U.S. patent application number 15/569215 was filed with the patent office on 2018-12-13 for solid lubricant, lubricating coating agent for metal material, surface-treated metal material, and method for forming lubricating coating for metal material.
This patent application is currently assigned to Nihon Parkerizing Co., Ltd.. The applicant listed for this patent is Nihon Parkerizing Co., Ltd.. Invention is credited to Shinobu Komiyama, Kenichiro Oshita.
Application Number | 20180355275 15/569215 |
Document ID | / |
Family ID | 57199794 |
Filed Date | 2018-12-13 |
United States Patent
Application |
20180355275 |
Kind Code |
A1 |
Oshita; Kenichiro ; et
al. |
December 13, 2018 |
SOLID LUBRICANT, LUBRICATING COATING AGENT FOR METAL MATERIAL,
SURFACE-TREATED METAL MATERIAL, AND METHOD FOR FORMING LUBRICATING
COATING FOR METAL MATERIAL
Abstract
Provided is a solid lubricant that is non-black in color and
capable of reducing industrial waste (environmental conservation),
and further capable of achieving a balance among excellent
lubricity, moisture absorption resistance, and corrosion resistance
in a heavy working region, and a lubricating coating agent
including the solid lubricant. A solid lubricant including carrier
particles including a lipophilic lubricating component that is at
least one of an oil, an extreme-pressure agent, a soap, and a wax
between particles of and/or between layers of at least one layered
clay mineral selected from the group consisting of natural products
and synthetic products of a smectite group, a vermiculite group, a
mica group, a brittle mica group, a pyrophyllite group, and a
kaolinite group.
Inventors: |
Oshita; Kenichiro; (Tokyo,
JP) ; Komiyama; Shinobu; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Nihon Parkerizing Co., Ltd. |
Tokyo |
|
JP |
|
|
Assignee: |
Nihon Parkerizing Co., Ltd.
Tokyo
JP
|
Family ID: |
57199794 |
Appl. No.: |
15/569215 |
Filed: |
March 4, 2016 |
PCT Filed: |
March 4, 2016 |
PCT NO: |
PCT/JP2016/056763 |
371 Date: |
October 25, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 125/30 20130101;
C10M 2201/0663 20130101; C10N 2050/08 20130101; C10M 2203/1065
20130101; C09D 7/40 20180101; C10M 101/02 20130101; C10M 145/38
20130101; C10M 2207/2835 20130101; C10M 173/02 20130101; C10M
111/02 20130101; C10M 105/40 20130101; C10M 169/041 20130101; C10M
2223/0415 20130101; C10M 101/04 20130101; C10M 2203/003 20130101;
C09D 5/03 20130101; C10M 103/06 20130101; C10M 2205/143 20130101;
C10M 105/24 20130101; C10M 111/04 20130101; C10M 2201/14 20130101;
C10M 2209/109 20130101; C09D 201/00 20130101; C09D 5/02 20130101;
C10M 107/04 20130101; C10M 107/34 20130101; C10M 2207/126 20130101;
C10M 2209/1045 20130101; C10M 105/74 20130101; C10M 2201/1033
20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10M 103/06 20060101 C10M103/06; C10M 101/04 20060101
C10M101/04; C10M 107/34 20060101 C10M107/34; C10M 101/02 20060101
C10M101/02; C10M 105/40 20060101 C10M105/40; C10M 105/74 20060101
C10M105/74; C10M 105/24 20060101 C10M105/24; C10M 107/04 20060101
C10M107/04; C10M 111/04 20060101 C10M111/04; C10M 111/02 20060101
C10M111/02; C10M 145/38 20060101 C10M145/38 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 27, 2015 |
JP |
2015-090838 |
Claims
1. A solid lubricant comprising carrier particles including a
lipophilic lubricating component that is at least one of an oil, an
extreme-pressure agent, a soap, and a wax between particles of
and/or layers of at least one layered clay mineral selected from
the group consisting of natural products and synthetic products of
a smectite group, a vermiculite group, a mica group, a brittle mica
group, a pyrophyllite group, and a kaolinite group.
2. The solid lubricant according to claim 1, wherein an aspect
ratio is 3 to 150 in a cross section of the layered clay
mineral.
3. The solid lubricant according to claim 1, wherein the lipophilic
lubricating component has a solubility parameter (SP value) of 10
or less.
4. The solid lubricant according to claim 1, wherein the layered
clay mineral is 40.degree. or more in water contact angle.
5. The solid lubricant according to claim 1, wherein the layered
clay mineral is 30 .mu.m or less in average particle size.
6. The solid lubricant according to claim 1, wherein an inclusion
amount of the lipophilic lubricating component is 5 mass % or more
in mass ratio to a total mass of the carrier particles.
7. The solid lubricant according to claim 1, wherein the layered
clay mineral has Mohs hardness of 2 or less.
8. The solid lubricant according to claim 1, wherein the solid
lubricant is used for a lubricating coating agent for plastic
working of a metal material.
9. A water-based lubricating coating agent for a metal material,
wherein a component comprising at least the solid lubricant
according to claim 1 is dispersed in water, and wherein a
concentration of the solid lubricant is 5 mass % or higher in mass
ratio to a mass of a total solid content in the lubricating coating
agent.
10. An oil-based lubricating coating agent for a metal material,
wherein a component comprising at least the solid lubricant
according to claim 1 is dispersed in an oil, and wherein a
concentration of the solid lubricant is 5 mass % or higher in mass
ratio to a mass of a total solid content in the lubricating coating
agent.
11. A powder-based lubricating coating agent for a metal material,
which contains a component comprising at least the solid lubricant
according to claim 1, wherein a concentration of the solid
lubricant is 5 mass % or higher in mass ratio to a mass of a total
solid content in the lubricating coating agent.
12. A surface-treated metal material wherein a coating obtained by
using the lubricating coating agent for a metal material according
to claim 9 is formed on/over a metal material surface to be 0.5
g/m.sup.2 or more as a dried coating amount.
13. A method for forming a lubricating coating for a metal
material, the method comprising a contact step of bringing a metal
material into contact with the lubricating coating agent for a
metal material according to claim 9.
14. The method for forming a lubricating coating for a metal
material according to claim 13, the method further comprising a
chemical conversion treatment step of coating a surface of the
metal material with a chemical conversion coating before the
contact step.
15. A surface-treated metal material wherein a coating obtained by
using the lubricating coating agent for a metal material according
to claim 10 is formed on/over a metal material surface to be 0.5
g/m2 or more as a dried coating amount.
16. A method for forming a lubricating coating for a metal
material, the method comprising a contact step of bringing a metal
material into contact with the lubricating coating agent for a
metal material according to claim 10.
17. The method for forming a lubricating coating for a metal
material according to claim 16, the method further comprising a
chemical conversion treatment step of coating a surface of the
metal material with a chemical conversion coating before the
contact step.
18. A surface-treated metal material wherein a coating obtained by
using the lubricating coating agent for a metal material according
to claim 11 is formed on/over a metal material surface to be 0.5
g/m2 or more as a dried coating amount.
19. A method for forming a lubricating coating for a metal
material, the method comprising a contact step of bringing a metal
material into contact with the lubricating coating agent for a
metal material according to claim 11.
20. The method for forming a lubricating coating for a metal
material according to claim 19, the method further comprising a
chemical conversion treatment step of coating a surface of the
metal material with a chemical conversion coating before the
contact step.
Description
TECHNICAL FIELD
[0001] The present invention relates to a solid lubricant for
imparting excellent lubricity to the surface of a metal material
such as iron and steel, stainless steel, aluminum, and titanium, a
lubricating coating agent including the solid lubricant, and a
lubricating coating formed with the use thereof, as well as
techniques related thereto. More particularly, the present
invention is directed to a solid lubricant which can be used for
plastic working such as forging, wire drawing, tube drawing, and
heading of the metal material, for press molding of a plate
material, and in sliding parts of various devices, and a
lubricating coating agent including the solid lubricant, and
further including no black-based lubricant such as molybdenum
disulfide or graphite.
BACKGROUND ART
[0002] In general, in plastic working of metal materials such as
iron and steel and stainless steels, for the purposes of preventing
from seizure and galling caused by metal contact between materials
to be worked and tools, and imparting corrosion resistance,
coatings that have lubricity and corrosion resistance are provided
on the metal material surfaces. Such coatings include two types: a
reactive type of forming, on a metal material surface, a chemical
conversion coating by chemical reaction, and then further forming a
lubricant thereon; and a non-reactive type of physically forming a
lubricant on a metal material surface.
