agent may be a monohydric alcohol
or a polyhydric alcohol. From the standpoint of preventing adhesion
of the metal from the workpieces and increased working resistance
to achieve superior working efficiency and tool life, C1-40
monohydric alcohols are preferred, C1-25 alcohols are more
preferred and C8-18 alcohols are most preferred. More specifically,
there may be mentioned as examples the alcohols composing the
aforementioned base oil esters. These alcohols may be
straight-chain or branched and either saturated or unsaturated, but
from the standpoint of preventing sticking, they are preferably
saturated.
[0087] The (C-2) carboxylic acid oiliness agent may be a monobasic
or polybasic acid. From the standpoint of preventing adhesion of
the metal from the workpieces and increased working resistance to
achieve superior working 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. More
specifically, there may be mentioned as examples the carboxylic
acids composing the esters for the aforementioned base oils. These
carboxylic acids may be straight-chain or branched and either
saturated or unsaturated, but from the standpoint of preventing
sticking they are preferably saturated carboxylic acids.
[0088] As examples of the (C-3) unsaturated carboxylic acid
sulfides there may be mentioned sulfides of unsaturated carboxylic
acids among the aforementioned (C-2) carboxylic acids. As specific
examples there may be mentioned sulfides of oleic acid.
[0089] As examples of C1-30 hydrocarbon groups represented by
R.sup.1 in the (C-4) compounds represented by general formula (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.
[0090] The hydroxyl 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.
[0091] As examples of C1-30 hydrocarbon groups represented by
R.sup.2 in the (C-5) compounds represented by general formula (2)
above, there may be mentioned the same examples of C1-30
hydrocarbon groups represented by R.sup.1 in general formula (1),
and the preferred examples are also the same. The hydroxyl 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.
[0092] As examples of the (C-6) polyoxyalkylene compounds there may
be mentioned compounds represented by the following general
formulas (3) and (4). R.sup.3O--(R.sup.4O).sub.e--R.sup.5 (3)
[wherein R.sup.3 and R.sup.5 each independently represent hydrogen
or a C1-30 hydrocarbon group, R.sup.4 represents C2-4 alkylene, and
e represents an integer such that the number-average molecular
weight is 100-3500.] A-[(R.sup.6O).sub.f--R.sup.7].sub.g (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.6 represents C2-4
alkylene, R.sup.7 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 sane number as the number
of hydrogens removed from the hydroxyl group of A.]
[0093] In general formula (3), at least one of R.sup.3 and R.sup.5
is preferably hydrogen. As examples of C1-30 hydrocarbon groups
represented by R.sup.3 and R.sup.5 there may be mentioned the same
examples of C1-30 hydrocarbon groups represented by R.sup.1 of
general formula (1) above, and the preferred examples are also the
same. As specific examples of C2-4 alkylene groups represented by
R.sup.4 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.
[0094] As specific examples of polyhydric alcohols having 3-10
hydroxyl groups in A of general formula (4) above, there may be
mentioned polyhydric alcohols such as glycerin, polyglycerin (dimer
to tetramer of glycerin such as diglycerin, triglycerin and
tetraglycerin), trimethylolalkanes (trimethylolethane,
trimethylolpropane, trimethylolbutane) and their dimer to tetramer,
pentaerythritol, dipentaerythritol, 1,2,4-butanetriol,
1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol,
sorbitol, sorbitan, sorbitol-glycerin condensation products,
adonitol, arabitol, xylitol, mannitol, iditol, talitol, dulcitol
and allitol; and sugars such as xylose, arabinose, ribose,
rhamnose, glucose, fructose, galactose, mannose, sorbose,
cellobiose, mantose, isomantose, trehalose and sucrose. Preferred
among these are glycerin, polyglycerin, trimethylolalkanes and
their dimer to tetramer, pentaerythritol, dipentaerythritol,
sorbitol and sorbitan.
[0095] As examples of C2-4 alkylene groups represented by R.sup.6
there may be mentioned the same examples of C2-4 alkylene groups
represented by R.sup.4 in general formula (3) above. As examples of
C1-30 hydrocarbon groups represented by R.sup.7 there may be
mentioned the same examples of C1-30 hydrocarbon groups represented
by R.sup.1 in general formula (1) above, and the preferred examples
are also the same. At least one of the g R.sup.7 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.
[0096] The alcohols in the (C-7) ester oiliness agents may be
monohydric alcohols or polyhydric alcohols, and the carboxylic
acids may be monobasic acids or polybasic acids. The "ester"
referred to here is distinct from the triester which is the
essential component of the first and second oils for metal working.
Throughout the following explanation, the former will be referred
to as "ester oiliness agent" for convenience.
[0097] The alcohol composing the (C-7) ester oiliness agent may be
a monohydric alcohol or polyhydric alcohol, and the acid composing
the ester oiliness agent may be a monobasic acid or polybasic
acid.
[0098] As monohydric alcohols there may be used C1-24, preferably
C1-12 and even more preferably C1-8 alcohols, which may be
straight-chain or branched and may be 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 decanol, 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 thereof.
[0099] As polyhydric alcohols there may be used C2-10 and
preferably C2-6 alcohols. As specific examples of C2-10 polyhydric
alcohols there may be mentioned dihydric alcohols such as ethylene
glycol, diethylene glycol, polyethylene glycol (trimer to
pentadecamer of ethylene glycol), propylene glycol, dipropylene
glycol, polypropylene glycol (trimer to pentadecamer of propylene
glycol), 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; polyhydric alcohols such as glycerin,
polyglycerin (dimer to octamer of glycerin, such as diglycerin,
triglycerin, tetraglycerin and the like), trimethylolalkanes
(trimethylolethane, trimethylolpropane, trimethylolbutane) and
their dimer to octamer, pentaerythritol and its dimer to tetramer,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensation product, adonitol, arabitol, xylitol and mannitol;
sugars such as xylose, arabinose, ribose, rhamnose, glucose,
fructose, galactose, mannose, sorbose, cellobiose, maltose,
isomaltose, trehalose and sucrose; and mixtures thereof.
[0100] Preferred among these polyhydric alcohols are C2-6
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol (trimer to decamer of ethylene glycol),
propylene glycol, dipropylene glycol, polypropylene glycol (trimer
to decamer 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) and
their dimer to tetramer, pentaerythritol, dipentaerythritol,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensation product, adonitol, arabitol, xylitol and mannitol, and
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.
[0101] The alcohol composing the ester oiliness agent may be a
monohydric alcohol or a polyhydric alcohol as mentioned above, but
it is preferably a polyhydric alcohol from the viewpoint of
preventing adhesion of the metal from the workpieces and increased
working resistance to achieve superior working efficiency and tool
life, more easily obtaining a low pour point and improving the
handleability in winter season and cold climates. Using a
polyhydric alcohol ester will result in improved precision of the
finishing surface of the workpiece and an even greater
anti-abrasive effect for tool blades during cutting and
grinding.
[0102] In most cases a C2-24 fatty acid will be used as the
monobasic acid among acids for the ester oiliness 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; 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; and
mixtures thereof. From the viewpoint of preventing adhesion of the
metal from the workpieces and increased working resistance to
achieve superior working efficiency and tool life, as well as
handleability, 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.
