DESCRIPTION
Title of Invention
LUBRICATING AGENT COMPOSITION FOR PLASTIC
PROCESSING
5 Technical Field
[0001] The present invention relates to a lubricating agent composition
for plastic processing.
Background Art
[0002] The known lubricating agents for plastic processing of metals
10 include compositions comprising sulfur compounds, chlorine
compounds, phosphoric acid esters or the like added to lubricant base
oils. Each of these components are combined as appropriate for the
required performance.
[0003] Of the components mentioned, chlorine compounds have been
15 used because they are effective when difficulty is encountered in
working stainless steel plates. However, consideration of the natural
environment in recent years has spurred development of lubricating
agents for plastic processing that do not employ chlorine-based
compounds (non-chlorine-based lubricating agents for plastic
20 processing). Examples of proposed lubricating agents for plastic
processing that contain no chlorine compoimds include the
aforementioned sulfur compounds and phosphoric acid esters, as well as
zinc dithiophosphate-containing compounds (see PTLs 1 to 3, for
example).
25 Citation List
Patent Literature
1
FPl 1-0531-00
B
[0004] [PTL 1] Japanese Unexamined Patent Application Publication
HEI No. 9-328696
[PTL 2] Japanese Unexamined Patent Application Publication No.
2000-73083
5 [PTL 3] Japanese Unexamined Patent Application Publication No.
2002-285181
Summary of Invention
Technical Problem
[0005] However, with ever increasing performance being demanded of
10 lubricating agents for plastic processing in recent years, sufficient
performance is not always achieved even with the lubricating agents for
plastic processing described in PTLs 1 to 3. It is especially difficult to
obtain sufficient workability under some difficult working conditions,
such as those that tend to result in seizing.
15 [0006] The present invention has been accomplished in light of the
circumstances described above, and its object is to provide a lubricating
agent composition for plastic processing that can give the same
workability as conventional chlorine-based plastic processing oils.
Solution to Problem
20 [0007] In order to solve the problems described above, the invention
provides a lubricating agent composition for plastic processing
comprising 0.1 to 40% by mass of zinc dithiophosphate represented by
the following general formula (1), 30 to 70%) by mass of a sulfiir-based
extreme pressure agent and 10 to 60% by mass of an organic acid salt,
25 based on the total mass of the composition.
[Chemical Formula 1]
^R.
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Zn-
S
II ,
•S P—0R2 (1)
1 "J
[In formula (1), R and R may be the same or different, and each
represents a Cl-18 straight-chain or branched-chain alkyl group.]
Advantageous Effects of Invention
5 [0008] The lubricating agent composition for plastic processing of the
invention is an environmentally friendly lubricating agent composition
containing no chlorine compounds, which exhibits the notable effect of
providing satisfactory lubricity, when a steel sheet, stainless steel plate,
surface-treated steel sheet, aluminum alloy sheet or the like is subjected
10 to plastic processing such as press molding, bend molding, pultrusion
molding or ironing molding.
Brief Description of Drawings
[0009] Fig. 1 is a schematic cross-sectional view showing the
construction of a burring tester used in the examples.
15 Description of Embodiments
[0010] Preferred embodiments of the invention will now be explained.
[0011] The lubricating agent composition for plastic processing
according to an embodiment comprises 0.1 to 40% by mass of zinc
dithiophosphate represented by the following general formula (1), 30 to
20 70% by mass of a sulfur-based extreme pressure agent and 10 to 60%
by mass of an organic acid salt, based on the total mass of the
composition.
[Chemical Formula 2]
%
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Zn- •S P—0R2
I ,
(1)
1 0
[0012] In general formula (1), R and R may be the same or different,
and each represents a CI-18 straight-chain or branched-chain alkyl
group. The number of carbon atoms of R and R is preferably 2-12,
5 more preferably 3-10 and most preferably 4-8, from the viewpoint of
improving workability. The alkyl groups represented by R and R
may be straight-chain or branched, but are preferably branched.
[0013] The content of zinc dithiophosphate represented by general
formula (1) is no less than 0.1% by mass and no more than 40% by
10 mass, based on the total mass of the composition. From the viewpoint
of workability and corresponding cost effectiveness, the content is
preferably 0.3 to 30% by mass, more preferably 0.7 to 25% by mass and
even more preferably 1 to 20% by mass.
[0014] In the lubricating agent composition for plastic processing
15 according to this embodiment, the zinc content from the zinc
dithiophosphate is preferably 0.01 to 4% by mass, more preferably 0.03
to 3% by mass and even more preferably 0.05 to 2% by mass, based on
the total mass of the composition.
[0015] Preferred for use as sulfiir-based extreme pressure agents are
20 dihydrocarbyl polysulfide, sulfiirized esters (including sulfurized fats
and oils), and sulfide mineral oils.
[0016] Dihydrocarbyl polysulfide is a sulfiir-based compound
commonly known as polysulfide or olefin sulfide, and specifically it is a
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•K
compound represented by the following general formula (2).
R^-Sa-R^ (2)
[In formula (2), R^ and R'* may be the same or different, and each
represents a C3-20 straight-chain or branched alkyl, C6-20 aryl, C7-20
5 alkylaryl or C7-20 arylalkyl group, and a is an integer of 2 to 6 and
preferably an integer of 2 to 5.]
[0017] R^ and R"^ in general formula (2) are more preferably each
separately a C3-18 branched alkyl group derived from ethylene or
propylene, and are most preferably C6-15 branched alkyl groups
10 derived from ethylene or propylene.
[0018] Sulfurized esters include, specifically, sulfrirized fats and oils,
which are animal or vegetable fats and oils such as beef tallow, lard,
fish oil, rapeseed oil or soybean oil, that have been sulfidized by any
desired method, and unsaturated fatty acid esters obtainable by the
15 reaction of unsaturated fatty acids (including oleic acid, linolic acid, and
fatty acids extracted from the aforementioned animal or vegetable fats
and oils) with various alcohols, that have been sulfidized by any desired
method, as well as mixtures of animal or vegetable fats and oils and
unsaturated fatty acid esters, that have been sulfidized by any desired
20 method.
[0019] Sulfidized mineral oils are obtainable by dissolving elemental
sulfiir in mineral oils. There are no particular restrictions on the
mineral oil used in the sulfidized mineral oil for the invention, and
specifically, it may be a paraffinic mineral oil, naphthene-based mineral
25 oil or the like that has been purified by subjecting a lube-oil distillate
obtainable by the atmospheric distillation or vacuum distillation of
FPll-0531-00
crude oil, to an appropriate combination of refining treatments such as
solvent deasphalting, solvent extraction, hydrotreatment, solvent
dewaxing, catalytic dewaxing, hydrorefming, sulfuric acid cleaning and
white clay treatment.
5 [0020] Among sulfur-based extreme pressure agents, dihydrocarbyl
polysulfide and sulfurized esters are preferred from the viewpoint of
improving workability.