[0003] Lubricating coatings that have a two-layer structure
obtained by forming, on a metal material surface, a chemical
conversion coating such as a phosphate coating or an oxalate
coating that has a role as a carrier, and then further applying a
lubricant such as a lime soap, a molybdenum disulfide, or an oil,
and lubricating coatings that have a three-layer structure
(chemical conversion coating/metal soap coating/unreacted soap
coating) obtained by applying a chemical conversion coating, and
then reactive coating with a reactive soap such a sodium stearate
are widely used in the case of the former reactive type. In
particular, the latter lubricating coatings that have the
three-layer structure are known to be capable of producing stable
and excellent lubricity even in heavy working regions.
[0004] However, the chemical conversion treatment with the chemical
reaction and the reactive soap require solution management,
temperature management for controlling the chemical reaction,
removal and disposal of sludge as a reaction by-product, and
disposal renewal due to solution deterioration. For the purpose of
global environmental conservation in recent years, the reduction of
industrial waste has become a great problem. To that end,
lubricating coating agents and treatment methods which produce no
waste have been desired.
[0005] As a lubricating coating agent for solving the problem
mentioned previously, Patent Literature 1 discloses a water-based
lubricant for cold plastic working of metal materials, which
includes: (A) at least one water-soluble inorganic salt selected
from sodium tetraborate, borax, potassium tetraborate, and sodium
sulfate; (B) at least one solid lubricant selected from metal soaps
composed of calcium stearate, barium stearate, and zinc stearate,
mica, and PTFE; (C) at least one oil component selected from a
mineral oil, animal and plant oils, and an ester oil; (D) a
surfactant for homogeneously emulsifying the oil component in water
and homogeneously dispersing the solid lubricant in water; and (E)
water, where the weight ratio (B/A) of the solid lubricant to the
water-soluble inorganic salt is 0.05/1 to 2/1, and the weight ratio
(C/(A+B)) of the oil component to the total amount of the
water-soluble inorganic salt and the solid lubricant is 0.05/1 to
1/1, and the solid lubricant and the oil component are
homogeneously dispersed and emulsified respectively. This
lubricating coating agent is a non-reactive coating-type lubricant
without the generation of sludge unlike the chemical conversion
treatment with the chemical reaction and the reactive soap, and
without solution deterioration. However, the water-soluble
inorganic salt which serves as a main constituent of a coating has
the problem of possibly causing lubricity to be deteriorated
through the moisture absorption from moisture vapor in the
atmosphere, and there has been thus a need for re-drying before
working or control for lowering humidity in the plant.
[0006] Moreover, the lubricant included in the lubricating coating
insufficiently follows to area expansions of metal surfaces under
severe conditions on the degree of working, and has problems such
as lubricity decreased, thereby leading to galling.
[0007] In addition, in the fields of cold plastic working and
sliding coatings, molybdenum disulfide has been used as a solid
lubricant since a long time ago. This is due in large part to the
low friction and favorable abrasion resistance of the lubricating
coating containing molybdenum disulfide. However, the lubricating
coating agent containing molybdenum disulfide is black, which
problematically contaminates working environments. In addition, the
expensiveness and poor economy of molybdenum disulfide are also
reasons of demand for the development of non-black solid
lubricants.
CITATION LIST
Patent Literature
[0008] Patent Literature 1: JP 3517522 B2
SUMMARY OF INVENTION
Technical Problem
[0009] To deal with the challenge and problem of the prior art
mentioned previously, a main object of the present invention is to
provide a solid lubricant that is non-black in color and capable of
reducing industrial waste (environmental conservation), and further
capable of achieving a balance among excellent lubricity, moisture
absorption resistance, and corrosion resistance in a heavy working
region, and a lubricating coating agent including the solid
lubricant.
Solution to Problem
[0010] The inventors have found, as a result of earnest studies for
solving the problem mentioned previously, the problem can be solved
by a solid lubricant characterized in that it includes carrier
particles including therein a specific lipophilic lubricating
component between particles of and/or between layers of a specific
layered clay mineral, and a lubricating coating agent for a metal
material, which uses the solid lubricant, thereby leading to the
completion of the present invention.
[0011] More specifically, a solid lubricant according to the
present invention is a solid lubricant characterized in that it
includes carrier particles including a lipophilic lubricating
component that is at least one of an oil, an extreme-pressure
agent, a soap, and a wax between particles of and/or between layers
of at least one layered clay mineral selected from the group
consisting of natural products and synthetic products of a smectite
group, a vermiculite group, a mica group, a brittle mica group, a
pyrophyllite group, and a kaolinite group.
[0012] Furthermore, the aspect ratio in a cross section of the
layered clay mineral is 3 to 150, preferably 5 to 100, and further
preferably 5 to 30.
[0013] The lipophilic lubricating component preferably has a
solubility parameter (SP value) of 10 or less, further preferably 9
or less.
[0014] Furthermore, the layered clay mineral is preferably
40.degree. or more, and further preferably 60.degree. or more in
water contact angle.
[0015] Furthermore, the layered clay mineral is preferably 30 .mu.m
or less, more preferably 20 .mu.m or less, and further preferably
10 .mu.m or less in average particle size.
[0016] The solid lubricant is characterized in that the inclusion
amount of the lipophilic lubricating component between the
particles and/or between the layers is preferably 5 mass % or more,
and further preferably 8 mass % or more in mass ratio to the total
mass of the carrier particles.
[0017] The layered clay mineral preferably has Mohs hardness of 2
or less, and further preferably 1.
[0018] The solid lubricant can be used in a preferred manner in a
lubricating coating agent for plastic working of metallic
materials, in particular, a lubricating coating agent for cold
plastic working.
[0019] The problem mentioned previously can be also solved by a
lubricating coating agent for a metal material, characterized in
that the lubricating coating agent contains the solid lubricant
mentioned previously.
[0020] The lubricating coating agent for a metal material according
to the present invention is a water-based lubricating coating agent
for a metal material, where a component including the solid
lubricant is dispersed in water, and the lubricating coating agent
is characterized in that the concentration of the solid lubricant
is 5 mass % or more in mass ratio to the mass of the total solid
content in the lubricating coating agent.
[0021] In addition, the problem mentioned previously can be also
solved by an oil-based lubricating coating agent for a metal
material, where a component including the solid lubricant is
dispersed in an oil. In this case, the concentration of the solid
lubricant is 5 mass % or more in mass ratio to the mass of the
total solid content in the lubricating coating agent.
[0022] Furthermore, the problem mentioned previously can be also
solved by a powder-based lubricating coating agent for a metal
material, which contains a component including the solid lubricant
according to the present invention. In this case, the concentration
of the solid lubricant is 5 mass % or more in mass ratio to the
mass of the total solid content in the lubricating coating
agent.
[0023] The problem mentioned previously can be also solved by a
surface-treated metal material characterized in that a coating
obtained by using the previously mentioned lubricating coating
agent for a metal material is formed on/over a metal material
surface to be 0.5 g/m.sup.2 or more as a dried coating amount.
[0024] A method for forming a lubricating coating and a method for
manufacturing a surface-treated metal material have only to include
a contact step of bringing a metal material into contact with the
previously mentioned lubricating coating agent for a metal
material. As a further preferred method, a method for forming a
lubricating coating for a metal material and a method for
manufacturing a surface-treated metal material can be applied,
which are characterized in that the methods include, before the
contact step mentioned previously, a cleanup step of cleaning up
the surface of a metal material by at least one cleanup means from
the group of shot blasting, sandblasting, alkaline degreasing, and
acid cleaning.
[0025] In the previously mentioned method for forming a lubricating
coating and method for manufacturing a surface-treated metal
material, a chemical conversion treatment step of coating the
surface of the metal material with a chemical conversion coating
can be also further applied before the contact step.
Effects of Invention
[0026] According to the present invention, the solid lubricant
characterized in that it includes the carrier particles including
the lipophilic lubricating component between the particles of
and/or the layers of the layered clay mineral, the lubricating
coating agent for a metal material, the surface-treated metal
material, and the method for forming a lubricating coating for a
metal material are applied, thereby achieving a non-black color and
great environmental conservation, producing excellent lubricity in
a stable manner even in a heavy working region, and thus making it
possible to prevent seizure and galling, and further achieving
excellent operability such as the moisture absorption resistance of
the lubricating coating, and further, excellent corrosion
resistance.