[0103] 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
[0104] The combination of the alcohol and acid in the (C-7) ester
oiliness agent may be as desired and is not particularly
restricted, but the following esters may be mentioned as examples
of ester oiliness agents to be used for the invention. [0105]
(C-7-1) Esters of monohydric alcohols and monobasic acids [0106]
(C-7-2) Esters of polyhydric alcohols and monobasic acids [0107]
(C-7-3) Esters of monohydric alcohols and polybasic acids [0108]
(C-7-4) Esters of polyhydric alcohols and polybasic acids [0109]
(C-7-5) Mixed esters of monohydric alcohol and polyhydric alcohol
mixtures with polybasic acids [0110] (C-7-6) Mixed esters of
polyhydric alcohols with monobasic acid and polybasic acid mixtures
[0111] (C-7-7) Mixed esters of monohydric alcohol and polyhydric
alcohol mixtures with monobasic acids and polybasic acids
[0112] When a polyhydric alcohol is used as the alcohol component,
the ester may be a total ester wherein all of the hydroxyl groups
of the Polyhydric alcohol are esterified, or it may be a partial
ester wherein a Portion of the hydroxyl groups remain as hydroxyl
groups without esterification. Also, when a polybasic acid is used
as the carboxylic acid component, the ester may be a total ester
wherein all of the carboxyl groups of the polybasic acid are
esterified, or it may be a partial ester wherein a portion of the
carboxyl groups remain as carboxyl groups without
esterification.
[0113] There are no particular restrictions on the total number of
carbon atoms of the ester oiliness agent, but from the viewpoint of
preventing adhesion of the metal from the workpieces and increased
working resistance to achieve superior working efficiency and tool
life, the total number of carbon atoms of the ester is preferably 7
or more, more preferably 9 or more and most preferably 11 or more.
From the standpoint of minimizing staining and corrosion and of
compatibility with organic materials, the ester preferably has a
total number of carbon atoms of not greater than 60, more
preferably not greater than 45, even more preferably not greater
than 26, yet more preferably not greater than 24 and most
preferably not greater than 22.
[0114] As polyhydric alcohols of the (C-8) polyhydric alcohol
hydrocarbylethers there are usually used those with 2-10 and
preferably 2-6 hydroxyl groups. As specific examples of C2-10
polyhydric alcohols there may be mentioned dihydric alcohols such
as ethylene glycol, diethylene glycol, polyethylene glycol (trimer
to pentadecamer of ethylene glycol), propylene glycol, dipropylene
glycol, Polypropylene glycol (trimer to pentadecamer of propylene
glycol), 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; polyhydric alcohols such as glycerin,
polyglycerin (dimer to octamer of glycerin, such as diglycerin,
triglycerin, tetraglycerin and the like), trimethylolalkanes
(trimethylolethane, trimethylolpropane, trimethylolbutane) and
their dimer to octamer, pentaerythritol and its dimer to tetramer,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensation product, adonitol, arabitol, xylitol and mannitol;
sugars such as xylose, arabinose, ribose, rhamnose, glucose,
fructose, galactose, mannose, sorbose, cellobiose, maltose,
isomaltose, trehalose and sucrose; and mixtures thereof.
[0115] Preferred among these polyhydric alcohols are C2-6
polyhydric alcohols such as ethylene glycol, diethylene glycol,
polyethylene glycol (trimer to decamer of ethylene glycol),
propylene glycol, dipropylene glycol, polypropylene glycol (trimer
to decamer 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) and their
dimer to tetramer, pentaerythritol, dipentaerythritol,
1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol,
1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin
condensation product, adonitol, arabitol, xylitol and mannitol, and
mixtures thereof. More preferred are ethylene glycol, propylene
glycol, neopentyl glycol, glycerin, trimethylolethane,
trimethylolpropane, pentaerythritol, sorbitan and mixtures thereof
Glycerin is most preferred among these from the viewpoint of
preventing adhesion of the metal from the workpieces and increased
working resistance to achieve superior working efficiency and tool
life.
[0116] As (C-8) polyhydric alcohol hydrocarbylethers there may be
used ones obtained by hydrocarbyletherification of all or a portion
of the hydroxyl groups of the aforementioned polyhydric alcohols.
From the standpoint of preventing adhesion of the metal from the
workpieces and increased working resistance to achieve superior
working efficiency and tool life, preferably a portion of the
hydroxyl groups of the polyhydric alcohol are hydrocarbyletherified
(partial etherification). Here, a hydrocarbyl group 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,
C7-18 arylalkyl, or the like.
[0117] 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.
[0118] 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.
[0119] 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).
[0120] 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-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) and straight-chain
or branched dodecylphenyl (including all structural isomers).
[0121] 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).
[0122] From the viewpoint of preventing adhesion of the metal from
the workpieces and increased working resistance to achieve superior
working efficiency and tool life, C2-18 straight-chain or branched
alkyl and C2-18 straight-chain or branched alkenyl groups are
preferred, and C3-12 straight-chain or branched alkyl and oleyl (a
residue obtained by removing the hydroxyl group from oleyl alcohol)
are more preferred.
[0123] A monoamine is preferred for use as the (C-9) amine oiliness
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 number of carbon atoms of the monoamine, and when the monoamine
has two or more hydrocarbon groups it is the total number of carbon
atoms.
[0124] Monoamines to be used for the invention include primary
monoamines, secondary monoamines and tertiary monoamines, although
primary monoamines are preferred from the standpoint of Preventing
adhesion of the metal from the workpieces and increased working
resistance to achieve superior working efficiency and extended tool
life.
[0125] 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
preventing adhesion of the metal from the workpieces and increased
working resistance to achieve superior working efficiency and tool
life. The alkyl and alkenyl groups may be straight-chain or
branched, but are Preferably straight-chain from the standpoint of
preventing adhesion of the metal from the workpieces and increased
working resistance to achieve superior working efficiency and tool
life.
[0126] 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. From
the viewpoint of preventing adhesion of the metal from the
workpieces and increased working resistance to achieve superior
working efficiency and tool life, C12-24 primary monoamines are
preferred, C14-20 primary monoamines are more preferred and C16-18
primary monoamines are even more preferred.
[0127] According to the invention, one selected from among the
aforementioned oiliness agents (C-1) to (C-9) may be used, or a
mixture of two or more thereof may be used. From the viewpoint of
preventing adhesion of the metal from the workpieces and increased
working resistance to achieve superior working efficiency and tool
life, it is preferably one or a mixture of two or more selected
from among (C-2) carboxylic acid oiliness agents and (C-9) amine
oiliness agents.
[0128] The content of the (C) oiliness agent is not particularly
restricted, but from the standpoint of preventing adhesion of the
metal from the workpieces and increased working resistance to
achieve Superior working efficiency and tool life, it is preferably
not less than 0.01% by mass, more preferably not less than 0.05% by
mass and even more preferably not less than 0.1% by mass based on
the total oil 5 for metal working. From the standpoint of
stability, the oiliness agent content is preferably not greater
than 15% by mass, more preferably not greater than 10% by mass and
even more preferably not greater than 5% by mass based on the total
oil for metal working.
[0129] The first and second oils for metal working according to the
invention preferably also contain (D) an extreme-pressure agent,
from the viewpoint of preventing adhesion of the metal from the
workpieces and increased working resistance to achieve superior
working efficiency and tool life. Particularly when the (D)
extreme-pressure agent is used together with the (C) oiliness agent
described above, the components work synergistically to prevent
adhesion of the metal from the workpieces and increased working
resistance and achieve an even more excellent working efficiency
and tool life. As described hereunder, the first and second oils
for metal working may be used as lubricating oils for sections
other than machine tool working sections, in which case they
preferably contain the (C) oiliness agent.
[0130] As the (D) extreme-pressure agents there may be mentioned
the (D-1) sulfur compounds and (D-2) phosphorus compounds described
below.
[0131] There are no particular restrictions on (D-1) sulfur
compounds so long as the properties as an oil for metal working are
not impaired, but preferred for use are dihydrocarbyl polysulfide,
sulfurized esters, sulfurized mineral oils, zinc dithiophosphate
compounds, zinc dithiocarbaminate compounds, molybdenum
dithiophosphate compounds and molybdenum thiocarbaminate.