[0021] The content of the sulfur-based extreme pressure agent is 30 to
70% by mass based on the total mass of the composition, and from the
10 viewpoint of workability and cost effectiveness for the content, it is
preferably 33 to 67% by mass, more preferably 36 to 64% by mass and
even more preferably 40 to 60% by mass.
[0022] In the lubricating agent composition for plastic processing
according to this embodiment, the sulfur content from the sulfur-based
15 extreme pressure agent is preferably 5 to 25% by mass, more preferably
7 to 23% by mass, even more preferably 8 to 22% by mass and most
preferably 10 to 21% by mass.
[0023] An organic acid salt used is preferably a sulfonate, phenate,
salicylate, or a mixture thereof As cationic components of these
20 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 anmionia, CI-3 alkyl group-containing
alkylamines (monomethylamine, dimethylamine, trimethylamine,
monoethylamine, diethylamine, triethylamine, monopropylamine,
25 dipropylamine, tripropylamine, etc.), CI-3 alkanol group-containing
alkanolamines (monomethanolamine, dimethanolamine,
FPll-0531-00
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
5 earth metal as the cationic component of the organic acid salt will tend
to result in even higher workability.
[0024] The total base value of the organic acid salt is preferably 50-500
mgKOH/g, more preferably 100-470 mgKOH/g and even more
preferably 150-420 mgKOH/g. If the total base value of the organic
10 acid salt is less than 100 mgKOH/g the workability will tend to be
unsatisfactory, while organic acid salts with a total base value of greater
than 500 mgKOH/g are also not preferred because they are generally
very difficult to produce and obtain. The total base value [mgKOH/g]
referred to here is the total base value determined by the perchloric acid
15 method, as measured according to JIS K2501: "Petroleum Product And
Lubricating Oils - Neutralization Value Test Method", Section 7.
[0025] A sulfonate used may be one produced by any desired process.
For example, there may be used alkali metal salts, alkaline earth metal
salts or amine salts of alkylaromatic sulfonic acids obtainable by the
20 sulfonation of alkyl aromatic compounds with molecular weights of 100
to 1500 and preferably 200 to 700, or mixtures of the aforementioned
salts. The alkylaromatic sulfonic acids referred to here may be
synthetic sulfonic acids, including sulfonated alkyl aromatic compounds
from mineral oil lube-oil distillates and petroleum sulfonic acids such as
25 "mahogany acids" as by-products from white oil production, or
sulfonated alkylbenzenes having straight-chain or branched-chain alkyl
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groups, obtainable by the alkylation of benzene with polyolefins, or as
by-products in production plants for alkylbenzenes used as starting
materials for detergents, or sulfonated alkylnaphthalenes such as
dinonylnaphthalene. Also included are neutral (normal salt) sulfonates
5 obtainable by the reacting the aforementioned alkylaromatic sulfonic
acids with alkali metal bases (alkali metal oxides or hydroxides),
alkaline earth metal bases (alkaline earth metal oxides or hydroxides) or
the aforementioned amines (ammonia, alkylamines or alkanolamines);
basic sulfonates obtainable by the heating neutral (normal salt)
10 sulfonates with an excess of an alkali metal base, alkaline earth metal
base or amine in the presence of water; carbonate overbased (ultrabasic)
sulfonates obtainable by the reacting neutral (normal salt) sulfonates
with alkali metal bases, alkaline earth metal bases or amines in the
presence of carbon dioxide gas; and borate overbased (ultrabasic)
15 sulfonates produced by reacting neutral (normal salt) sulfonates with
alkali metal bases, alkaline earth metal bases or amines and boric acid
compounds such as boric acid or boric anhydride, or by reacting
carbonate overbased (ultrabasic) sulfonates with boric acid compounds
such as boric acid or boric anhydride; as well as mixtures of the
20 foregoing.
[0026] Phenates include, specifically, neutral phenates obtainable by the
reacting alkylphenols having one or two C4-20 alkyl groups with alkali
metal bases (alkali metal oxides or hydroxides), alkaline earth metal
bases (alkaline earth metal oxides or hydroxides) or the aforementioned
25 amines (ammonia, alkylamines or alkanolamines), in the presence or in
the absence of elemental sulfur; basic phenates, obtainable by the
8
FPl 1-0531-00
heating neutral phenates with an excess of an alkali metal base, alkaline
earth metal base or amine in the presence of water; carbonate overbased
(ultrabasic) phenates obtainable by the reacting neutral phenates with
alkali metal bases, alkaline earth metal bases or amines in the presence
5 of carbon dioxide gas; and borate overbased (ultrabasic) phenates
produced by reacting neutral phenates with alkali metal bases, alkaline
earth metal bases or amines and boric acid compounds such as boric
acid or boric anhydride, or by reacting carbonate overbased (ultrabasic)
phenates with boric acid compounds such as boric acid or boric
10 anhydride; as well as mixtures of the foregoing,
[0027] Salicylates include, specifically, neutral salicylates obtainable by
the reaction of alkylsalicylic acids having one or two C4-20 alkyl
groups with alkali metal bases (alkali metal oxides or hydroxides),
alkaline earth metal bases (alkaline earth metal oxides or hydroxides) or
15 the aforementioned amines (ammonia, alkylamines or alkanolamines),
in the presence or in the absence of elemental sulfur; basic salicylates,
obtainable by the heating neutral salicylates with an excess of an alkali
metal base, alkaline earth metal base or amine in the presence of water;
carbonate overbased salicylates obtainable by the reaction of neutral
20 salicylates with alkali metal bases, alkaline earth metal bases or amines
in the presence of carbon dioxide gas; and borate overbased (ultrabasic)
salicylates produced by reacting neutral salicylates with alkali metal
bases, alkaline earth metal bases or amines and boric acid compounds
such as boric acid or boric anhydride, or by reacting carbonate
25 overbased (ultrabasic) metal salicylates with boric acid compounds such
as boric acid or boric anhydride; as well as mixtures of the foregoing.
FPl 1-0531-00
[0028] As organic acid salts there are preferred calcium sulfonate,
amine sulfonate, sodium sulfonate, calcium phenate and calcium
salicylate, with calcium sulfonate, calcium phenate and calcium
salicylate being particularly preferred.
5 [0029] The content of the organic acid salt is preferably 10 to 60% by
mass, more preferably 20 to 57% by mass, even more preferably 25 to
53% by mass and yet more preferably 30 to 50% by mass based on the
total mass of the composition, from the viewpoint of workability and
cost effectiveness for the content.
10 [0030] In the lubricating agent composition for plastic processing
according to this embodiment, the content of the cationic component of
the organic acid salt is preferably 1 to 15% by mass, more preferably 2
to 12% by mass, even more preferably 3 to 11% by mass and most
preferably 4 to 8% by mass.