DESCRIPTION OF EMBODIMENTS
[0027] The present invention will be described in more detail.
First, the definition of a solid lubricant will be described.
According to Solid Lubrication Handbook (Japanese Society of
Tribologists: Yokendo Co., Ltd. (2009) 53), the solid lubricant
refers to a matter interposed between two objects for purposes such
as friction reduction, seizure prevention, and improved mold life
when the objects cause relative movement. In general, the solid
lubricant is used as one component of a lubricating coating for
plastic working, sliding members, press molding, and the like, and
specifically, layered clay minerals, inorganic salts, polymer
materials, soft metals, and the like are applied as the solid
lubricant.
[0028] In these solid lubricants, the layered clay minerals and the
inorganic salts preferably themselves have cleavage. Molybdenum
disulfide and graphite are typical examples thereof. The cleavage
refers to the property of splitting and fracturing at a crystal
face with the weakest atomic bonding force when a load is applied
to a solid lubricant. This property causes, in plastic working, the
solid lubricant to follow effective to an area expansion of the
worked surface during the working, thereby imparting slidability,
and at the same time, preventing galling.
[0029] A first feature of the present invention is that a cleavage
layered clay mineral includes a lipophilic lubricating component
between particles and/or between layers corresponding to cleavage
faces, thereby in addition to the action of the layered clay
mineral, further causing a solid lubricant to take a role as
carrier particles for causing the lipophilic lubricating component
to follow to an area expansion of the worked surface during
working. To explain in more detail, the layered clay mineral refers
to particles of two-dimensional layered crystals stacked parallel
and bonded. According to the present invention, the spaces between
surfaces of the layered crystals are defined as interlayer spaces.
Furthermore, when the previously mentioned layered crystals stacked
parallel and bonded are regarded as primary particles, multiple
primary particles may further aggregate (agglomerate) into larger
secondary particles (the layered clay mineral that folios the
secondary particles is referred to as an "aggregated layered clay
mineral"), and in this case, the spaces between the particles are
defined as inter-particle spaces. Both the interlayer spaces and
the inter-particle spaces are loosely bonded in a layered form,
which serve as cleavage faces that are capable of including a
lipophilic lubricating component according to the present
invention. The inclusion of the lipophilic lubricating component
between the particles of and/or between the layers of the cleavage
layered clay mineral allows the layered clay mineral and the
lipophilic lubricating component to follow at the same time, that
is, to take a role as carrier particles, even in working which is
high in working load and high in the area expansion factor of the
worked surface, such as cold plastic working, thereby imparting
slidability at the same time as the prevention of galling, and thus
allowing for improved lubricity. The previous techniques have never
achieved such a role taken as carrier particles. It is to be noted
that the "inclusion" herein means conditions that the lipophilic
lubricating component is trapped between the particles of and/or
between the layers of the layered clay mineral. More specifically,
in the carrier particles according to the present invention, when
the layered clay mineral is not cleaved, the lipophilic lubricating
component is held between the particles of and/or between the
layers of the layered clay mineral, and this condition is referred
to as an "inclusion" condition according to the present invention.
On the other hand, when the layered clay mineral is cleaved during
working, the lipophilic lubricating component included between the
particles of and/or between the layers of the layered clay mineral
exudes to the worked surface, and the exudation of the lipophilic
lubricating component follows along with the layered clay mineral
so as to wet the worked surface.
[0030] On the other hand, lubricating coating agents that use a
layered clay mineral including no lipophilic lubricating component
between particles and/or between the layers may cause coatings to
follow poorly to area expansions during working, due to the
shortage of slidability, thereby decreasing the lubricity, and thus
causing galling. Moreover, due to the high forming load, problems
may arise such as a short mold life.
[0031] According to the present invention, layered clay minerals
that are capable of including the lipophilic lubricating component
can include a smectite group of natural products and synthetic
products, a vermiculite group of natural products and synthetic
products, a mica group of natural products and synthetic products,
a brittle mica group of natural products and synthetic products, a
pyrophyllite group of natural products and synthetic products, and
a kaolinite group of natural products and synthetic products. These
layered clay minerals may be each used alone, or more than one
thereof may be used in combination.
[0032] In addition, a layered clay mineral with an organic
substance supported between layers of the layered clay mineral by
the method described in the International Publication WO
2012/086564 A may be used as the layered clay mineral mentioned
previously. Examples of the organic substance can include at least
one cationic organic compound (organic group+cationic group)
selected from organic ammonium compounds, organic phosphonium
compounds, and organic sulfonium compounds. In this regard, the
organic group of the organic compound is not particularly limited,
but preferred are straight-chain, branched-chain, and cyclic
(having a cyclic group) saturated hydrocarbon or unsaturated
hydrocarbon groups having 1 to 30 carbon atoms. In addition, the
hydrogen atoms bonded to the carbon atoms constituting the carbon
chains or the carbon rings may be substituted with other
substituent groups, some of the carbon atoms constituting the
carbon chains or the carbon rings may be substituted with other
atoms (such as O and S, for example), and furthermore, other
linkages (for example, ester linkages, ether linkages) may be
included between C--C chains. Preferred is an organic ammonium
compound composed of: an aliphatic hydrocarbon group (preferably
having 1 to 30 carbon atoms) which is advantageous for friction
reducing ability; and an ammonium group which is advantageous for
interlayer fixing ability. In this regard, chlorides, bromides,
iodides, nitrates, fluorides, hydroxides, and the like are
preferred as organic salts for use in the interlayer introduction
of the organic compound. Particularly preferred organic salts are
quaternary ammonium chlorides from which by-product salts are
easily removed by water rinsing (such as (capryl trimethyl ammonium
chlorides, lauryl trimethyl ammonium chlorides, stearyl trimethyl
ammonium chlorides, dicapryl dimethyl ammonium chlorides, dilauryl
dimethyl ammonium chlorides, and distearyl dimethyl ammonium
chlorides). Supporting the foregoing organic substances between the
layers of the layered clay mineral increases the interlayer
distance, and further hydrophobizes between layers of and the
surface of the layered clay mineral, thus advantageously allowing
the lipophilic lubricating component to be included more.
[0033] Furthermore, the layered clay mineral will be described in
more detail. Clay minerals are main-constituent minerals
constituting clay, layered silicate minerals (phyllosilicate
minerals), calcite, dolomite, feldspars, quartz, boiling stones
(zeolite), and others, minerals that have chain-like structures
(such as attapulgite, sepiolite), minerals that have no clearly
crystal structure (allophane), and the like are referred to as clay
minerals, and in general, layered silicate minerals among the clay
minerals are referred to as layered clay minerals.
[0034] The layered clay mineral forms a crystal structure that has
two-dimensional layers of positive and negative ions stacked
parallel and bonded, and this layered structure has therein two
structural units: one unit of a tetrahedral layer composed of
Si.sup.4+ and O.sup.2- surrounding the Si.sup.4+; the other of an
octahedral layer composed of Al.sup.3+ (or Mg.sup.2+, Fe.sup.2+, or
the like) and (OH).sup.- surrounding the Al.sup.3+.
[0035] In the tetrahedral layer, O located at four vertexes of the
tetrahedron and Si located in the center form tetrahedrons of
Si--O, which are linked to each other at the three vertexes to
spread two-dimensionally, thereby forming a layer lattice that has
a composition of Si.sub.4O.sub.10. The Si.sup.4+ is often
substituted with Al.sup.3+.
[0036] In the octahedral layer, octahedrons formed by (OH) or O
located at six vertexes of the octahedron and Al, Mg, Fe, or the
like located in the center are linked at each vertex to spread
two-dimensionally, thereby forming a layer lattice that has a
composition of Al.sub.2(OH).sub.6, Mg.sub.3(OH).sub.6, or the
like.
[0037] The octahedral layers include: a 3-octahedral type that has
lattice points all occupied with a divalent cation (such as
Mg.sup.2+) at the lattice point of cation surrounded by six anions;
and a 2-octahedral type that has 2/3 lattice points occupied with a
trivalent cation (such as Al.sup.3+) at the lattice point of
cation, and 1/3 lattice points remaining vacant.
[0038] There are two types of combinations of tetrahedral layers
and octahedral layers: one of the combinations is a 2:1 type
structure that has, as a unit, a linkage of two tetrahedral layers
and one octahedral layer sandwiched therebetween; and the other is
a 1:1 type structure that has, as a unit, a linkage of one
tetrahedral layer and one octahedral layer. The smectite group,
vermiculite group, mica group, and pyrophyllite group mentioned
previously refer to layered clay minerals that have the 2:1 type
structure, whereas the kaolinite group refers to layered clay
minerals that have the 1:1 type structure.