[0132] Dihydrocarbyl polysulfides are sulfur-based compounds
generally known as polysulfides or sulfurized olefins, and
specifically refer to compounds represented by the following
general formula (5): R.sup.8--S.sub.h--R.sup.9 (5) wherein R.sup.8
and R.sup.9 are 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.]
[0133] As specific examples of R.sup.8 and R.sup.9 in general
formula (5) above 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.8 and R.sup.9 of general formula (5) are C3-18 alkyl
groups derived from propylene, 1-butene or isobutylene, or C6-8
aryl and alkylaryl groups, and as examples of such groups there may
be mentioned alkyl groups such as isopropyl, propylene
dimer-derived branched hexyl (including all branched isomers),
propylene trimer-derived branched nonyl (including all branched
isomers), propylene tetramer-derived branched dodecyl (including
all branched isomers), propylene pentamer-derived branched
pentadecyl (including all branched isomers), propylene
hexamer-derived branched octadecyl (including all branched
isomers), sec-butyl, tert-butyl, 1-butene dimer-derived branched
octyl (including all branched isomers), isobutylene dimer-derived
branched octyl (including all branched isomers), 1-butene
trimer-derived branched dodecyl (including all branched isomers),
isobutylene trimer-derived branched dodecyl (including all branched
isomers), 1-butene tetramer-derived branched hexadecyl (including
all branched isomers) and isobutylene tetramer-derived branched
hexadecyl (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).
[0134] From the standpoint of preventing adhesion of the metal from
the workpieces and increased working resistance to achieve superior
working efficiency and tool life, R.sup.8 and R.sup.9 in general
formula (5) above are each preferably ethylene- or
propylene-derived C3-18 branched alkyl groups and most preferably
ethylene- or propylene-derived C6-15 branched alkyl groups.
[0135] As specific examples of sulfurized esters there may be
mentioned esters obtained by using desired methods for
sulfurization of animal and vegetable oils 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) with various alcohols;
and mixtures thereof.
[0136] Sulfurized mineral oils are obtained by dissolving elemental
sulfur in mineral oils. The mineral oils used for sulfurized
mineral oils according to the invention are not particularly
restricted, and specifically there may be mentioned paraffin-based
mineral oils or naphthene-based mineral oils which are lube-oil
distillates obtained by atmospheric distillation and vacuum
distillation of crude oil, with refinement by appropriate
combinations of refining treatments such as solvent deasphalting,
solvent extraction, hydrocracking, solvent dewaxing, catalytic
dewaxing, hydrotreating, sulfuric acid treating and clay treatment.
The elemental sulfur may be used in any of various forms such as
bulk, powder or molten liquid forms, but using elemental sulfur in
powder or molten liquid form is preferred as it allows efficient
dissolution in the base oil. Molten liquid elemental sulfur permits
mixture of liquids and is therefore advantageous by notably
shortening the time required for dissolution, but it must be
handled at above the melting point of elemental sulfur and
therefore necessitates special heating equipment and the like, such
that it is not always easy to manage given the risk associated with
handling in high-temperature environments. In contrast, elemental
sulfur powder is inexpensive and easy to manage while its
dissolution time is sufficiently short, and it is therefore
particularly preferred. There are no particular restrictions on the
sulfur content of the sulfurized mineral oil for the invention, but
normally it is preferably 0.05-1.0% by mass and more preferably
0.1-0.5% by mass based on the total sulfirized mineral oil
weight.
[0137] Zinc dithiophosphate compounds, zinc dithiocarbaminate
compounds, molybdenum dithiophosphate compounds and molybdenum
dithiocarbaminate compounds are compounds represented by the
following general formulas (6) to (9). ##STR3## [wherein R.sup.10,
R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16,
R.sup.17, R.sup.18, R.sup.19, R.sup.20R, R.sup.21, R.sup.22,
R.sup.23, R.sup.24 and R.sup.25 may be the same or different, and
each represents a C1 or greater hydrocarbon group, and X.sup.1 and
X.sup.2 each represents oxygen or sulfur].
[0138] As specific examples of hydrocarbon groups represented by
R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15,
R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21,
R.sup.22, R.sup.23, R.sup.24 and R.sup.25 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), methylethylcyclopentyl (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), dimethylethylcyclopentyl (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).
[0139] According to the invention, using at least one of the
aforementioned sulfur compounds selected from the group consisting
of dihydrocarbyl polysulfides and sulfurized esters is preferred in
order to achieve an even higher level of improvement in working
efficiency and tool life by preventing adhesion of the metal from
the workpieces and preventing increase in working resistance.
[0140] As specific examples of (D-1) 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, and
metal salts of the phosphorus compounds represented by the
following general formulas (10) and (11). These phosphorus
compounds may be esters of phosphoric acid, phosphorous acid or
thiophosphoric acid with alkanols or polyether alcohols, or they
may be derivatives thereof. ##STR4## [wherein X.sup.3, X.sup.4 and
X.sup.5 may be the same or different and each represents oxygen or
sulfur, with at least two from among X.sup.3, X.sup.4 and X.sup.5
being oxygen, and R.sup.26, R.sup.27 and R.sup.28 may be the same
or different and each represents hydrogen or a C1-30 hydrocarbon
group.] ##STR5## [X.sup.6, X.sup.7, X.sup.8 and X.sup.9 may be the
same or different and each represents oxygen or sulfur, with at
least three from among X.sup.6, X.sup.7, X.sup.8 and X.sup.9 being
oxygen, and R.sup.29, R.sup.30 and R.sup.31 may be the same or
different and each represents hydrogen or a C1-30 hydrocarbon
group.]
[0141] 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 and xylenyldiphenyl phosphate; [0142] 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
and dioleyl acid phosphate; [0143] 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, triheptylamines and trioctylamines of the
aforementioned acidic phosphoric acid esters; [0144] as chlorinated
phosphoric acid esters there may be mentioned tris-dichloropropyl
phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate
and polyoxyalkylene-bis[di(chloroalkyl)]phosphate; [0145] 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 and tricresyl phosphite; [0146] 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.
[0147] For metal salts of the phosphorus compounds represented by
general formulas (10) and (11) 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.26-R.sup.31 in the formulas.
[0148] 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).
[0149] 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,
methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl,
dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl
(with any positions of substitution of the alkyl groups on the
cycloalkyl groups).
[0150] 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).
[0151] 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).
[0152] 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).
[0153] The C1-30 hydrocarbon groups represented by
R.sup.26-R.sup.31 are preferably C1-30 alkyl groups or C6-24 aryl
groups, and are more preferably C3-18 alkyl groups and even more
preferably C4-12 alkyl groups.
[0154] Here, R.sup.26, R.sup.27 and R.sup.28 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.26,
R.sup.27 and R.sup.28 are the aforementioned hydrocarbon groups,
more preferably 1-2 are the aforementioned hydrocarbon groups and
even more preferably two are the aforementioned hydrocarbon
groups.]
[0155] Also, R.sup.29, R.sup.30 and R.sup.31 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.29,
R.sup.30 and R.sup.31 are the aforementioned hydrocarbon groups,
more preferably 1-2 are the aforementioned hydrocarbon groups and
even more preferably two are the aforementioned hydrocarbon
groups.]
[0156] In the phosphorus compounds represented by general formula
(10), at least two of X.sup.3--X.sup.5 must be oxygen, but
preferably all of X.sup.3--X.sup.5 are oxygen.
[0157] Also, in the phosphorus compounds represented by general
formula (11), at least three of X.sup.6--X.sup.9 must be oxygen,
but preferably all of X.sup.6--X.sup.9 are oxygen.