15 [0031] The lubricating agent composition for plastic processing
according to this embodiment may by one comprising a zinc
dithiophosphate represented by general formula (1) above, a sulfurbased
extreme pressure agent and an organic acid salt, and it may
further contain a lubricant base oil. Preferred lubricant base oils are
20 mineral oils and synthetic hydrocarbon oils.
[0032] The mineral oil may be, for example, a paraffinic mineral oil or
naphthenic mineral oil obtainable by the applying an appropriate
combination of refining treatments such as solvent deasphalting, solvent
extraction, hydrotreatment, solvent dewaxing, catalytic dewaxing,
25 catalytic dewaxing, hydrorefining, sulfiiric acid cleaning or white clay
treatment, on a lube-oil distillate obtainable by the atmospheric
10
FPl 1-0531-00
distillation and vacuum distillation of crude oil.
[0033] From the viewpoint of improving workability, the %Cp of the
mineral oil is preferably no less than 40 and no more than 80, more
preferably no less than 45 and no more than 75 and most preferably no
5 less than 50 and no more than 70. Here "%Cp" refers to the %Cp
value measured according to "Standard Test Method for Calculation
Distribution and Structural Group Analysis of Petroleum Oils by the nd-
M Method" based specified by ASTM D-3238.
[0034] A synthetic oil may be, specifically, a poly-a-olefin such as a
10 propylene oligomer, polybutene, polyisobutylene, a 1-octene oligomer, a
1-decene oligomer, a co-oligomer of ethylene and propylene, a cooligomer
of ethylene and 1-octene or a co-oligomer of ethylene and 1-
decene, or a hydrogenated form thereof; an isoparafRn; an alkylbenzene
such as a monoalkylbenzene, dialkylbenzene or polyalkylbenzene; or an
15 alkylnaphthalene such as a monoalkylnaphthalene, dialkylnaphthalene
or polyalkylnaphthalene, any of which may be used alone or in
combinations of two or more.
[0035] The lubricating agent composition for plastic processing of this
embodiment may further comprise one or more phosphorus-based
20 extreme pressure agents, oil agents or antioxidants.
[0036]
Phosphorus-based extreme pressure agent
The lubricating agent composition for plastic processing of this
embodiment may further contain a phosphorus-based extreme pressure
25 agent because an improving effect will be obtained for high machining
efficiency and tool life. Specific phosphorus-based extreme pressure
11
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^^B
agents include phosphoric acid esters, acidic phosphoric acid esters,
acidic phosphoric acid ester amine salts, chlorinated phosphoric acid
esters, phosphorous acid esters and phosphorothionates. These
phosphorus compounds are esters of phosphoric acid, phosphorous acid
5 or thiophosphoric acid with alkanols or polyether alcohols, or
derivatives thereof.
[0037] Of these phosphorus-based extreme pressure agents, phosphoric
acid esters, acidic phosphoric acid esters and acidic phosphoric acid
ester amine salts are preferred because a higher improving effect can be
10 obtained for machining efficiency and tool life.
[0038] The phosphorus-based extreme pressure agent may be used at
any content, but from the viewpoint of improving machining efficiency
and tool life, it is preferably 1% by mass or greater, more preferably 2%
by mass or greater and even more preferably 3% by mass or greater
15 based on the total mass of the composition. From the viewpoint of
improving tool life, it is preferably no greater than 20% by mass, more
preferably no greater than 15% by mass and even more preferably no
greater than 10% by mass based on the total mass of the composition.
[0039]
20 Oil agent
The lubricating agent composition for plastic processing of this
embodiment preferably further contains an oil agent from the viewpoint
of further increasing the machining efficiency and tool life. The oil
agent may be an alcohol, a carboxylic acid, an unsaturated carboxylic
25 acid sulfide, a compound represented by the following general formula
(3), a compound represented by the following general formula (4), a
12
FPl 1-0531-00
^
polyoxyalkylene compound, an ester, a polyhydric alcohol hydrocarbyl
ether or an amine.
[Chemical Formula 3]
(HO)b-p- -p-(R=)c (3)
[In formula (3), R^ represents a Cl-30 hydrocarbon group, c represents
an integer of 1 to 6, and b represents an integer of 0 to 5.]
[Chemical Formula 4]
(HO)d-Tr -T—(R')e <^)
[In formula (4), R^ represents a Cl-30 hydrocarbon group, d represents
10 an integer of 1 to 6, and e represents an integer of 0 to 5.]
[0040] Among alcohols, a monohydric alcohol may be a C3-18 straightchain
alcohol, a C3-18 branched alcohol or a C5-10 cycloalkyl alcohol
or alkylcycloalkyl alcohol. Specifically, these include straight-chain or
branched propanols (including n-propanol and 1-methylethanol),
15 straight-chain or branched butanols (including n-butanol, 1-
methylpropanol and 2-methylpropanol), straight-chain or branched
pentanols (including n-pentanol, 1-methylbutanol, 2-methylbutanol and
3-methylbutanol), straight-chain or branched hexanols (including nhexanol,
1-methylpentanol, 2-methylpentanol and 3-methylpentanol),
20 straight-chain or branched heptanols (including n-heptanol, 1-
methylhexanol, 2-methylhexanol, 3-methylhexanol, 4-methylhexanol,
5-methylhexanol and 2,4-dimethylpentanol), straight-chain or branched
13
FPl 1-0531-00
octanols (including n-octanol, 2-ethylhexanol, 1-methylheptanol and 2-
methylheptanol), straight-chain or branched nonanols (including nnonanol,
1-methyloctanol, 3,5,5-trimethylhexanol and l-(2'-
methylpropyl)-3-methylbutanol), straight-chain or branched decanols
5 (including n-decanol and iso-decanol), straight-chain or branched
undecanols (including n-undecanol), straight-chain or branched
dodecanols (including n-dodecanol and iso-dodecanol), straight-chain or
branched tridecanols, straight-chain or branched tetradecanols
(including n-tetradecanol and iso-tetradecanol), straight-chain or
10 branched pentadecanols, straight-chain or branched hexadecanols
(including n-hexadecanol and iso-hexadecanol), straight-chain or
branched heptadecanols, straight-chain or branched octadecanols
(including n-octadecanol and iso-octadecanol), cyclopentanol,
cyclohexanol, methylcyclohexanol, dimethylcyclohexanol,
15 cycloheptanol, and the like.
[0041] Of alcohols for this embodiment, preferred polyhydric alcohols
are polyhydric alcohols with 2 to 8 hydroxyl groups.