[0039] With regard to the relationship between the hydrophilicity
of the layered clay mineral and the crystal structure, for example,
as for kaolin, the layered clay mineral has the 1:1 crystal
structure, which is believed to exhibit hydrophilicity due to the
orientation of octahedrons with hydrophilic groups (such as OH) at
the surface. On the other hand, in the case of the 2:1 crystal
structure, there is believed to be a strong tendency to be lower in
hydrophilicity than the 1:1 structure, because of the orientation
of tetrahedrons having hydrophobic groups (SiO) at the surface.
[0040] To explain layered clay minerals that belong to the
respective groups in more detail, the smectite group includes
montmorillonite, beidellite, nontronite, saponite, iron saponite,
hectorite, sauconite, and stevensite, the vermiculite group
includes di.vermiculite and tri.vermiculite, the mica group
includes muscovite, palagonite, illite, phlogopite, biotite,
lepidolite, and lepidolite, the brittle mica group includes
margarite and clintonite, the pyrophyllite group includes
pyrophyllite and talc, and the kaolinite group includes kaolinite,
dickite, nacrite, halloysite, chrysotile, lizardite, and
antigorite. These layered clay minerals can be all used for a
lubricating coating agent for metal materials according to the
present invention, but among these minerals, particularly preferred
is at least one selected from the two layered clay minerals that
belong to the pyrophyllite group mentioned above. The reason is
because the layered clay minerals that belong to the pyrophyllite
group are low in Mohs hardness and excellent in lipophilicity.
[0041] Next, in the solid lubricant according to the present
invention, the lipophilic lubricating component included between
the particles of and/or between the layers of the layered clay
mineral mentioned previously is at least one selected from an oil,
an extreme-pressure agent, a soap, and a wax.
[0042] At least one selected from the group consisting of mineral
oils, animal and plant oils, and synthetic oils can be used as the
oil. More specifically, for example, naphthenic mineral oil or
paraffinic mineral oil-based machine oils, turbine oils, spindle
oils, and the like can be used as the mineral oils. For example,
palm oils, rapeseed oils, coconut oils, castor oils, beef tallow,
pork oils, whale oils, fish oils, or these components with ethylene
oxide added thereto (for example, polyoxyethylene castor oils
(ethylene oxide adducts)) can be used as the animal and plant oils.
Ester oils (for example, esters of polyhydric alcohols such as
ethylene glycol and trimethylolpropane and fatty acids such as
stearic acid, oleic acid, and linoleic acid (e.g.,
trimethylolpropane trioleate)), silicone oils (for example,
polydimethylsiloxane and polydiphenylsiloxane), and the like can be
used as the synthetic oils. Hydrophobic organic compounds (for
example, organic ammonium compounds, organic phosphonium compounds,
organic sulfonium compounds, organic amine compounds) can be also
used as synthetic oils for the lipophilic lubricating component
according to the present invention. The naphthenic mineral oils are
preferred as the mineral oils; the palm oils and the castor oils of
the plant oils, and the oils with ethylene oxide added thereto
(polyoxyethylene plant oils (ethylene oxide adducts)) are preferred
as the animal and plant oils; and the ester oils
(trimethylolpropane trioleate) are preferred as the synthetic
oils.
[0043] An agent that effectively develops an extreme-pressure
effect at the friction surface between a metal material and a tool
during working is preferred as the extreme-pressure agent. Examples
of such an extreme-pressure agent can include sulphurized olefins,
sulfurized esters, sulphites, thiocarbides, phosphate esters,
phosphite esters, molybdenum dithiocarbamate (MoDTC), molybdenum
dithiophosphate (MoDTP), zinc dithiophosphate (ZnDTP), and
tricresyl phosphate, and the phosphates (tricresyl phosphate) are
preferred. According to the present invention, while it is also
possible for the oil and the extreme-pressure agent to be each
included alone in the layered clay mineral, it is preferable to use
the oil and the extreme-pressure agent in combination in order to
achieve higher lubricity. In this case, the ratio between the oil
and the extreme-pressure agent preferably falls within the range of
1: 0.03 to 1:1 in mass ratio. When the ratio between the oil and
the extreme-pressure agent is 1:0.03 to 1:1 in mass ratio, the
lubricity is further improved with an extreme-pressure action
imparted. When the ratio between the oil and the extreme-pressure
agent exceeds 1:1, the extreme-pressure action is nearly
saturated.
[0044] It is preferable to use, as the soap, an alkali metal salt
of a fatty acid (such as stearic acid, myristic acid, palmitic
acid) having 12 to 26 carbon atoms, or a metal soap obtained by
reacting a fatty acid (such as stearic acid, myristic acid,
palmitic acid) having 12 to 26 carbon atoms and at least one metal
selected from zinc, calcium, barium, aluminum, and magnesium. In
addition, the soap preferably has a melting point of 100 to
250.degree. C. An alkali metal salt of a stearic acid and a metal
soap (zinc stearate) obtained by reacting a fatty acid having 12 to
26 carbon atoms and zinc are more preferred as the soap.
[0045] The wax is not to be considered particularly specified in
terms of structure and type, but preferably has a melting point of
70 to 150.degree. C., because the wax is melted by heat generated
during working, thereby developing lubricity. Waxes that have a
melting point in this range include, for example, microcrystalline
waxes, polyethylene waxes, polypropylene waxes, and carnauba waxes,
and polyethylene waxes are preferred.
[0046] Next, in order to achieve excellent lubricity, it is
important for the lipophilic lubricating component to be included
between particles of and/or between layers of the layered clay
mineral in a more efficient manner. Parameters regarding the
efficiency of the inclusion will be described. First, the
parameters of the lipophilic lubricating component include a
solubility parameter (SP value, unit (cal/cm.sup.3).sup.1/2). The
solubility parameter refers to a parameter for solubility or
compatibility in a two-component system. The solubility or
compatibility is supposed to be better as the solubility parameters
of the components are closer in value to each other. Various
methods are disclosed for the measurement method. For example,
methods such as a method of evaluation from solubility in a solvent
with a known SP value, a Fedors method based on theoretical
calculation, and a turbidimetric titration method are typical
measurement methods. The turbidimetric titration method devised by
K. WSuh, et al. was applied to the method for measuring the SP
value according to the present invention (J. Appl. Polym. Sci., 12,
2359 (1968)). In accordance with the turbidimetric titration
method, the SP value of the lipophilic lubricating component can be
evaluated by dissolving the lipophilic lubricating component in a
good solvent with a known SP value, and carry out turbidimetric
titration with a poor solvent that is higher in SP value than the
good solvent and a poor solvent that is lower in SP value than the
good solvent. The SP value of water is approximately 23, and as the
SP value of a target component is lower than that of water, the
lipophilicity is higher.
[0047] The lipophilic lubricating component for use in the present
invention preferably has an SP value of 10 or less, and further
preferably 9 or less. When the SP value of the lipophilic
lubricating component exceeds 10, the amount of the lipophilic
lubricating component included between the layers of the layered
clay mineral may be decreased due to decreased lipophilicity,
thereby decreasing the lubricity. In addition, due to the decreased
hydrophobicity of the lubricating component, the barrier properties
against corrosive factors such as water and chlorine may be
decreased, thereby decreasing the corrosion resistance. The lower
limit of the SP value of the lipophilic lubricating component is
not to be considered particularly specified, but for example, 7 or
more.
[0048] In the case of using two or more types in mixture in the
lipophilic lubricating component (for example, the oil and the
extreme-pressure agent), as long as the difference is 1.5 or less
between the respective SP values, excellent compatibility can
achieve higher lubricity.
[0049] Furthermore, the solid lubricant according to the present
invention has preferably lipophilic properties between layers of
and on the surface of the layered clay mineral. Parameters therefor
include a water contact angle. The water contact angle at the
surface of the layered clay mineral alone may be preferably
40.degree. or more, further preferably 60.degree. or more. The
upper limit of the water contact angle at the layered clay mineral
is not to be considered particularly specified, but for example,
150.degree. or less. When the water contact angle at the surface of
the layered clay mineral alone is 40.degree. or more, the lubricity
and the corrosion resistance are further improved. In addition, in
the combination of the layered clay mineral alone and the
lipophilic lubricating component, further preferably, the water
contact angle at the layered clay mineral alone is 40.degree. or
more, and the previously mentioned lipophilic lubricating component
has an SP value of 10 or less. As long as the water contact angle
at the layered clay mineral alone is 40.degree. or more, and as
long as the previously mentioned lipophilic lubricating component
has an SP value of 10 or less, the inclusion of the lipophilic
lubricating component between the particles and/or between the
layers can be achieved in a more efficient manner, because of high
mutual lipophilicity and affinity.