[0158] As examples of phosphorus compounds represented by general
formula (10) there may be mentioned phosphorous acid and
monothiophosphorous acid; phosphorous acid monoesters and
monothiophosphorous acid monoesters having one of the
aforementioned C1-30 hydrocarbon groups; phosphorous acid diesters
and monothiophosphorous acid diesters having two of the
aforementioned C1-30 hydrocarbon groups; phosphorous acid triesters
and monothiophosphorous acid triesters having three of the
aforementioned C1-30 hydrocarbon groups; and mixtures thereof.
[0159] Among these, phosphorous acid monoesters and phosphorous
acid diesters are preferred, and phosphorous acid diesters are
especially preferred.
[0160] As examples of phosphorus compounds represented by general
formula (11) there may be mentioned phosphoric acid and
monothiophosphoric acid; phosphoric acid monoesters and
monothiophosphoric acid monoesters having one of the aforementioned
C1-30 hydrocarbon groups; phosphoric acid diesters and
monothiophosphoric acid diesters having two of the aforementioned
C1-30 hydrocarbon groups; phosphoric acid triesters and
monothiophosphoric acid triesters having three of the
aforementioned C1-30 hydrocarbon groups; and mixtures thereof.
Among these, phosphoric acid monoesters and phosphoric acid
diesters are preferred, and phosphoric acid diesters are especially
preferred.
[0161] As metal salts of the phosphorus compounds represented by
general formula (10) and (11) there may be mentioned salts of the
aforementioned phosphorus compounds wherein all or a portion of the
acidic hydrogens are neutralized with a metal base. As such metal
bases there may be mentioned metal oxides, metal hydroxides, metal
carbonates and metal chlorides, and as the metals thereof there may
be mentioned specifically 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 and manganese. Preferred among these are
alkaline earth metals such as calcium and magnesium, and zinc.
[0162] 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 two moles of a phosphoric acid diester
(with one OH group), for example, a compound having the structure
represented by formula (12) below may be obtained as the major
component, although Polymerized molecules may also be present.
##STR6##
[0163] 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 formula (13) below may
be obtained as the major component, although polymerized molecules
may also be present. ##STR7##
[0164] Two or more of these may also be used in admixture.
[0165] According to the invention, phosphoric acid esters, acidic
Phosphoric acid esters and acidic phosphoric acid ester amine salts
are preferred among the aforementioned phosphorus compounds from
the standpoint of preventing adhesion of the metal from the
workpieces and increase in working resistance to achieve superior
working efficiency and tool life.
[0166] As described hereunder, the oil for metal working of the
invention may be applied for purposes other than metal working, and
when the oil for metal working 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 for metal working of the invention
is used as a hydraulic oil, a phosphoric acid ester is preferred.
When it is used for both a sliding surface oil and a hydraulic oil,
it is preferred to employ 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.
[0167] The oil for metal working of the invention may contain
either the (D-1) sulfur compound or (D-2) phosphorus compound, or
it may Contain both. From the standpoint of preventing adhesion of
the metal from the workpieces and increase in working resistance to
achieve superior working efficiency and tool life, it preferably
contains a (D-2) phosphorus compound or both a (D-1) sulfur
compound and (D-2) phosphorus compound, and more preferably it
contains both a (D-1) sulfur compound and (D-2) phosphorus
compound.
[0168] The content of the (D) extreme-pressure agent may be as
desired, but from the standpoint of preventing adhesion of the
metal from the workpieces and increase in working resistance to
achieve superior working efficiency and tool life, it is preferably
not less than 0.005% by mass, more preferably not less than 0.01%
by mass and even more preferably not less than 0.05% by mass based
on the total amount of the oil for metal working. From the
viewpoint of preventing abnormal abrasion, the extreme pressure
agent content is preferably not greater than 15% by mass, more
preferably not greater than 10% by mass and even more preferably
not greater than 7% by mass, based on the total weight of the oil
for metal working.
[0169] According to the invention, either a (C) oiliness agent or
(D) extreme-pressure agent may be used, but from the standpoint of
preventing adhesion of the metal from the workpieces and increase
in working resistance to achieve even better improvement in working
efficiency and tool life, preferably a (C) oiliness agent and (D)
extreme-pressure agent are used in combination.
[0170] The first and second oils for metal working according to the
invention preferably also contain (E) an organic acid salt, from
the viewpoint of preventing adhesion of the metal from the
workpieces and increase in working resistance to achieve superior
working efficiency and tool life. As organic acid salts there are
preferably used sulfonates, phenates and salicylates, as well as
mixtures thereof. As cationic Components of these organic acid
salts there may be mentioned alkali metals such as sodium and
potassium; alkaline earth metals such as magnesium, calcium and
barium; amines including ammonia, C1-3 alkyl group-containing
alkylamines (monomethylamine, dimethylamine, trimethylamine,
monoethylamine, diethylamine, triethylamine, monopropylamine,
dipropylamine, tripropylamine, etc.), C1-3 alkanol group-containing
alkanolamines (monomethanolamine, dimethanolamine,
trimethanolamine, monoethanolamine, diethanolamine,
triethanolamine, monopropanolamine, dipropanolamine,
tripropanolamine, etc.), and zinc, among which alkali metals and
alkaline earth metals are preferred, 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.
[0171] The sulfonate used may be one produced by any desired
process. For example, there may be used an alkali metal salt,
alkaline earth metal salt or amine salt of an alkylaromaticsulfonic
acid obtained by sulfonation of an alkylaromatic compound with a
molecular weight of 100-1500 and preferably 200-700, or a mixture
thereof. As the alkylaromaticsulfonic acid 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 and are obtained by alkylation of
benzene with polyolefins, or sulfonated alkylnaphthalenes such as
dinonylnaphthalene. There may also be mentioned neutral sulfonates
obtained by reacting an alkylaromaticsulfonic acid with an alkali
metal base (alkali metal oxide, hydroxide or the like), an alkaline
earth metal base (alkaline earth metal oxide, hydroxide or the
like) or one of the aforementioned amines (ammonia, alkylamine,
alkanolamine, etc.); basic sulfonates obtained by heating a neutral
sulfonate with an excess of an alkali metal salt, alkaline earth
metal salt or amine in the presence of water; "carbonated overbased
sulfonates" obtained by reacting a neutral sulfonate with an alkali
metal salt, alkaline earth metal salt or amine in the presence of
carbon dioxide gas; "borated overbased sulfonates" produced by
reacting a neutral sulfonate with an alkali metal salt, alkaline
earth metal salt or amine and a boric acid compound such as boric
acid or boric anhydride, or by reacting a carbonated overbased
sulfonate with a boric acid compound such as boric acid or boric
anhydride; and mixtures of these compounds.
[0172] As phenates there may be mentioned, specifically, neutral
phenates obtained by reacting an alkylphenol having one or two
C4-20 alkyl groups with an alkali metal base (alkali metal oxide,
hydroxide or the like), an alkaline earth metal base (alkaline
earth metal oxide, hydroxide or the like) or one of the
aforementioned amines (ammonia, alkylamine, alkanolamine, etc.) in
the presence or in the absence of elemental sulfur; basic phenates
obtained by heating a neutral phenate with an excess of an alkali
metal salt, alkaline earth metal salt or amine in the presence of
water; "carbonated overbased phenates" obtained by reacting a
neutral phenate with an alkali metal salt, alkaline earth metal
salt or amine in the presence of carbon dioxide gas; "borated
overbased phenates" produced by reacting a neutral phenate with an
alkali metal salt, alkaline earth metal salt or amine and a boric
acid compound such as boric acid or boric anhydride, or by reacting
a carbonated overbased phenate with a boric acid compound such as
boric acid or boric anhydride; and mixtures of these compounds.