[0042] Specific examples of dihydric alcohols (diols) include ethylene
glycol, 1,2-propane diol (propylene glycol), 1,3-propane diol, 1,4-
20 butane diol, 1,2-butane diol, 2-methyl-1,2-propane diol, 2-methy 1-1,3-
propane diol, 1,3-butane diol, 1,4-butane diol, 1,2-pentane diol, 1,3-
pentane diol, 1,4-pentane diol, 1,5-pentane diol, neopentyl glycol, 1,6-
hexane diol, 2-ethyl-2-methyl-1,3-propane diol, 1,7-heptane diol, 2-
methyl-2-propyl-1,3-propane diol, 2,2-diethyl-l,3-propane diol, 1,8-
25 octane diol, 1,9-nonane diol, 1,10-decane diol, 1,11-undecane diol and
1,12-dodecane diol. Specific examples of trihydric and greater
14
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^
alcohols include polyhydric alcohols such as trimethylolethane,
trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-
(trimethylolpropane), pentaerythritol, di-(pentaerythritol), tri-
(pentaerythritol), glycerin, polyglycerin, 1,3,5-pentane triol, sorbitol,
5 sorbitan, sorbitolglycerin condensation product, adonitol, arabitol,
xylitol and mannitol, saccharides such as xylose, arabinose, ribose,
rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose,
maltose, isomaltose, trehalose, sucrose, raffinose, gentianose and
melezitose, as well as partial etherified forms and methyl glucosides
10 (glucosides) of the same. Preferred among these are hindered alcohols
such as neopentyl glycol, trimethylolethane, trimethylolpropane,
trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane),
pentaerythritol, di-(pentaerythritol) and tri-(pentaerythritol).
[0043] Among alcohols, it is preferred to use saturated monohydric
15 alcohols with branched-chains, from the viewpoint of workability.
When a polyhydric alcohol is used, it may be a partial ester in which
some of the hydroxyl groups have been esterified.
[0044] The carboxylic acid may be a monobasic acid or a polybasic
acid. From the viewpoint of obtaining higher machining efficiency
20 and tool life, CI-40 monovalent carboxylic acids are preferred, C5-25
carboxylic acids are more preferred, and C5-20 carboxylic acids are
most preferred. These carboxylic acids may be straight-chain or
branched and either saturated or unsaturated, but from the viewpoint of
preventing stickiness, they are preferably saturated carboxylic acids.
25 [0045] Specifically, a C2-24 fatty acid will usually be used as a
monobasic acid, and such fatty acids may be straight-chain or branched
15
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f^
and either saturated or unsaturated. Specific examples include
saturated fatty acids such as acetic acid, propionic acid, straight-chain or
branched butanoic acids, straight-chain or branched pentanoic acids,
straight-chain or branched hexanoic acids, straight-chain or branched
5 heptanoic acids, straight-chain or branched octanoic acids, straightchain
or branched nonanoic acids, straight-chain or branched decanoic
acids, straight-chain or branched undecanoic acids, straight-chain or
branched dodecanoic acids, straight-chain or branched tridecanoic acids,
straight-chain or branched tetradecanoic acids, straight-chain or
10 branched pentadecanoic acids, straight-chain or branched hexadecanoic
acids, straight-chain or branched heptadecanoic acids, straight-chain or
branched octadecanoic acids, straight-chain or branched
hydroxyoctadecanoic acids, straight-chain or branched nonadecanoic
acids, straight-chain or branched eicosanoic acids, straight-chain or
15 branched heneicosanoic acids, straight-chain or branched docosanoic
acids, straight-chain or branched tricosanoic acids and straight-chain or
branched tetracosanoic acids, and unsaturated fatty acids such as acrylic
acid, straight-chain or branched butenoic acids, straight-chain or
branched pentenoic acids, straight-chain or branched hexenoic acids,
20 straight-chain or branched heptenoic acids, straight-chain or branched
octenoic acids, straight-chain or branched nonenoic acids, straight-chain
or branched decenoic acids, straight-chain or branched undecenoic acids,
straight-chain or branched decenoic acids, straight-chain or branched
tridecenoic acids, straight-chain or branched tetradecenoic acids,
25 straight-chain or branched pentadecenoic acids, straight-chain or
branched hexadecenoic acids, straight-chain or branched heptadecenoic
16
FPl 1-0531-00
acids, straight-chain or branched octadecenoic acids, straight-chain or
branched hydroxyoctadecenoic acids, straight-chain or branched
nonadecenoic acids, straight-chain or branched eicosenoic acids,
straight-chain or branched heneicosenoic acids, straight-chain or
5 branched docosenoic acids, straight-chain or branched tricosenoic acids
and straight-chain or branched tetracosenoic acids, as well as mixtures
of the foregoing. Particularly preferred among these, from the
standpoint of improving the machining efficiency and tool life and the
handleability, are C3-20 saturated fatty acids, C3-22 unsaturated fatty
10 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.
15 [0046] Polybasic acids include C2-16 dibasic acids and trimellitic acid.
Such C2-16 dibasic acids may be straight-chain or branched, and either
saturated or unsaturated. Specific examples include ethanedioic acid,
propanedioic acid, straight-chain or branched butanedioic acids,
straight-chain or branched pentanedioic acids, straight-chain or
20 branched hexanedioic acids, straight-chain or branched heptanedioic
acids, straight-chain or branched octanedioic acids, straight-chain or
branched nonanedioic acids, straight-chain or branched decanedioic
acids, straight-chain or branched undecanedioic acids, straight-chain or
branched dodecanedioic acids, straight-chain or branched tridecanedioic
25 acids, straight-chain or branched tetradecanedioic acids, straight-chain
or branched heptadecanedioic acids, straight-chain or branched
17
FPl 1-0531-00
#
hexadecanedioic acids, straight-chain or branched hexenedioic acids,
straight-chain or branched heptenedioic acids, straight-chain or
branched octenedioic acids, straight-chain or branched nonenedioic
acids, straight-chain or branched decenedioic acids, straight-chain or
5 branched undecenedioic acids, straight-chain or branched decenedioic
acids, straight-chain or branched tridecenedioic acids, straight-chain or
branched tetradecenedioic acids, straight-chain or branched
heptadecenedioic acids, straight-chain or branched hexadecenedioic
acids, and mixtures of the foregoing.
10 [0047] Examples of sulfides of unsaturated carboxylic acids include
sulfides of unsaturated acids among the carboxylic acids mentioned for
(B) above. Sulfide of oleic acid is a specific example.
[0048] Examples of CI-30 hydrocarbon groups represented by R^ for
the compound represented by general formula (3) above, include CI-30
15 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 groups. Among these, Cl-30
straight-chain or branched alkyl groups are preferred, CI-20 straightchain
or branched alkyl groups are more preferred, CI-10 straight-chain
20 or branched alkyl groups are even more preferred, and CI-4 straightchain
or branched alkyl groups are most preferred. Examples of CI-4
straight-chain or branched alkyl groups include methyl, ethyl, straightchain
or branched propyl and straight-chain or branched butyl groups.
[0049] The hydroxyl may be substituted at any position, but in the case
25 of two or more hydroxyl groups they are preferably substituted at
adjacent carbon atoms. The letter c is preferably an integer of 1 to 3,
18
FPl 1-0531-00
#
and even more preferably 2. The letter b is preferably an integer of 0
to 3, and even more preferably 1 or 2. Examples of compounds
represented by general formula (3) include p-tert-butylcatechol.