[0050] The inclusion amount of the lipophilic lubricating component
is preferably 5 mass % or more, and further preferably 8 mass % or
more in mass ratio to the total mass of the carrier particles. When
the inclusion amount falls below 5 mass %, the lubricity during
working may be decreased, thereby causing galling. In addition, the
corrosion resistance may be also decreased. The upper limit of the
inclusion amount of the lipophilic lubricating component is not to
be considered particularly limited, but for example, 50 mass % or
lower.
[0051] The layered clay mineral for use in the solid lubricant
according to the present invention preferably has Mohs hardness of
2 or less from the perspective of lubricity. Further preferred Mohs
hardness is 1. The reason is because while the solid lubricant is
broken to follow in the direction of area expansion at the surface
worked in plastic working or press working, there is a tendency to
achieve a lower friction coefficient and a better carrier property
for the lipophilic lubricating component as the layered clay
mineral is lower in Mohs hardness, and as a result, better
lubricity is achieved. The "carrier property" herein means that as
a result of decreasing the friction coefficient of the layered clay
mineral, the layered clay mineral is made more likely to follow in
the direction of area expansion, and the lipophilic lubricating
component is thus made likely to follow, along with the layered
clay mineral, in the direction of area expansion at the worked
surface. It is to be noted that the Mohs hardness can be measured
with a Mohs scale. More specifically, 10 types (10-level Mohs
hardness from 1 to 10:1 for the softest and 10 for the hardest) of
minerals that differ in hardness are adopted as reference
materials, thereby evaluating whether the surface of the target
material is scratched by a reference material or not. When the
surface is not scratched, the reference material with higher
hardness is used and evaluated until being scratched. When the
surface is scratched, it is confirmed that the surface of the
reference material is reversely scratched by the target material,
thereby determining the Mohs hardness of the substance. This is
because the materials can scratch each other as long as the
materials have the same hardness.
[0052] The solid lubricant including the lipophilic lubricating
component according to the present invention can be used as a solid
lubricant for any lubricating coating agent of: water-based
lubricating coating agent; oil-based lubricating coating agent;
powder-based lubricating coating agent.
[0053] In the case of use as a solid lubricant for water-based
lubricating coating agents, the solid lubricant according to the
present invention may be dispersed in water with a surfactant or
the like. The concentration of the solid lubricant is adjusted to
be 5 mass % or more, more preferably 20 mass % or more in mass
ratio to the mass of the total solid content (coating component) in
the lubricating coating agent. The solid lubricant concentration of
5 mass % or more can enhance the lubricity dramatically, and the
concentration of 20 mass % or more can further enhance the
lubricity. On the other hand, the upper limit of the concentration
of the solid lubricant is not to be considered particularly
limited, but for example, 95 mass % or lower, preferably 80 mass %
or lower.
[0054] In addition, the basic idea about the concentration of the
total solid content (coating component) including the solid
lubricant is that the concentration is adjusted appropriately such
that the dried coating amount is 0.5 g/m.sup.2 or more. However,
the appropriate total solid content concentration in the
lubricating coating agent may possibly vary depending on the
condition (such as roughness) of the metal surface and the required
degree of working, but typically, the concentration of the total
solid content (coating component) including the solid lubricant in
the lubricating coating agent is preferably 3 mass % or more when
the total mass (also including water) of the lubricating coating
agent is regarded as 100 mass %. The concentration lower than the
foregoing concentration reduces the dried coating amount, thereby
leading to failure to achieve expected lubricity in some cases. On
the other hand, the upper limit of the concentration of the total
solid content is not to be considered particularly limited, but for
example, 70 mass % or lower, more preferably 50 mass % or
lower.
[0055] Further, the concentration of the total solid content
(coating component) with respect to the total mass (also including
water) of the lubricating coating agent can be measured by the
following method. More specifically, the lubricating coating agent
is collected in a defined amount into a container made of Teflon
(registered trademark), and the collection amount is weighed
accurately. Thereafter, volatile components such as water are
evaporated in an oven at 110.degree. C. for 2 hours, and the amount
of residue (non-volatile component) is weighed accurately. The
total solid content concentration is calculated from the following
formula with the respective weighing values. It is to be noted that
the weighing value after drying in the following formula
corresponds to "the mass of the total solid content (coating
component)" in calculating the concentration of the solid lubricant
in the water-based lubricating coating agent.
total solid content concentration (mass %)=[(weighing value after
drying)/(weighing value before drying)].times.100
[0056] The components of the previously mentioned water-based
lubricating coating agent other than the solid lubricant include a
base component for a lubricating coating and/or a binder component.
Specifically, at least one selected from a water-soluble inorganic
salt, a water-soluble organic salt, a water-based resin, an
oil-based resin, an oil, an extreme-pressure agent, a soap, and a
wax can be applied. The combination of the solid lubricant
according to the present invention with the foregoing components
can form the solid lubricant more strongly to metal material
surfaces, thereby making it possible to produce lubricity even in
severer worked regions. It is to be noted that the water-soluble
inorganic salt and the water-soluble organic salt, as well as the
water-based resin have moisture absorption properties, and have the
property of being likely to decrease the lubricity. However, in the
lubricating coating agent according to the present invention, the
solid lubricant composed of the carrier particles including the
lipophilic lubricating component between the layers of and/or
between the particles of the layered clay mineral makes a large
contribution on lubricity, and the moisture absorption of the
component added as a base component for a lubricating coating
and/or a binder component, such as the water-soluble inorganic
salt, the water-soluble organic salt, and the water-based resin has
substantially no problem.
[0057] Specifically, the water-soluble inorganic salt has at least
one selected from the group consisting of sulfates, silicates,
borates, molybdates, vanadates, tungstates, phosphates, and
condensed phosphates. The water-soluble organic salt has at least
one selected from the group consisting of malates, succinates,
citrates, and tartrates. The cations of these salts have at least
one selected from the group consisting of a sodium ion, a potassium
ion, a lithium ion, an ammonium ion, amines (such as ethylamine),
and alkanolamines (such as monoethanolamine and diethanolamine).
Among these salts, the tungstates, the borates, and the condensed
phosphates are particularly superior as a base component for a
lubricating coating and a binder, thereby making it possible to
achieve high lubricity.
[0058] As the water-based resin, that is, water-soluble or
water-dispersible polymer resin, at least one can be selected from
polymer resins of 1,000 to 1,000,000 in weight average molecular
weight. In addition, the water-dispersible polymer resin is
preferably 0.5 to 50 .mu.m in average particle size (volumetric
basis). The type of the polymer resin is not particularly limited
as long as the polymer resin has coating formability, and stable
solubility or dispersibility, but for example, polymer resins can
be used, such as acrylic resins, urethane resins, epoxy resins,
phenolic resins, hydroxyethyl cellulose, carboxymethyl cellulose,
and polyvinyl alcohol. It is to be noted that the weight average
molecular weight of the polymer resin can be measured by a gel
permeation chromatography method (GPC method).
[0059] In addition, the oil, the extreme-pressure agent, the soap,
and the wax are also intended to serve as lipophilic lubricating
components, and according to the present invention, serves as
components to be included between the particles of and/or between
the layers of the layered clay mineral, but can be also used as a
base component for a coating. The same as those included between
the particles of and/or between the layers of the layered clay
mineral may be used for the oil, the extreme-pressure agent, the
soap, and the wax that can be used as a base component for a
lubricating coating or a binder.
[0060] In the case of using the oil and the extreme-pressure agent
as a base component of the water-based lubricating coating agent
according to the present invention, the lubricity is enhanced more
when the oil is used in combination with the extreme-pressure
agent. The ratio between the oil and the extreme-pressure agent
preferably falls within the range of 1:0.03 to 1:1 in mass
ratio.