[0173] As salicylates there may be mentioned, specifically, neutral
salicylates obtained by reacting an alkylsalicylic acid having one
or two C4-20 alkyl groups with an alkali metal base (alkali metal
oxide, hydroxide or the like), an alkaline earth metal base
(alkaline earth metal oxide, hydroxide or the like) or one of the
aforementioned amines (ammonia, alkylamine, alkanolamine, etc.) in
the presence or in the absence of elemental sulfur; basic
salicylates obtained by heating a neutral salicylate with an excess
of an alkali metal salt, alkaline earth metal salt or amine in the
presence of water; "carbonated overbased salicylates obtained by
reacting a neutral salicylate with an alkali metal salt, alkaline
earth metal salt or amine in the presence of carbon dioxide gas;
"borated overbased salicylates" produced by reacting a neutral
salicylate with an alkali metal salt, alkaline earth metal salt or
amine and a boric acid compound such as boric acid or boric
anhydride, or by reacting a carbonated overbased salicylate with a
boric acid compound such as boric acid or boric anhydride; and
mixtures of these compounds.
[0174] The total 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 the 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] determined by the perchlorate method, with measurement
according to JIS K 2501 "Petroleum Products and
Lubricants--Determination of Neutralization Number", Section 7.
[0175] 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 oil for
metal working. If the content of the (E) organic acid salt is below
this lower limit, the improving effect of the addition on the
working efficiency and tool life by preventing adhesion of the
metal from the workpieces and increase in working resistance will
tend to be unsatisfactory, while if it is above the aforementioned
upper limit the stability of the oil for metal working will be
reduced and deposits will tend to form.
[0176] According to the invention, the an (E) organic acid salt may
be used alone, or an organic acid salt may be used in combination
with other additives. From the standpoint of preventing adhesion of
the metal from the workpieces and increase in working resistance to
achieve superior working 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.
[0177] The first and second oils for metal working according to the
invention also preferably contain (F) an antioxidant. Addition of
(F) an antioxidant can prevent sticking caused by degradation of
the constituent components, while further enhancing the heat and
oxidation stability.
[0178] As (F) antioxidants to be used there may be mentioned
phenol-based antioxidants, amine-based antioxidants, zinc
dithiophosphate-based antioxidants, and antioxidants used as food
additives.
[0179] 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 (14) and (15). ##STR8## [wherein R.sup.32 represents C1-4
alkyl, R.sup.33 represents hydrogen or C1-4 alkyl, and R.sup.34
represents hydrogen, C1-4 alkyl or a group represented by the
following general formula (i) or (ii): ##STR9## (wherein R.sup.35
represents C1-6 alkylene and R.sup.36 represents C1-24 alkyl or
alkenyl), ##STR10## (wherein R.sup.37 represents C1-6 alkylene,
R.sup.38 represents C1-4 alkyl, R.sup.39 represents hydrogen or
C1-4 alkyl, and k represents 0 or 1).] ##STR11## [wherein R.sup.40
and R.sup.42 may be the same or different and each represents C1-4
alkyl, R.sup.41 and R.sup.43 may be the same or different and each
represents hydrogen or C1-4 alkyl, R.sup.44 and R.sup.45 may be the
same or different and each represents C1-6 alkylene, and A is C1-18
alkylene or a group represented by the following general formula
(iii): --R.sup.46--S--R.sup.47-- (iii) (wherein R.sup.46 and
R.sup.47 may be the same or different and each represents C1-6
alkylene).]
[0180] 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 (16), and p,p.alpha.-dialkyldiphenylamines
represented by the following general formula (17). ##STR12##
[wherein R.sup.48 represents hydrogen or alkyl] ##STR13## [wherein
R.sup.49 and R.sup.50 may be the same or different and each
represents alkyl.]
[0181] 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.
[0182] As zinc dithiophosphate-based antioxidants to be used for
the invention there may be mentioned, specifically, zinc
dithiophosphates represented by the following general formula (18).
##STR14## [wherein R.sup.51, R.sup.52, R.sup.53 and R.sup.54 may be
the same or different and each represents a hydrocarbon group.]
[0183] Antioxidants employed as food additives may also be used,
and although these partially overlap with the aforementioned
phenol-based antioxidants, there may be mentioned as examples
2,6-di-tert-butyl-p-cresol (DBPC),
4,4'-ethylenebis(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-distertobutyl-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 (TBP).
[0184] 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 especially preferred.
[0185] There are no particular restrictions on the content of the
(F) antioxidant, 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
oil for metal working. Since no corresponding effect can be
expected with larger amounts of addition, the content is preferably
not greater than 10% by mass, more preferably not greater than 5%
by mass and most preferably not greater than 3% by mass.
[0186] The first and second oils for metal working 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 acryl 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
deactivating agents such as benzotriazole and thiadiazole;
defoaming agents such as methylsilicone, fluorosilicone and
polyacrylate; and non-ash powders such as alkenylsuccinic imides,
benzylamines and Polyalkenylamineaminoamides. The contents of such
publicly known additives when used in combination are not
particularly restricted, but they are generally added in amounts so
that the total content of the publicly known additives is 0.1-10%
by mass based on the total weight of the oil for metal working.
[0187] The first and second oils for metal working 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 environmental burden. The
chlorine concentration is preferably not greater than 1000 ppm by
weight, more preferably not greater than 500 ppm by weight, even
more preferably not greater than 200 ppm by weight and most
preferably not greater than 100 ppm by weight, based on the total
weight of the oil for metal working.
[0188] No particular restrictions are placed on the kinematic
viscosity of the first and second oils for metal working of the
invention, but from the viewpoint of facilitating supply to working
sites, the kinematic viscosity at 40.degree. C. is preferably not
greater than 200 mm.sup.2/s, more preferably 100 mm.sup.2/s, even
more preferably 75 mm.sup.2/s and most preferably 50 mm.sup.2/s.
The lower limit is preferably 1 mm.sup.2/s, even more preferably 3
mm2/s and most preferably 5 mm.sup.2/s.
[0189] The first and second oils for metal working of the invention
having the composition described above exhibit excellent machining
performance including working efficiency and tool life and
excellent handleability, and may therefore be suitably used for a
wide range of purposes in the field of metal working. Here, metal
working refers to metal working in general, without being
restricted to cutting and grinding.
[0190] The first and second oils for metal working of the invention
may be applied for metal working with ordinary oil supply systems,
but they are preferably used as oils for metal working in minimum
quantity lubrication (MQL) system in order to exhibit a more
notable effect. As such types of metal working there may be
mentioned, specifically, cutting, grinding, rolling, forging,
pressing, punching and rolling. Among these, the first and second
oils for metal working are highly useful for use in cutting,
grinding and rolling.
[0191] There are no particular restrictions on the materials for
workpieces to which the first and second oils for metal working of
the invention may be applied, but the oils for metal working of the
invention are suitable as non-ferrous metal working oils, and
exhibit especially superior performance as aluminum or aluminum
alloy working oils.
[0192] The first and second oils for metal working of the invention
can be used as lubricating oils for sections other than working
sites of machine tools, such as a sliding surface oils, bearing
section oils, hydraulic equipment oils or the like, and are
therefore highly useful from the standpoint of allowing savings in
space and energy for machine tools.
[0193] A sliding surface oil according to the invention is a
lubricating oil used in guiding mechanisms for sliding movement
between two surfaces in contact, such as those of structural
members of machine tools used for cutting and grinding. For
example, in a machine tool which sets a workpiece on a table
capable of moving a bed and moves the table to transport the
workpiece toward a cutting/grinding tool, the sliding surface
between the table and the bed is lubricated with a sliding surface
oil. Or in a machine tool which fixes a cutting/grinding tool on a
platform capable of moving over a bed and moves the platform to
transport the tool toward a workpiece, the sliding surface between
the platform and bed is also lubricated with a sliding surface
oil.