[0050] Examples of CI-30 hydrocarbon groups represented by R^, for
5 compounds represented by general formula (4) above, include the same
examples of CI-30 hydrocarbon groups represented by R^ in general
formula (2), and the preferred ones 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
10 atoms. The letter d is preferably an integer of 1 to 3, and even more
preferably 2. The letter e is preferably an integer of 0 to 3, and even
more preferably 1 or 2. Examples of compounds represented by
general formula (4) include 2,2-dihydroxynaphthalene and 2,3-
dihydroxynaphthalene.
15 [0051] Examples of polyoxyalkylene compounds include compounds
represented by the following general formula (5) or (6).
R^O-(R^O)rR^ (5)
n Q
[In formula (5), R and R each independently represent hydrogen or a
Q
CI-30 hydrocarbon group, R represents a C2-4 alkylene group, and f
20 represents an integer such that the number-average molecular weight is
100 to 3500.]
A-[(R^°OVR^^]h (6)
[In formula (6), A represents the residue after removing some or all of
the hydrogens of the hydroxyl groups of a polyhydric alcohol having 3
25 to 8 hydroxyl groups, R^° represents a C2-4 alkylene group, R^^
represents hydrogen or a CI-30 hydrocarbon group, g represents an
19
FPl 1-0531-00
#
integer such that the number-average molecular weight is 100 to 3500,
and h represents the same number as the number of hydrogens removed
from the hydroxyl groups of A.]
[0052] In general formula (5), at least one of R^ and R^ is preferably
5 hydrogen. Examples of CI-30 hydrocarbon groups represented by R
and R^ include the same examples of CI-30 hydrocarbon groups
represented by R^ in general formula (3), and the preferred ones are also
the same. Specific examples of C2-4 alkylene groups represented by
o
R include ethylene, propylene (methylethylene) and butylene
10 (ethylethylene) groups. The letter f is preferably an integer such that
the number-average molecular weight is 300 to 2000, and more
preferably an integer such that the number-average molecular weight is
500 to 1500.
[0053] As specific examples of polyhydric alcohols having 3 to 8
15 hydroxyl groups composing A in general formula (6) above, there may
be used the same polyhydric alcohols mentioned as examples of
alcohols as oil agents.
[0054] For an ester, the alcohol composing it may be either a
monohydric alcohol or a polyhydric alcohol, and the carboxylic acid
20 may be either a monobasic acid or a polybasic acid. As monohydric
alcohols and polyhydric alcohols there may be used the same
monohydric alcohols and polyhydric alcohols mentioned for examples
of alcohols as oil agents.
[0055] The alcohol composing an ester oil agent may be a monohydric
25 alcohol or a polyhydric alcohol as mentioned above, but it is preferably
a polyhydric alcohol from the viewpoint of achieving superior
20
FPl 1-0531-00
machining efficiency and tool life, more easily obtaining a low pompoint
and improving the handleability in winter season and cold
climates. Trivalent alcohols are particularly preferred. Using a
polyhydric alcohol ester will result in improved workability and a
5 greater continuous workability effect.
[0056] Also, the acid composing an ester oil agent may be a monobasic
acid or a polybasic acid, mentioned above as carboxylic acids for oil
agents. The alkyl groups of a carboxylic acid may be straight-chain or
branched and either saturated or unsaturated, but are preferably straight-
10 chain and unsaturated.
[0057] When a polyhydric alcohol is used as the alcohol component,
the ester may be a complete 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
15 esterification. Also, when a polybasic acid is used as the carboxylic
acid component, the ester may be a complete 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.
20 [0058] There are no particular restrictions on the total number of carbon
atoms of the ester oil agent, but firom the standpoint of improving the
machining efficiency and tool life, esters with 7 or more carbon atoms
are preferred, esters with 9 or more are more preferred, and esters with
11 or more are most preferred. From the standpoint of minimizing
25 staining and corrosion, and of compatibility with organic materials,
esters with no more than 60 carbon atoms are preferred, esters with no
21
FPll-0531-00
#
more than 45 are more preferred, esters with no more than 26 are even
more preferred, esters with no more than 24 are yet more preferred, and
esters with no more than 22 are most preferred.
[0059] Polyhydric alcohols composing hydrocarbyl ethers of polyhydric
5 alcohols are the same polyhydric alcohols as for the alcohol compound
of the present invention.
[0060] Of these polyhydric alcohols, there are preferred ethylene glycol,
diefhylene glycol, polyethylene glycol (3- to 10-mers of ethylene
glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3-
10 to 10-mers of propylene glycol), 1,3-propane diol, 2-methyl-l,2-
propane diol, 2-methy 1-1,3-propane diol, neopentyl glycol, glycerin,
diglycerin, triglycerin, trimethylolalkane (trimethylolethane,
trimethylolpropane, trimethylolbutane and the like), and their 2- to 4-
mers, and divalent to hexavalent polyhydric alcohols such as
15 pentaerythritol, dipentaerythritol, 1,2,4-butane triol, 1,3,5-pentane triol,
1,2,6-hexane triol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol
glycerin condensation product, adonitol, arabitol, xylitol and mannitol,
as well as mixtures of the foregoing. Even more preferred are ethylene
glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolethane,
20 trimethylolpropane, pentaerythritol, sorbitan, and their mixtures.
Among these, glycerin is most preferred from the standpoint of
increasing machining efficiency and tool life.
[0061] As hydrocarbyl ethers of polyhydric alcohols there may be used
ones obtainable by the hydrocarbyletherification of all or a portion of
25 the hydroxyl groups of the aforementioned polyhydric alcohols. From
the standpoint of increasing machining efficiency and tool life, there are
22
FPl 1-0531-00
#
preferred polyhydric alcohols with hydrocarbyletherification of a
portion of the hydroxyl groups (partially etherified products). Here,
"hydrocarbyl group" refers to a CI-24 hydrocarbon group such as CI-24
alkyl, C2-24 alkenyl, C5-7 cycloalkyl, C6-11 alkylcycloalkyl, C6-10
5 aryl, C7-18 alkylaryl or C7-18 arylalkyl.
[0062] From the viewpoint of increasing machining 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 obtainable by the removing the
10 hydroxyl group fi*om oleyl alcohol) are more preferred.
[0063] A monoamine is preferred for use as the amine. The number of
carbon atoms of the monoamine is preferably 6 to 24 and more
preferably 12 to 24. The number of carbon atoms referred to here is
the total number of carbon atoms present in the monoamine, and when
15 the monoamine has two or more hydrocarbon groups, it is the total
number of carbon atoms.
[0064] Monoamines to be used for the invention include primary
monoamines, secondary monoamines and tertiary monoamines,
although primary monoamines are preferred JBrom the standpoint of
20 increasing machining efficiency and tool life.