[0061] In the lubricating coating agent, any of non-ionic
surfactants, anionic surfactants, amphoteric surfactants, and
cationic surfactants can be used as a surfactant that disperses, in
water, the solid lubricant according to the present invention and
the oil and the extreme-pressure agent as base components. The
non-ionic surfactants include, but not particularly limited
thereto, for example, polyoxyethylene alkyl esters obtained from
polyoxyethylene alkyl ether, polyoxyalkylene (ethylene and/or
propylene) alkyl phenyl ether, or polyethylene glycol (or ethylene
oxide) and a higher fatty acid (for example, 12 to 18 carbon
atoms); and polyoxyethylene sorbitan alkyl esters composed of
obtained from sorbitan, polyethylene glycol, and a higher fatty
acid (for example, 12 to 18 carbon atoms). The anionic surfactants
include, but not particularly limited thereto, for example, fatty
acid salts, sulfates, sulfonates, phosphates, and dithiophosphates.
The amphoteric surfactants include, but not particularly limited
thereto, for example, amino acid-type and betaine-type
carboxylates, sulfates, sulfonates, and phosphates. The cationic
surfactants include, but not particularly limited thereto, for
example, aliphatic amine salts and quaternary ammonium salts. These
surfactants can be each used alone, or two or more of the
surfactants can be used in combination.
[0062] The concentration of the surfactant is preferably 0.5 to 20
mass % in mass ratio to the mass of the total solid content
(coating component) in the lubricating coating agent. When the
proportion of the surfactant exceeds 20 mass %, the dispersibility
of the solid lubricant is improved, while the lubricating coating
may become fragile, thereby decreasing the lubricity. On the other
hand, when the proportion falls below 0.5 mass %, the
dispersibility of the solid lubricant is worsened, thereby making
it impossible to form any uniform lubricating coating.
[0063] Furthermore, the oil and the extreme-pressure agent included
in the layered clay mineral, or the oil and the extreme-pressure
agent as a base component for a lubricating coating may be blended
with a viscosity index improver for the purpose of achieving higher
lubricity. Specifically, at least one viscosity index improver
selected from polymethacrylates, olefin copolymers, and
polyisobutylenes can be used. The viscosity index (JIS K2283) is
preferably 100 or more, and more preferably 200 or more.
[0064] The concentration of the viscosity index improver is 1 to 10
mass %, more preferably 1 to 5 mass % in mass ratio to the total
amount of the oil and/or the extreme-pressure agent. The addition
of the viscosity index improver can suppress the decrease in oil
viscosity due to a temperature increase during working. Thus, the
amounts of the oil and extreme-pressure agent that can follow along
with the solid lubricant are increased, thereby making it possible
to make a further improvement in lubricity.
[0065] Next, in the case of using the solid lubricant according to
the present invention for an oil-based lubricating coating agent,
the oil alone, the extreme-pressure agent alone, or the oil and the
extreme-pressure agent combined at 1:0.03 to 1:1 in mass ratio may
be used as a base oil. In this case, the concentration of the solid
lubricant is 5 mass % or more, more preferably 20 mass % or more,
and further preferably 30 mass % or more in mass ratio to the mass
of the total solid content in the lubricating coating agent. The
lubricity can be further enhanced as the concentration of the solid
lubricant is increased to 5 mass % or more, 20 mass % or more, and
30 mass % or more. On the other hand, the upper limit of the
concentration of the solid lubricant is not to be considered
particularly limited, but for example, 95 mass % or lower,
preferably 80 mass % or lower.
[0066] In this case, the same as those used for the water-based
lubricating coating agent mentioned previously may be applied for
the oil, the extreme-pressure agent, the soap, the wax, the
oil-based resin, and the viscosity index improver as a base
component.
[0067] Furthermore, an oil-based resin that is dissoluble or
dispersible in an oil may be added as a binder. Specifically, at
least one resin of 1,000 to 1,000,000 in weight average molecular
weight selected from the group consisting of acrylic resins,
urethane resins, epoxy resins, phenolic resins, and the like can be
used as a binder. In addition, the additive concentration is not
particularly limited, but preferably falls within the range of 3 to
50 mass % in mass ratio to the total solid content of the
lubricating coating.
[0068] In the case of using the solid lubricant according to the
present invention as a powder-based lubricating coating agent, the
solid lubricant may be used in a way that the concentration of the
solid lubricant is adjusted to 5 mass % or more, more preferably 30
mass % or more in mass ratio to the total solid content mass in the
lubricating coating agent. The adjustment of the solid lubricant
concentration to 5 mass % or more can enhance the lubricity
dramatically, and the adjustment thereof to 30 mass % or more can
further increase the lubricity. As the powder-based lubricating
coating agent, the solid lubricant itself may be applied directly
to a metal material by an electrostatic powder coating or the like,
and used (in this case, the concentration of the solid lubricant is
100 mass %), and a polymer resin may be used as a binder for the
solid lubricant. The type of such a polymer resin is not
particularly limited, but a powder resin of 1,000 to 1,000,000 in
weight average molecular weight and 0.5 to 30 .mu.m in average
particle size can be applied, such as an acrylic resin, a urethane
resin, an epoxy resin, a phenolic resin, a hydroxyethyl cellulose,
a carboxymethyl cellulose, and a polyvinyl alcohol.
[0069] A surface-treated metal material according to the present
invention is characterized in that the above-described lubricating
coating agent for metal materials according to the present
invention is provided on/over a metal material surface to achieve a
coating amount of 0.5 g/m.sup.2 or more as a dry coating amount.
The set coating amount may be determined appropriately depending on
the working level required. However, when the coating amount falls
below 0.5 g/m.sup.2, the lubricating coating may fail to fully coat
a metal material surface depending on the roughness of the surface,
and attention is thus required in terms of lubricity and corrosion
resistance. In addition, the upper limit of the coating amount is
not particularly specified, but even when the coating is formed in
excess of 40 g/m.sup.2, lubricity improved enough to meet the
formation can be no longer expected, which is not economical, and
problems may be even caused, such as defectively even application,
defective adhesion, and the production of indentation by the
remaining coating.
[0070] A method for forming a lubricating coating for a metal
material according to the present invention and a method for
manufacturing a surface-treated metal material according to the
present invention are characterized by including a contact step of
bringing a metal material into contact with the lubricating coating
agent for metal materials according to the present invention.
Specifically, an immersion method, a flow coating method, a spray
method, brush coating, a liquid electrostatic coating method, and
the like can be applied in the case of the water-based lubricating
coating agent and the oil-based lubricating coating agent. For the
application, the surface has only to be covered sufficiently with
the lubricating coating agent according to the present invention,
and there is no particular limit on the application time. There is
a need to dry the water-based lubricating coating agent after
applying the agent. For the drying, the agent may be left at room
temperature, but preferably at 60 to 150.degree. C. for 1 to 30
minutes.
[0071] In the case of the water-based lubricating coating agent, in
order to enhance drying characteristics, it is preferable to warm
the metal material to 60 to 100.degree. C., and bring the warmed
metal material into contact with the water-based lubricating
coating agent. It is to be noted that the metal material may be
brought into contact with the water-based lubricating coating agent
warmed to 50.degree. C. to 90.degree. C. Thus, the drying
characteristics are improved significantly, thereby making drying
possible at room temperature in some cases, and thus making it
possible to reduce the thermal energy loss.
[0072] The method for applying the powder-based lubricating coating
agent is not particularly limited, but it is preferable to apply an
electrostatic powder coating method from the perspective of ease of
controlling the even application and coating thickness.
[0073] Furthermore, in order to improve the adhesion of the
lubricating coating, it is preferable to clean up the metal
material by at least one approach selected from the group
consisting of shot blasting, sandblasting, alkaline degreasing, and
acid cleaning (cleanup step) before the lubricating coating
treatment (contact step). In this regard, the cleanup is intended
to remove oxide scale grown by annealing or the like, and various
types of contamination (e.g., oil). In particular, in recent years,
reduced wastewater treatment burdens have been desired due to
environmental concerns. In this case, the absence of wastewater can
be achieved just by cleaning up the metal material surface by shot
blasting, and then carrying out the contact step with the use of
the lubricating coating agent according to the present
invention.
[0074] The lubricating coating agent for metal materials according
to the present invention is a non-reactive lubricating coating
agent that involves no chemical conversion reaction, but after
forming a chemical conversion coating in advance on the metal
material surface (chemical conversion treatment step), the
lubricating coating according to the present invention can be
formed thereon, and used. Components for such a chemical conversion
coating include: a phosphate of at least one selected from Zn, Fe,
Mn, Ni, Co, Ca, Mg, and Al (metal material: iron and steel,
aluminum, magnesium, and the like); an iron oxalate (metal
material: stainless steel); an aluminum fluoride (metal material:
aluminum); and a zirconium oxide (metal material: iron and steel,
aluminum, magnesium, and the like). The application of the chemical
conversion treatment further improves the lubricity, thereby making
it possible to maintain excellent lubricity, for example, even in
poor environments such as high-humidity environments.