[0194] Such sliding surface oils must have satisfactory friction
properties, including a small friction coefficient on the sliding
surface and high anti-stick-slip properties. When stick-slip occurs
on the sliding surface such as the working table of a machine tool,
the frictional vibration is transferred to the workpiece thereby
lowering the working precision, or in some cases the vibration may
shorten the tool life. When the first and second oils for metal
working of the invention are used as sliding surface oils these
phenomena can be satisfactorily prevented, but a phosphorus
compound is preferably further added from the standpoint of
friction properties.
[0195] Lubrication methods such as oil bearing lubrication and mist
bearing lubrication are employed for lubrication of bearing
sections, and a first or second oil composition for metal working
according to the invention can be used for either type of
method.
[0196] Oil bearing lubrication is a lubricating system whereby a
lubricating oil is supplied directly as a liquid to the bearing
section for smooth sliding of the section, and the bearing section
is also cooled by the lubricating oil. Because such a lubricating
oil for bearing lubrication is used at high-temperature sections it
must be resistant to thermal degradation, i.e. it must have
excellent heat resistance, and the first and second oils for metal
working can also be suitably used for such oil bearing
lubrication.
[0197] Mist bearing lubrication is a lubricating system wherein the
lubricating oil is atomized with a mist generator and the atomized
oil is supplied to the bearing sections with a gas such as air to
achieve smooth sliding of the sections, and since a cooling effect
is provided by the air at the high-temperature sections such as
bearing sections, this type of lubricating system is becoming more
commonly used in recent years for machine tools. Because such a
lubricating oil for mist lubrication is used at high-temperature
sections it must also be resistant to thermal degradation, i.e. it
must have excellent heat resistance, and the first and second oils
for metal working can also be suitably used for such mist bearing
lubrication.
[0198] Hydraulic equipment accomplishes operation and control of
machines by oil pressure, and hydraulic oil with a lubricating,
sealing and cooling effect is used in hydraulic control sections
that govern machine operation. Hydraulic oil is used by compressing
lubricating oil at high pressure with a pump to produce oil
pressure and move equipment, and therefore the lubricating oil must
have high lubricity and high oxidation stability and thermal
stability; the first and second oils for metal working can also be
used as hydraulic oils. When the first and second oils for metal
working are used as hydraulic oils, they preferably also contain
phosphorus compounds for further improved lubricity.
[0199] An example of a cutting and grinding method using first and
second oils for metal working according to the invention will now
be explained.
[0200] FIG. 1 is a schematic diagram showing an example of a
machine tool suitable for use in a cutting/grinding method with a
minimum quantity lubrication system. The machine tool shown in FIG.
1 comprises a table 2 which is movable in the direction of the
arrow on a bed 1, and a tool 11 which is supported on support means
10 and is rotatable in the direction of the arrow. An oil according
to the invention is housed in an oil feeding tank 12, and during
cutting/grinding of a workpiece 3 placed on the table 2, compressed
air fed from a compressed air injection port 18 is supplied,
together with the oil of the invention in mist form, from the
working oil feeding section 13 toward the working site. The oil of
the invention housed in the oil feeding tank 12 is supplied from
the sliding surface oil feeding section 14 to the sliding surface
16 between the bed 1 and the table 2, while also being supplied
from the bearing oil feeding section 15 to the bearing section
between the support means 10 and tool 11, for lubrication of the
sliding surface 16 and the bearing section 17.
[0201] Thus, by using oils containing the same ester for
lubrication of Cutting/grinding sites, machine tool sliding
surfaces and bearing sections in a cutting and grinding process
with a minimum quantity lubrication system according to the
invention, it is possible to achieve improved workability and
improved operating efficiency for cutting and grinding in the
minimum quantity lubrication system.
[0202] Moreover, for cutting and grinding in a minimum quantity
lubrication system according to the invention, as shown in FIG. 1,
it is preferred to use the same oil as the cutting/grinding oil,
the sliding surface oil and the bearing oil in order to eliminate
the need for separate oil supply tanks for supply of different
oils, thereby allowing savings in space and energy for machine
tools.
[0203] Also, while not shown in FIG. 1, the oil of the invention
housed in the oil feeding tank 12 may also be supplied to hydraulic
equipment in the machine tool for use of the oil of the invention
as a hydraulic oil.
EXAMPLES
[0204] The present invention will now be explained in further
detail by examples and comparative examples, with the understanding
that the invention is in no way limited by the examples.
Examples 1-21, Comparative Examples 1-2
[0205] For Examples 1-21 and Comparative Examples 1-2, oils for
metal working were prepared having the compositions listed in
Tables 1-6, using the base oils and additives listed below. Tables
1-6 also show the kinematic viscosity at 40.degree. C. and the
moisture content of each obtained oil for metal working. The fatty
acid composition and total degree of unsaturation of the base oils
A4 are listed in Table 7.
(Base Oils)
[0206] A1: Trimethylolpropane and oleic acid triester (kinematic
viscosity at 40.degree. C.: 46 mm.sup.2/s) [0207] A2: Neopentyl
glycol and oleic acid diester (kinematic viscosity at 40.degree.
C.: 24 mm.sup.2/s) [0208] A3: Isodecyl alcohol and adipic acid
diester (kinematic viscosity at 40.degree. C.: 14 mm.sup.2/s)
[0209] A4: High-oleic rapeseed oil (kinematic viscosity at
40.degree. C.: 39 mm.sup.2/s) [0210] B1: Hydrogenated 1-decene
dimer (kinematic viscosity at 40.degree. C.: 4.5 mm .sup.2/s)
[0211] B2: Hydrogenated 1-decene trimer (kinematic viscosity at
40.degree. C.: 19 mm.sup.2/s) [0212] B3: White oil (kinematic
viscosity at 40.degree. C.: 5 mm.sup.2/s) (Additives) [0213] C1:
Oleyl alcohol [0214] C2: Oleylamine [0215] C3: Oleic acid [0216]
C4: Glycerin monooleate [0217] D1: Tricresyl phosphate [0218] D2:
Sulfurized ester
[0219] The oils for metal working of Examples 1-21 and Comparative
Examples 1-2 were subjected to the following evaluation tests.
[0220] [Tapping Test]
[0221] A tapping test was conducted with a minimum quantity
lubrication System (MQL) or an ordinary oil supply system.
[0222] For testing with the MQL, each oil for metal working and
standard oil for comparison (DIDA: diisodecyl adipate) was used
alternately in a tapping test under the conditions listed below,
and the tapping energy for each was measured.
(Tapping Conditions)
[0223] Tool: Nut tap M8 (P=1.25 mm) [0224] Lower hole diameter:
.phi.7.2 mm [0225] Workpiece: AC8A (t=10 mm) [0226] Cutting speed:
9.0 m/min (Oil Supply System) [0227] Oil for metal working:
Spraying under conditions of 25 ml/h oil composition, with 0.2 MPa
compressed air [0228] DIDA: Direct spraying of the working site
under conditions of 4.3 ml/min without using compressed air.
[0229] For testing with the ordinary oil supply system, each oil
for metal working and standard oil for comparison (DIDA: diisodecyl
adipate) was used alternately in a tapping test under the
conditions listed below, and the tapping energy for each was
measured.
(Tapping Conditions)
[0230] Tool: Nut tap M8 (P=1.25 mm) [0231] Lower hole diameter:
.phi.7.2 mm [0232] Workpiece: AC8A (t=10 mm) [0233] Cutting speed:
9.0 m/min (Oil Supply System) [0234] Oil for metal working and
DIDA: Direct spraying of the working site under conditions of 4.3
ml/min without using compressed air.