[0065] 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 fi*om the standpoint of increasing
25 machining efficiency and tool life. The alkyl and alkenyl groups may
be straight-chain or branched, but are preferably straight-chain fi-om the
23
FPl 1-0531-00
#
standpoint of increasing machining efficiency and tool life.
[0066] Specific examples of preferred monoamines include hexylamine
(including all isomers), heptylamine (including all isomers), octylamine
(including all isomers), nonylamine (including all isomers), decylamine
5 (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
10 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) (which includes oleylamine and the like), and
15 mixtures of two or more of the foregoing. Among these, CI2-24
primary monoamines are preferred, CI4-20 primary monoamines are
more preferred and CI6-18 primary monoamines are even more
preferred, from the standpoint of increasing machining efficiency and
tool life.
20 [0067] According to this embodiment, one type selected from among
the aforementioned oil agents may be used, or a mixture of two or more
thereof may be used. From the viewpoint of increasing machining
efficiency and tool life, one or a mixture of two or more selected from
among carboxylic acids and esters is preferred.
25 [0068] There are no particular restrictions on the oil agent content, but
from the viewpoint of improving workability, it is preferably 0.1% by
24
FPl 1-0531-00
dp
mass or greater, more preferably 0.5% by mass or greater and even
more preferably 1% by mass or greater, based on the total mass of the
composition. From the viewpoint of stability, the oil agent content is
preferably no greater than 20% by mass, more preferably no greater
5 than 15% by mass and even more preferably no greater than 10% by
mass based on the total mass of the composition. No commensurate
effect is obtained with excessive addition, while no effect is obtained
with insufficient addition.
[0069]
10 Antioxidant
The lubricating agent composition for plastic processing of this
embodiment preferably further contains an antioxidant. Addition of an
antioxidant can prevent sticking caused by degradation of the
constituent components, while further enhancing the heat and oxidation
15 stability.
[0070] Antioxidants that may be used include phenol-based
antioxidants, amine-based antioxidants, and antioxidants used as food
additives.
[0071] Phenol-based antioxidants include any phenol-based compounds
20 that can be used as antioxidants for lubricant oils, without any particular
restrictions, among which alkylphenol compounds are preferred
examples.
[0072] Amine-based antioxidants include any amine-based compounds
that are used as antioxidants for lubricant oils, without any particular
25 restrictions, with preferred examples including phenyl-a-naphthylamine,
N-p-alkylphenyl-a-naphthylamines and p,p'-dialkyldiphenylamines, and
25
FPll-0531-00
specifically 4-butyl-4'-octyldiphenylamine, phenyl-a-naphthylamine,
octylphenyl-a-naphthylamine and dodecylphenyl-a-naphthylamine, as
well as mixtures of the foregoing.
[0073] Antioxidants employed as food additives may also be used, and
5 they partially overlap with the aforementioned phenol-based
antioxidants, with examples including 2,6-di-tert-butyl-p-cresol (DBPC),
4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tertbutylphenol),
4,4'-thiobis(6-tert-butyl-o-cresol), ascorbic acid (vitamin
C), fatty acid esters of ascorbic acid, tocopherol (vitamin E), 3,5-di-tert-
10 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).
[0074] Preferred among these antioxidants are phenol-based
15 antioxidants, amine-based antioxidants and the aforementioned ones
that are employed as food additives. The use of food additive
antioxidants is more preferred when biodegradability is a primary
concern, and of these, ascorbic acid (vitamin C), fatty acid esters of
ascorbic acid, tocopherol (vitamin E), 2,6-di-tert-butyl-p-cresol (DBPC),
20 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, with
ascorbic acid (vitamin C), fatty acid esters of ascorbic acid, tocopherol
25 (vitamin E), 2,6-di-tert-butyl-p-cresol (DBPC) and 3,5-di-tert-butyl-4-
hydroxyanisole being more preferred.
26
FPl 1-0531-00
[0075] There are no particular restrictions on the antioxidant content,
but in order to maintain satisfactory heat and oxidation stability, the
content is preferably 0.01% by mass or greater, even more preferably
0.05% by mass or greater and most preferably 0.1% by mass or greater,
5 based on the total mass of the composition. Since no further increase
in effect can be expected with addition in greater amounts, the content is
preferably no greater than 10% by mass, more preferably no greater
than 5% by mass and most preferably no greater than 3% by mass.
[0076]
10 Other additives
The lubricating agent composition for plastic processing according to
this embodiment may also contain conventional known additives in
addition to those mentioned above. Examples of such additives
include extreme pressure agents other than the aforementioned
15 phosphorus-based extreme pressure agents and sulfur-based extreme
pressure agents; wetting agents such as diethylene glycol monoalkyl
ethers; film-forming agents such as acrylic polymers, paraffin wax,
microwax, slack wax, polyolefin wax and the like; water displacement
agents such as fatty acid amine salts; solid lubricants such as graphite,
20 graphite fluoride, molybdenum disulfide, boron nitride and polyethylene
powder; corrosion inhibitors such as amines, alkanolamines, amides,
carboxylic acids, carboxylic acid salts, sulfonic acid salts, phosphoric
acids, phosphoric acid salts and partial esters of polyhydric alcohols;
metal inactivating agents such as benzotriazole and thiadiazole;
25 antifoaming agents such as methylsilicone, fluorosilicone and
polyacrylate; and non-ash powders such as alkenylsuccinic acid imides,
27
FPl 1-0531-00
benzylamines and polyalkenylamineaminoamides. The contents of
such known additives when used in combination are not particularly
restricted, but they are generally added in amounts so that the total
content of the known additives is 0.1 to 10% by mass based on the total
5 mass of the composition.
[0077] The lubricating agent composition for plastic processing of this
embodiment may contain a chlorine-based additive such as a chlorinebased
extreme pressure agent as mentioned above, but from the
viewpoint of improving safety and reducing environmental load, it
10 preferably does not contain a chlorine-based additive. Also, the
chlorine concentration is preferably no greater than 1000 ppm by weight,
more preferably no greater than 500 ppm by weight, even more
preferably no greater than 200 ppm by weight, and most preferably no
greater than 100 ppm by weight, based on the total mass of the
15 composition.
[0078] The lubricating agent composition of this embodiment is used
for plastic processing of a metal material. It is most preferably used
for materials that are difficult to process, such as steel sheets, stainless
steel plates, surface-treated steel sheets, aluminum alloy sheets and
20 titanium alloys. It is also preferably used under difficult processing
conditions, such as press molding, bending, pultrusion molding, ironing
molding and forging.
Examples
[0079] The present invention will now be explained in greater detail
25 based on examples and comparative examples, with the understanding
that these examples are in no way limitative on the invention.