[0075] In the method for manufacturing the solid lubricant
according to the present invention, parameters for efficiently
including the lipophilic lubricating component between particles of
and/or between layers of the layered clay mineral include three of:
(1) the lipophilicity of the layered clay mineral and the SP value
of the lipophilic lubricating component; (2) inclusion method; and
(3) the average particle size and aspect ratio of the layered clay
mineral. The lipophilicity (water contact angle) of the layered
clay mineral and the SP value of the lipophilic lubricating
component are adapted as mentioned previously.
[0076] Examples of the inclusion method include, as an example, in
the case of an oil and an extreme-pressure agent that are liquid at
room temperature, an method of adding the oil and the
extreme-pressure agent in predetermined amounts to a powder of the
layered clay mineral, and causing the mineral to include therein
the oil and the agent while stirring. In addition, in the case of
desiring the inclusion achieved in a short period of time and
desiring the increased inclusion amount, it is preferable to apply
a so-called reduced-pressure impregnation method of, not simply the
addition/stirring, but mixing the layered clay mineral, the oil,
and the extreme-pressure agent in a decompression tank, and then
returning the pressure to the atmospheric pressure, a method of
inclusion with the oil warmed and thus reduced in viscosity, or the
like. On the other hand, methods for the inclusion of a soap or a
wax that is solid at room temperature include a method of turning
the soap or the wax into a liquid at a temperature equal to or
higher than the melting point thereof, and then mixing the liquid
with the layered clay mineral, thereby causing the layers to
include the liquid therebetween, and a method of applying the
lubricant to a metal material surface, and then putting the
material in an oven kept at a temperature equal to or higher than
the melting point, thereby causing the layers to include the soap
or the wax therebetween during the drying. In each case, mixing
with the lipophilic lubricating component in an amount equal to or
larger than the amount includable between the layers can interpose
the lipophilic lubricating component not only between the layers,
but also between the particles.
[0077] The layered clay mineral is preferably 0.5 to 30 .mu.m, more
preferably 1 to 20 .mu.m, and further preferably 1 to 10 urn in
average particle size. The average particle size of 30 .mu.m or
less makes the lipophilic lubricating component likely to be
included between the layers, thus improving the lubricity and the
corrosion resistance. In addition, as the average particle size is
reduced to 30 .mu.m or less, 20 .mu.m or less, and 10 .mu.m or
less, the lubricity is further improved. Even when the average
particle size is less than 0.5 .mu.m, the lubricity and the
corrosion resistance are favorable, and the average particle size
is selected from the perspective of cost (manufacturing
cost)-effectiveness (lubricity and corrosion resistance).
[0078] Furthermore, the aspect ratio in a cross section of the
layered clay mineral preferably falls within the range of 3 to 150,
more preferably 5 to 100, further preferably 5 to 30. The aspect
ratio in excess of 150 reduces the inclusion amount of the
lipophilic lubricating amount, thereby possibly decreasing the
lubricity and the corrosion resistance in some cases. In addition,
the lubricity is further improved as the aspect ratio is reduced to
150 or less, 100 or less, and 30 or less. In contrast, when the
aspect ratio falls below 3, the inclusion amount of the lipophilic
lubricating component has no problem, but due to the layered clay
mineral particles increased in thickness, the following performance
of the lubricating coating may be decreased, thereby deteriorating
the lubricity.
[0079] The average particle sizes of the water-dispersible polymer
resin and layered clay mineral can be measured by a laser
diffraction method (volumetric basis). The average particle size of
the layered clay mineral according to the present invention is
intended for primary particles, and in order to keep as much as
possible from being affected by secondary particles as aggregates
of the primary particles, particle sizes are measured after
enhancing redispersion (breaking secondary particles of the primary
particles aggregated, thereby separating the secondary particles
again into primary particles) with ultrasonic for approximately 3
to 5 minutes in advance. Thus, the average particle size for
substantially primary particles can be measured by eliminating as
much as possible the influence of secondary particles of the
primary particles aggregated. Therefore, the average particle size
of the layered clay mineral according to the present invention
refers to an average value on a volumetric basis for the particle
sizes of the primary particles of the layered clay mineral.
[0080] In addition, the aspect ratio according to the present
invention is supposed to be defined as an aspect ratio in a cross
section of the layered clay mineral, and obtained from the
following formula. More specifically, the layered clay mineral for
use in the present invention have plate-like or scale-like
particles of two-dimensionally layered crystals stacked parallel
and bonded as mentioned previously, and the proportion of the
length of a planar part (that is, a crystal face parallel to a
cleavage face) to the thickness of the particle (the length in a
direction perpendicular to the cleavage face) corresponds to the
aspect ratio in a cross section of the layered clay mineral. The
thickness of the layered clay mineral particle and the length of
the planar part can be measured at a magnification on the order of
3000 times with a scanning electron microscope (SEM). It is to be
noted that the thickness of the layered clay mineral particle
refers to a thickness that can be observed in the case of
observation at approximately 3000-fold magnification with a SEM,
but is not necessarily considered to mean the thickness of a unit
lattice.
aspect ratio=length of planar part of particle/thickness of
particle
[0081] As just described, the lipophilicity of the layered clay
mineral and the SP value of the lipophilic lubricating component as
well as the average particle size and aspect ratio of the layered
clay mineral are adapted to fall within the specific ranges,
thereby making it possible to ensure, in a more reliable manner,
that the inclusion amount of the lipophilic lubricating component
into the layered clay mineral is 5 mass % or more. Furthermore, the
reduced-pressure impregnation method, the method of mixing, with
the layered clay mineral, a soap or a wax turned into a liquid at a
temperature equal to or higher than the melting point thereof,
thereby causing the particles and the layers to include the soap or
the wax therebetween, or a method of applying the lubricant to a
metal material surface, and then putting the material in an oven
kept at a temperature equal to or higher than the melting point,
thereby causing the particles and layers to include the soap or the
wax therebetween during the drying is used, thereby making it
possible to further increase the inclusion amount of the lipophilic
lubricating component.
EXAMPLES
[0082] Effects of the present invention will be verified with
reference to examples and comparative examples. Here are details of
the respective components for manufacturing lubricating coating
agents for metal material for use in the examples and comparative
examples.
[0083] [Description of Raw Material for Use in Manufacture of
Lubricating Coating Agent]
[0084] Here are details of layered clay minerals (before the
inclusion of the lipophilic lubricating component) used for tests.
The average particle size of the layered clay mineral was measured
by a laser diffraction method on a volumetric basis under the
following conditions after the redispersion of the layered clay
mineral into primary particles with ultrasonic in water for 3
minutes in advance.
[0085] name of measurement machine: LA-920 from Horiba, Ltd.
[0086] data loading frequency: 10 times
[0087] calculation frequency: 30 times
[0088] ultrasound intensity: 7
[0089] ultrasound time: 3 minutes
[0090] dispersion medium circulation speed: 3
[0091] In addition, the aspect ratio was calculated from the
thickness of the particle (the length in a direction perpendicular
to a cleavage face) and the length of the planar part (that is, the
crystal face parallel to the cleavage face) by observation of the
layered clay mineral at a magnification of 3000 times with a
scanning electron microscope. The layered clay mineral was
subjected to an organic treatment in accordance with the method
described in International Publication WO 2012/086564 A. The water
contact angle was measured with a bed of layered clay mineral
powder between two copper plates (50.times.50 mm), which was
pressed at a tightening force of 100 kgf into the form of a
coating. An automatic contact angle meter DM-501 from Kyowa
Interface Science Co., Ltd. was used for the measurement.