[0235] Next, the measured values of the tapping energy for both the
MQL and ordinary oil supply systems were used to calculate the
tapping energy efficiency (%) by the formula shown below. The
results are shown in Tables 1-6. In the tables, a higher value for
the tapping energy efficiency indicates higher lubricity. Tapping
energy efficiency (%)=(tapping energy using DIDA)/(tapping energy
using oil composition)
[0236] [Wear Resistance Evaluation Test]
[0237] Each oil for metal working was subjected to wear testing by
a high-speed four-ball test for 30 minutes with a rotation rate of
1800 rpm and a load of 392 N. and the wear scar diameter was
measured for evaluation of the anti-wear property of each oil. The
results are shown in Tables 1-6.
[0238] [Oil Mist Property Evaluation Test]
[0239] Each oil for metal working was supplied to a minimum
quantity lubrication system and the oil mist property was
evaluated. Specifically, each oil for metal working was ejected
through an MQL supply Port under conditions of 0.2 MPa compressed
air, 25 ml/h oil composition to produce an oil mist, and the amount
of oil mist collected on a glass dish placed at a position
corresponding to the working point was measured. The results are
shown in Tables 1-6. TABLE-US-00001 TABLE 1 Example Example Example
Example 1 2 3 4 Composition A1 70 70 70 -- [% by mass] A2 -- -- --
70 A3 -- -- -- -- A4 -- -- -- -- B1 30 -- -- 30 B2 -- 30 -- -- B3
-- -- 30 -- C1 -- -- -- -- C2 -- -- -- -- C3 -- -- -- -- C4 -- --
-- -- D1 -- -- -- -- D2 -- -- -- -- Kinematic viscosity at
40.degree. C. [mm.sup.2/s] 20 36 20 14 Moisture content [ppm] 250
250 250 250 Working property MQL 110 105 107 118 (tapping energy
efficiency [%]) Normal oil feeding 123 121 120 120 Anti-wear
property 0.70 0.67 0.71 0.70 (Wear scar diameter [.mu.m]) Mist
property 18.0 15.5 16.5 22.5 (collected mist [mg/h])
[0240] TABLE-US-00002 TABLE 2 Example Example Example Example 5 6 7
8 Composition A1 -- -- -- -- [% by mass] A2 70 -- -- -- A3 -- 70 70
-- A4 -- -- -- 70 B1 -- 30 -- 30 B2 -- -- -- -- B3 30 -- 30 -- C1
-- -- -- -- C2 -- -- -- -- C3 -- -- -- -- C4 -- -- -- -- D1 -- --
-- -- D2 -- -- -- -- Kinematic viscosity at 40.degree. C.
[mm.sup.2/s] 14 10 10 28 Moisture content [ppm] 250 250 250 250
Working property MQL 115 115 114 115 (tapping energy efficiency
[%]) Normal oil feeding 119 118 118 121 Anti-wear property 0.71
0.72 0.70 0.69 (Wear scar diameter [.mu.m]) Mist property 19.2 18.0
16.3 17.5 (collected mist [mg/h])
[0241] TABLE-US-00003 TABLE 3 Example Example Example Example 9 10
11 12 Composition A1 -- 70 70 70 [% by mass] A2 -- -- -- -- A3 --
-- -- -- A4 70 -- -- -- B1 -- 30 30 30 B2 -- -- -- -- B3 30 -- --
-- C1 -- 5 -- -- C2 -- -- 5 -- C3 -- -- -- 5 C4 -- -- -- -- D1 --
-- -- -- D2 -- -- -- -- Kinematic viscosity at 40.degree. C.
[mm.sup.2/s] 28 20 20 20 Moisture content [ppm] 250 250 250 250
Working property MQL 117 120 118 122 (tapping energy efficiency
[%]) Normal oil feeding 120 128 126 129 Anti-wear property 0.71
0.65 0.67 0.62 (Wear scar diameter [.mu.m]) Mist property 15.3 17.5
17.8 18.5 (collected mist [mg/h])
[0242] TABLE-US-00004 TABLE 4 Example Example Example Example 13 14
15 16 Composition A1 70 70 70 70 [% by mass] A2 -- -- -- -- A3 --
-- -- -- A4 -- -- -- -- B1 30 30 30 30 B2 -- -- -- -- B3 -- -- --
-- C1 -- -- -- -- C2 -- -- -- -- C3 -- -- -- -- C4 5 -- -- -- D1 --
5 -- 5 D2 -- 10 10 Kinematic viscosity at 40.degree. C.
[mm.sup.2/s] 20 20 21 21 Moisture content [ppm] 250 250 250 250
Working property MQL 121 115 115 118 (tapping energy efficiency
[%]) Normal oil feeding 131 127 126 130 Anti-wear property 0.64
0.54 0.56 0.52 (Wear scar diameter [.mu.m]) Mist property 18.2 18.1
18.4 18.0 collected mist [mg/h])
[0243] TABLE-US-00005 TABLE 5 Example Example Example Example 17 18
19 20 Composition A1 70 70 70 70 [% by mass] A2 -- -- -- -- A3 --
-- -- -- A4 -- -- -- -- B1 30 30 30 30 B2 -- -- -- -- B3 -- -- --
-- C1 -- -- -- -- C2 -- -- -- -- C3 -- -- -- -- C4 5 5 5 -- D1 5 --
5 -- D2 -- 10 10 -- Kinematic viscosity at 40.degree. C.
[mm.sup.2/s] 21 22 23 20 Moisture content [ppm] 250 250 250 1000
Working property MQL 128 125 129 124 (tapping energy efficiency
[%]) Normal oil feeding 135 133 138 130 Anti-wear property 0.52
0.52 0.50 0.68 (Wear scar diameter [.mu.m]) Mist property 18.5 18.1
17.8 17.2 (collected mist [mg/h])
[0244] TABLE-US-00006 TABLE 6 Example 21 Comp. Ex. 1 Comp. Ex. 2
Composition A1 100 -- -- [% by mass] A2 -- -- -- A3 -- -- -- A4 --
-- -- B1 -- 100 -- B2 -- -- 100 B3 -- -- -- C1 -- -- -- C2 -- -- --
C3 -- -- -- C4 -- -- -- D1 -- -- -- D2 -- -- -- Kinematic viscosity
at 40.degree. C. [mm.sup.2/s] 46 4.5 19 Moisture content [ppm] 250
25 25 Working property MQL 85 75 80 (tapping energy efficiency [%])
Normal oil feeding 109 95 92 Anti-wear property 0.71 0.89 0.85
(Wear scar diameter [.mu.m]) Mist property 9.2 9.5 10 (collected
mist [mg/h])
[0245] TABLE-US-00007 TABLE 7 Base oil A4 (High-oleic rapeseed oil)
Fatty acid composition Oleic acid 64 [% by mass] Linoleic acid 20
Palmitic acid 5 Stearic acid 2 Other fatty acids 9 C6-16 fatty acid
content [% by mass] 9 Total degree of unsaturation 0.26
Examples 22-36, Comparative Examples 3-8
[0246] For Examples 22-36 and Comparative Examples 3-8, oils for
metal working were prepared using the base oils and additives
listed below, with adjustment of the moisture content, to yield the
compositions and moisture contents listed in Tables 8-13. Tables
8-13 show the compositions of the oils for metal working with 100%
by mass as the total of the base oil and additive contents and
moisture contents. Tables 8-13 also show the kinematic viscosity at
40.degree. C. for each obtained oil for metal working. The base oil
A4 fatty acid compositions and total degrees of unsaturation are as
shown in Table 7 above.
(Ester Oils)
[0247] A5: Mixed ester of trimethylolpropane and oleic acid
triester and neopentylglycol and oleic acid diester (kinematic
viscosity at 40.degree. C.: 32 mm.sup.2/s) [0248] A3: Isodecyl
alcohol and adipic acid diester (kinematic viscosity at 40.degree.