28
FPl 1-0531-00
[0080]
[Examples 1 to 28, Reference Example 1, Comparative Examples 1 to
12]
For Examples 1 to 28, Reference Example 1 and Comparative Examples
5 1 to 12 there were prepared lubricating agent compositions having the
compositions shown in Tables 1 to 6, using the following components.
Component (A): Zinc dithiophosphate (The "zinc content" is the value
with inclusion of a diluent oil or the like.)
Al: Zinc dithiophosphate having the structure represented by general
1 0
10 formula (1), wherein R and R are C6 branched-chain (sec-)alkyl
groups (zinc content: 9.3% by mass).
A2: Zinc dithiophosphate having the structure represented by general
formula (1), wherein R and R are C4 or C5 straight-chain (pri-)alkyl
groups (zinc content: 10% by mass).
15 A3: Zinc dithiophosphate having the structure represented by general
formula (1), wherein R and R are C12 branched-chain (sec-)alkyl
groups (zinc content: 7.5% by mass).
A4: Zinc dithiophosphate having the structure represented by general
formula (1), wherein R and R are C18 branched-chain (pri-)alkyl
20 groups (zinc content: 11% by mass).
Component (B): Sulfur-based extreme pressure agent (The "sulfur
content" is the value with inclusion of a diluent oil or the like.)
Bl: Sulfurized ester (sulfurized fat or oil) (sulfur content: 28% by mass)
B2: di-t-Nonyl polysulfide (The t-nonyl group being derived from a
25 trimer of propylene; average number of sulfur atoms per molecule: 4.6;
sulfiir content: 38% by mass.)
29
FPl 1-0531-00
B3: Sulfurized lard (sulfur content: 19% by mass)
Component (C): Organic acid salt (The Ca and Na contents are the
values with inclusion of a diluent oil or the like.)
CI: Calcium sulfonate (base value: 403 mgKOH/g, Ca content: 15%)
5 C2: Sodium sulfonate (base value: 165 mgKOH/g, Na content: 11%)
C3: Calcium phenate (base value: 302 mgKOH/g, Ca content: 10%)
C4: Calcium salicylate (base value: 274 mgKOH/g, Ca content: 15%)
C5: Calcium sulfonate (base value: 101 mgKOH/g, Ca content: 18%)
C6: Calcium sulfonate (base value: 51 mgKOH/g, Ca content: 13%)
10 (D) Hydrocarbon oil
Dl: Mineral oil (40°C kinematic viscosity: 94 mm ^/s, %Cp = 67)
D2: Mineral oil (40°C kinematic viscosity: 101 mmVs, %Cp = 51)
D3: Mineral oil (40°C kinematic viscosity: 95 mmVs, %Cp = 78)
D4: Mineral oil (40°C kinematic viscosity: 96 mm^/s, %oCp = 44)
15 D5: Poly a-olefin (40°C kinematic viscosity: 98 mm Is)
Other additives
El: Acidic phosphoric acid ester (Mixture of mono n-octyl acid
phosphate and di n-octyl acid phosphate (phosphorus content: 11.6% by
mass).)
20 E2: Ester: Glycerin trioleate
E3: Fatty acid: Oleic acid
E4: Antioxidant: 2,6-di-tert-Butyl-p-cresol (DBPC)
E5: Chlorinated paraffin (chlorine content: 50% by mass)
[0081]
25 (Burring test)
Each of the lubricating agent compositions of Examples 1 to 28,
30
FPl 1-0531-00
Reference Example 1 and Comparative Examples 1 to 12 were used for
a burring test in the following manner.
Fig. 1 is a schematic cross-sectional view showing the construction of a
burring tester used for the test. The burring tester illustrated in Fig. 1
5 comprises a support 1 with a hollow interior, a die 2 disposed on the
support 1, a die cushion 3 provided in the hollow section of the support
1, a wrinkle holding member 4 disposed above the die 2, and a punch 5
provided above the die 2.
For the test, first a waste cloth impregnated with the lubricating agent
10 composition was used to coat the lubricating agent composition to 1 to 2
g/m on both sides of a test piece 6 (material: SUS304, outer diameter:
80 nrai, inner diameter: 4 mm, thickness: 2 mm). Next, the test piece 6
and a steel ball 7 (material: SUJ2, diameter: 15 mm) were placed on the
die 2, and while holding them with the wrinkle holding member 4, the
15 steel ball 7 was pressed firom above with the punch 5 while raising the
die cushion 3, thereby crumpling the test piece 6. The testing
temperature at this time was 100°C, and the crumpling rate ((thickness
of test piece 6 before deformation - the thickness of deformed section
after crumpling)/thickness of test piece 6 before test) was 62.5%, and
20 the machining speed was 10 mm/s. The presence or absence of seizing
and adhesion between the test piece 6 and steel ball 7 was visually
observed for each test piece.
The evaluation criteria for seizing were as follows.
S: Absolutely no seizing.
25 A: No seizing, but slight clouding of surface.
B: Some seizing.
31
FPl 1-0531-00
C: Seizing over entire surface.
The evaluation criteria for adhesion were as follows.
S: Absolutely no adhesion.
A: No adhesion, but slight clouding of surface.
5 B: Some adhesion.
C: Adhesion over entire surface.
The obtained results are shown in Tables 1 to 6.