C.: 14 mm.sup.2/s) [0249] A4: High-oleic rapeseed oil (kinematic
viscosity at 40.degree. C.: 39 mm.sup.2/s) (Additives) [0250] C1:
Oleyl alcohol [0251] C2: Oleylamine [0252] C3: Oleic acid [0253]
C4: Glycerin monooleate [0254] D1: Tricresyl phosphate [0255] D2:
Sulfurized ester
[0256] The oils for metal working of Examples 22-36 and Comparative
Examples 3-8 were subjected to the following evaluation tests.
[0257] [Tapping Test]
[0258] A tapping test was conducted with a minimum quantity
lubrication System (MQL) or an ordinary oil supply system.
[0259] For testing with the MQL, each oil for metal working and
Standard oil for comparison (DIDA: diisodecyl adipate, moisture
content: 50 ppm) was used alternately in a tapping test under the
conditions listed below, and the tapping energy for each was
measured.
[0260] (Tapping Conditions) [0261] Tool: Nut tap M8 (P=1.25 mm)
[0262] Lower hole diameter: .phi.7.2 mm [0263] Workpiece: AC8A
(t=10 mm) [0264] Cutting speed: 9.0 m/min (Oil Supply System)
[0265] Oil for metal working: Spraying under conditions of 25 ml/h
oil Composition, with 0.2 MPa compressed air. [0266] DIDA: Direct
spraying of the working site under conditions of 4.3 ml/min without
using compressed air.
[0267] For testing with the ordinary oil supply system, each oil
for metal working and standard oil for comparison (DIDA: diisodecyl
adipate, moisture content: 50 ppm) was used alternately in a
tapping test under the conditions listed below, and the tapping
energy for each was measured.
(Tapping Conditions)
[0268] Tool: Nut tap M8 (P=1.25 mm) [0269] Lower hole diameter:
.phi.7.2 mm [0270] Workpiece: AC8A (t=10 mm) [0271] Cutting speed:
9.0 m/min (Oil Supply System) [0272] Oil for metal working and
DIDA: Direct spraying of the working site under conditions of 4.3
ml/min without using compressed air.
[0273] Next, the measured values of the tapping energy for both the
MQL and ordinary oil supply systems were used to calculate the
tapping energy efficiency (%) by the formula shown below. The
results are shown in Tables 8-13. In the tables, a higher value for
the tapping energy efficiency indicates higher lubricity. Tapping
energy efficiency (%)=(tapping energy using DIDA)/(tapping energy
using oil composition)
[0274] [Anti-Wear Property Evaluation Test]
[0275] Each oil for metal working was subjected to wear testing by
a high-speed four-ball test for 30 minutes with a rotation rate of
1800 rpm and a load of 392 N, and the wear scar diameter was
measured for evaluation of the anti-wear property of each oil. The
results are shown in Tables 8-13.
[0276] [Storage Stability Test]
[0277] Each oil for metal working was allowed to stand at room
temperature for 2 weeks, and the presence or absence of water
separation was visually observed. The results are shown in Tables
8-13. TABLE-US-00008 TABLE 8 Example Example Example Example 22 23
24 25 Composition A5 99.965 99.900 99.700 -- [% by mass] A3 -- --
-- 99.700 A4 -- -- -- -- C1 -- -- -- -- C2 -- -- -- -- C3 -- -- --
-- C4 -- -- -- -- D1 -- -- -- -- D2 -- -- -- -- Moisture content
[ppm] 350 1000 3000 3000 Kinematic viscosity at 40.degree. C.
[mm.sup.2/s] 32 32 32 14 Working property MQL 93 95 97 100 (tapping
energy efficiency [%]) Normal oil feeding 115 121 124 122 Anti-wear
property 0.70 0.70 0.69 0.70 (Wear scar diameter [.mu.m]) Storage
stability - - - - (presence of water separation)
[0278] TABLE-US-00009 TABLE 9 Example Example Example Example 26 27
28 29 Composition A5 -- 94.700 94.700 94.700 [% by mass] A3 -- --
-- -- A4 99.700 -- -- -- C1 -- 5.000 -- -- C2 -- -- 5.000 -- C3 --
-- -- 5.000 C4 -- -- -- -- D1 -- -- -- -- D2 -- -- -- -- Moisture
content [ppm] 3000 3000 3000 3000 Kinematic viscosity at 40.degree.
C. [mm.sup.2/s] 39 32 32 32 Working property MQL 96 109 108 109
(tapping energy efficiency [%]) Normal oil feeding 124 129 129 130
Anti-wear property 0.72 0.67 0.68 0.67 (Wear scar diameter [.mu.m])
Storage stability - - - - (presence of water separation)
[0279] TABLE-US-00010 TABLE 10 Example Example Example Example 30
31 32 33 Composition A5 94.700 94.700 89.700 84.700 [% by mass] A3
-- -- -- -- A4 -- -- -- -- C1 -- -- -- -- C2 -- -- -- -- C3 -- --
-- -- C4 5.000 -- -- -- D1 -- 5.000 -- 5.000 D2 -- -- 10.000 10.000
Moisture content [ppm] 3000 3000 3000 3000 Kinematic viscosity at
40.degree. C. [mm.sup.2/s] 32 32 33 34 Working property MQL 112 110
108 113 (tapping energy efficiency [%]) Normal oil feeding 131 127
127 129 Anti-wear property 0.68 0.54 0.56 0.52 (Wear scar diameter
[.mu.m]) Storage stability - - - - (presence of water
separation)
[0280] TABLE-US-00011 TABLE 11 Example 34 Example 35 Example 36
Composition A5 89.700 84.700 81.700 [% by mass] A3 -- -- -- A4 --
-- -- C1 -- -- -- C2 -- -- -- C3 -- -- -- C4 5.000 5.000 5.000 D1
5.000 -- 3.000 D2 -- 10 10 Moisture content [ppm] 3000 3000 3000
Kinematic viscosity at 40.degree. C. [mm.sup.2/s] 33 34 35 Working
property MQL 116 113 119 (tapping energy efficiency [%]) Normal oil
feeding 135 133 138 Anti-wear property 0.52 0.54 0.51 (Wear scar
diameter [.mu.m]) Storage stability - - - (presence of water
separation)
[0281] TABLE-US-00012 TABLE 12 Comp. Ex. 3 Comp. Ex. 4 Comp. Ex. 5
Composition A5 99.995 -- -- [% by mass] A3 -- 99.995 -- A4 -- --
99.995 C1 -- -- -- C2 -- -- -- C3 -- -- -- C4 -- -- -- D1 -- -- --
D2 -- -- -- Moisture content [ppm] 50 50 50 Kinematic viscosity at
40.degree. C. [mm.sup.2/s] 32 14 39 Working property MQL 80 82 78
(tapping energy efficiency [%]) Normal oil feeding 100 100 103
Anti-wear property 0.71 0.73 0.73 (Wear scar diameter [.mu.m])
Storage stability - - - (presence of water separation)
[0282] TABLE-US-00013 TABLE 13 Comp. Ex. 6 Comp. Ex. 7 Comp. Ex. 8
Composition A5 97.000 -- -- [% by mass] A3 -- 97.000 -- A4 -- --
97.000 C1 -- -- -- C2 -- -- -- C3 -- -- -- C4 -- -- -- D1 -- -- --
D2 -- -- -- Moisture content [ppm] 30,000 30,000 30,000 Kinematic
viscosity at 40.degree. C. [mm.sup.2/s] 32 14 39 Working property
MQL 98 99 98 (tapping energy efficiency [%]) Normal oil feeding 129
125 127 Anti-wear property 0.71 0.70 0.71 (Wear scar diameter
[.mu.m]) Storage stability + + + (presence of water separation)
* * * * *