[0082][Table 1]
32
FPl 1-0531-00
¥
Component (A),
mass%
Al
A2
A3
A4
Zn content from component (A),
mass%
Component (B),
mass%
Bl
B2
B3
S content from component (B),
mass%
Component (C),
mass%
CI
C2
C3
C4
C5
C6
Cationic component from
component (C),
mass%
Hydrocarbon oil,
mass%
Other additives,
mass%
Burring test
Dl
D2
D3
D4
D5
El
E2
E3
E4
E5
Seizing
Adhesion
Example
1
5
-
-
-
0.47
55
--
15.4
40
-----
6.0
--------
--
S
s
Example
2
-
5
--
0.5
55
--
15.4
40
-----
6.0
--------
--
S
s
Example
3
-
-
5
-
0.38
55
--
15.4
40
--
---
6.0
--------
--
S
A
Example
4
-
--
5
0.55
55
--
15.4
40
-----
6.0
---
-
----
--
A
A
Example
5
5
---
0.47
-
55
-
20.9
40
-----
6.0
---
-
-
---
-
-
S
s
Example
6
5
---
0.47
--
55
10.5
40
-
----
6.0
-------- --
S
s
Example
7
5
---
0.47
55
--
15.4
-4
0
----
6.0
--
------
--
S
s
[0083] [Table 2]
33
FPl 1-0531-00
Component (A),
mass%
Al
A2
A3
A4
Zn content from component (A),
mass%
Component (B),
mass%
Bl
B2
B3
S content from component (B),
mass%
Component (C),
mass%
CI
C2
C3
C4
C5
C6
Cationic component from
component (C), mass%
Hydrocarbon oil,
mass%
Other additives,
mass%
Burring test
Dl
D2
D3
D4
D5
El
E2
E3
E4
E5
Seizing
Adhesion
Example
8
5
---
0.47
55
--
15.4
-
- 40
---
4.0
--
------
-
-
S
s
Example
9
5
---
0.47
55
-
-
15.4
--
-4
0
--
6.0
-
-
-------
-
S
s
Example
10
5
--
-
0.47
55
-
-
15.4
--
-- 40
-
7.2
-
-
-------
-
A
S
Example
11
5
--
-
0.47
55
-
-
15.4
--
--
-
40
5.2
--
-------
-
A
A
Example
12
1
---
0.09
40
--
11.2
30
-
----
4,5
29
-
-------
-
S
A
Example
13
1
---
0.09
40
--
11.2
30
-
----
4.5
-2
9
-
----
-- -
S
A
Example
14
1
-
--
0.09
40
-
-
11.2
30
-
---
-
4.5
--
29
-----
-
-
A
A
[0084][Table 3]
34
FPl 1-0531-00
#
Component (A),
mass%
Al
A2
A3
A4
Zn content from component (A),
mass%
Component (B),
mass%
Bl
B2
B3
S content from component (B),
mass%
Component (C),
mass%
CI
C2
C3
C4
C5
C6
Cationic component from
component (C), mass%
Hydrocarbon oil,
mass%
Other additives,
mass%
Burring test
Dl
D2
D3
D4
D5
El
E2
E3
E4
E5
Seizing
Adhesion
Example
15
1
--
-
0.09
40
--
11.2
30
-
----
4.5
---29
------
A
A
Example
16
20
--
-
1.86
40
-
-
11.2
30
-
----
4.5
10
---
-----
-
S
s
Example
17
0.3
--
-
0.028
40
--
11.2
30
-
----
4.5
29.7
-
-
-
-
-
----
A
A
Example
18
38
-
-
-
3.53
34
--
9.52
25
-
----
3.75
3
---
------
S
S
Example
19
1
---
0.09
60
--
16.8
30
-
----
4.5
9
---
------
S
S
Example
20
1
--
-
0.09
33
--
9.24
30
-----
4.5
36
---
------
A
A
Example
21
1
--
-
0.09
68
--
19.0
30
-
-
---
4.5
1
---
------
S
S
[0085][Table4]
35
FPl 1-0531-00
Component (A),
mass%
Al
A2
A3
A4
Zn content from component (A),
mass%
Component (B),
mass%
HI
32
33
S content from component (B),
mass%
Component (C),
mass%
CI
C2
C3
C4
C5
C6
Cationic component from
component (C), mass%
Hydrocarbon oil,
mass%
Other additives,
mass%
Burring test
Dl
D2
D3
D4
D5
El
E2
E3
E4
E5
Seizing
Adhesion
Example
22
1
-
--
0.09
40
11.2
50
-
-
---
7.5
9
-----
----
S
S
Example
23
1
-
-
-
0.09
40
11.2
11
-
---
-
1.65
44
----
-
----
A
A
Example
24
1
-
-
-
0.09
40
11.2
58
-
---
-
8.7
1
---
--
----
S
S
Example
25
1
-
--
0.09
40
11.2
30
-
----
4.5
18
----
10
-
-
1
-
s
s
Example
26
1
-
-
-
0.09
40
11.2
30
-
---
-
4.5
18
----
-
10
-
1
-
s
s
Example
27
1
-
--
0.09
40
11.2
30
-
----
4.5
18
-----
-
10
1
-
s
A
Example
28
1
-
--
0.09
40
11.2
30
-
----
4.5
24
---
5
-
--
--
A
A
[0086][Table 5]
36
FPl 1-0531-00
Component (A),
mass%
Al
A2
A3
A4
Zn content from component (A), mass%
Component (B),
mass%
Bl
B2
B3
S content from component (B), mass%
Component (C),
mass%
CI
C2
C3
C4
C5
C6
Cationic component from component
(C), mass%
Hydrocarbon oil,
mass%
Other additives,
mass%
Burring test
Dl
D2
D3
D4
D5
El
E2
E3
E4
E5
Seizing
Adhesion
Ref. Ex.
1
--------
4.5
30
--
---
-
29
--
-
----
1
40
S
S
Comp. Ex.
1
-----
60
--
16.8
40
--
-
-
-
6.0
---------
-
S
B
Comp. Ex.
2
30
---
2.79
----
70
--
---
10.5
----------
C
B
Comp. Ex.
3
25
---
2.33
75
--21
-
-
--
-
-
-----
-
---
-
B
B
Comp. Ex.
4
-
--------
100
--
---
15
----------
C
C
Comp. Ex.
5
100
---
9.3
----
--
---
-
----------
B
C
Comp. Ex.
6
--
---
100
--28
--
--
-
-
----------
A
C
[0087] [Table 6]
37
FPl 1-0531-00
• ^
Component (A),
mass%
Al
A2
A3
A4
Zn content &om component (A), mass%
Component (B),
mass%
Bl
B2
B3
S content from component (B), mass%
Component (C),
mass%
CI
C2
C3
C4
C5
C6
Cationic component from component (C),
mass%
Hydrocarbon oil,
mass%
Other additives,
mass%
Burring test
Dl
D2
D3
D4
D5
El
E2
E3
E4
E5
Seizing
Adhesion
Comp. Ex.
7
0.05
--
-
0.0045
58
-
-
16.2
41.95
-
--
--
6.29
-------
--
-
B
B
Comp. Ex.
8
44
--
-
4.1
37
-
-
10.4
19
-
----
2.85
---
--
--
---
B
S
Comp. Ex.
9
24
-
-
-
2.23
- 24
-
9.12
50
-----
7.5
---
-------
C
c
Comp. Ex.
10
1
--
-
0.09
-
73
-
27.7
26
-
---
-
3.90
-------
---
B
A
Comp. Ex.
11
30
---
2.79
-
64
-
24.3
6
-
-
---
0.90
---
---
-
-
--
C
B
Comp. Ex.
12
1
---
0.09
- 36
-
13.7
63
-
--
--
9.45
-
--
----
--
-
B
B
Explanation of Symbols
[0088] 1 ... Support, 2 ... die, 3 ... die cushion, 4
member, 5 ... punch, 6 ... test piece, 7 ... steel ball.
wrinkle holding
38

FPll-0531-00
CLAIMS
1. A lubricating agent composition for plastic processing comprising:
0.1 to 40% by mass of a zinc dithiophosphate represented by the
following general formula (1),
30 to 70% by mass of a sulfur-based extreme pressure agent and
10 to 60% by mass of an organic acid salt,
based on the total mass of the composition.
[Chemical Formula 1]
Zn-
S
II ,
-P 0R2
I ,
(1)
J 2
1 '7
10 [In formula (1), R and R may be the same or different, and each
represents a C1-18 straight-chain or branched-chain alkyl group.]