[0092] [Layered Clay Mineral]
[0093] <By Water Contact Angle>
[0094] A-1 kaolinite: average particle size 3 .mu.m, water contact
angle 20.degree., Mohs hardness 2
[0095] aspect ratio: 20
[0096] A-2 organic treated kaolinite: average particle size 3
.mu.m, water contact angle 40.degree., Mohs hardness 2
[0097] aspect ratio: 20
[0098] distearyl dimethyl ammonium chloride treated with an organic
matter corresponding to 0.2 molar quantity with respect to the
cation exchange capacity (CEC value)
[0099] A-3 organic treated kaolinite: average particle size 3
.mu.m, water contact angle 60.degree., Mohs hardness 2
[0100] aspect ratio: 20
[0101] distearyl dimethyl ammonium chloride treated with an organic
matter corresponding to 0.4 molar quantity with respect to the
cation exchange capacity (CEC value)
[0102] A-4 organic treated kaolinite: average particle size 3
.mu.m, water contact angle 110.degree., Mohs hardness 2
[0103] aspect ratio: 20
[0104] distearyl dimethyl ammonium chloride treated with an organic
matter corresponding to 1.0 molar quantity with respect to the
cation exchange capacity (CEC value)
[0105] <By Mohs Hardness>
[0106] A-5 talc: average particle size 3 .mu.m, water contact angle
110.degree., Mohs hardness 1
[0107] aspect ratio: 20
[0108] A-6 synthetic mica: average particle size 3 .mu.m, water
contact angle 110.degree., Mohs hardness 3
[0109] aspect ratio: 20
[0110] <By Average Particle Size>
[0111] A-7 talc: average particle size 0.5 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0112] aspect ratio: 20
[0113] A-8 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0114] aspect ratio: 20
[0115] A-9 talc: average particle size 20 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0116] aspect ratio: 20
[0117] A-10 talc: average particle size 30 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0118] aspect ratio: 20
[0119] A-11 talc: average particle size 40 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0120] aspect ratio: 20
[0121] <By Aspect Ratio>
[0122] A-12 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs
[0123] hardness 1
[0124] aspect ratio: 2.5
[0125] A-13 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0126] aspect ratio: 3
[0127] A-14 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0128] aspect ratio: 5
[0129] A-15 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0130] aspect ratio: 30
[0131] A-16 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0132] aspect ratio: 100
[0133] A-17 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0134] aspect ratio: 150
[0135] A-18 talc: average particle size 10 .mu.m, water contact
angle 110.degree., Mohs hardness 1
[0136] aspect ratio: 170
[0137] <Black Base>
[0138] A-19 molybdenum disulfide: average particle size 3 .mu.m,
water contact angle 120.degree., Mohs hardness 1
[0139] aspect ratio: 20
[0140] Here are lipophilic lubricating components. It is to be
noted that the previously mentioned turbidimetric titration method
was applied to the method for measuring the solubility parameter
(SP value).
[0141] <Oil>
[0142] B-1 plant oil: palm oil, SP value 8.5
[0143] B-2 plant oil: castor oil, SP value 9.0
[0144] B-3 plant oil: polyoxyethylene castor oil (product with 0.5
mol of ethylene oxide added), SP value 10.0
[0145] B-4 plant oil: polyoxyethylene castor oil (product with 1
mol of ethylene oxide added), SP value 11.6
[0146] B-5 mineral oil: naphthenic mineral oil, SP value 8.3
[0147] B-6 synthetic oil: trimethylolpropane trioleate, SP value
8.7
[0148] <Extreme-Pressure Agent>
[0149] B-7 tricresyl phosphate, SP value 8.9
[0150] <Soap>
[0151] B-8 zinc stearate, melting point 120.degree. C., SP value
8.7
[0152] <Wax>
[0153] B-9 polyethylene wax, melting point 110.degree. C., SP value
8.1
[0154] <Mixture of Oil and Extreme-Pressure Agent>
[0155] B-10 (B-1): (B-7)=1:0.02 (mass ratio)
[0156] B-11 (B-1): (B-7)=1:0.03 (mass ratio)
[0157] B-12 (B-1): (B-7)=1:0.1 (mass ratio)
[0158] B-13 (B-1): (B-7)=1:1 (mass ratio)
[0159] B-14 (B-1): (B-7)=1:1.1 (mass ratio)
[0160] Here are base components for lubricating coatings and
binders, used for tests.
[0161] <Base Component and Binder>
[0162] C-1 sodium tungstate
[0163] C-2 potassium tetraborate
[0164] C-3 sodium silicate No. 3
[0165] C-4 sodium tripolyphosphate
[0166] C-5 sodium tartrate
[0167] C-6 potassium stearate
[0168] C-7 acrylic resin: copolymerization product of
methylmethacrylate and n-butylacrylate, subjected to emulsion
polymerization with polyoxyethylene alkyl phenyl ether (molecular
weight: 150000 or more), average particle size 0.5 .mu.m, solid
content concentration 40 mass %
[0169] C-8 urethane resin (powder, molecular weight: 100000),
average particle size 3 .mu.m
[0170] Here is a surfactant used for tests.
[0171] <Surfactant>
[0172] D-1 polyoxyethylene sorbitol tetraoleate (60 mol ethylene
oxide added)
[0173] [Method for Inclusion of Lipophilic Lubricating Component
Between Particles and/or Between Layers of Layered Clay
Mineral]
[0174] As for the oil and extreme-pressure agent that are liquid at
room temperature, the oil and the extreme-pressure agent were added
to the layered clay mineral in proportions equal to or larger than
an includable amount (1:1 in mass ratio), and mixed with the use of
a mortar until being homogeneous in whole, thereby resulting in the
lubricating component included between particles and/or between
layers. Thereafter, the excess oil and extreme-pressure adhering to
the surface of the layered clay mineral were removed by immersion
in boiling water for 10 minutes, and the layered clay mineral was
left to dry at room temperature for 24 hours. Alternatively, in the
case of zinc stearate and wax which are poorly-soluble and solid at
room temperature, the lubricating component turned into a liquid at
a temperature equal to or higher than the melting points was added
to the layered clay mineral (1:1 in mass ratio), and mixed
therewith in a mortar until becoming fully homogeneous, thereby
resulting in the lubricating component included between particles
and/or between layers. Thereafter, the wax (or zinc stearate)
adhering to particle surfaces was removed by immersion for 10
minutes in an oil bath warmed to a temperature equal to the melting
point of the wax (or zinc stearate) or higher, thereafter, the oil
on the particle surfaces was removed by immersion in boiling water
for 10 minutes, and thereafter, the layered clay mineral was left
to dry at room temperature for 24 hours.
[0175] [Method for Measuring Inclusion Amount of Lipophilic
Lubricating Component]
[0176] The inclusion amount of the lipophilic lubricating component
was measured with the use of a total organic carbon meter
(TOC-5000/SSM-5000A from Shimadzu Corporation) equipped with a
solid sample burning system. The measuring method will be mentioned
in detail below. First, a lipophilic lubricating component alone
(lipophilic lubricating component itself) to be included was used
and burned completely at a furnace temperature of 700.degree. C.,
thereby creating a calibration curve of carbon
intensity-lubricating component amount. Next, measured is the
carbon intensity in carrier particles with the lipophilic
lubricating component included between particles of and/or between
layers of the layered clay mineral by the previously mentioned
method under the same condition, and the obtained value is
converted to the lubricating component amount.
inclusion amount (%)=(mass of lipophilic lubricating
component/total mass of carrier particle).times.100
[0177] [Method for Measuring Coating Amount of Lubricating
Coating]
[0178] With the use of a commercially available degreasing agent
(registered trademark: FINECLEANER E6400 from Nihon Parkerizing
Co., Ltd.), under the conditions of concentration 20 g/L and
temperature 60.degree. C., a test piece with a lubricating coating
formed was immersed for 30 minutes, thereby removing the
lubricating coating, and the coating amount was determined from the
difference in mass between before and after the immersion.
coating amount (g/m.sup.2)=(test piece mass before removing-test
piece mass after removing)/surface area of test piece
[0179] [Treatment Method]
[0180] <Step A (Water-Based Lubricating Coating Agent)>
[0181] (1) degreasing: a test piece (metal material) was immersed
for 10 minutes in a commercially available degreasing agent
(registered trademark: FINECLEANER E6400 from Nihon Parkerizing
Co., Ltd., concentration: 20 g/L) warmed to 60.degree. C.
[0182] (2) water washing: the degreased test piece was immersed for
10 seconds in tap water warmed to 60.degree. C.
[0183] (3) lubrication treatment (contact step): the test piece
washed with the water was immersed for 30 seconds in the
lubricating coating agent for metal materials (see Table 1), warmed
to 60.degree. C.
[0184] (4) drying: the test piece subjected to the lubrication
treatment was dried for 3 minutes at 80.degree. C.
[0185] <Step B (Water-Based Lubricating Coating Agent)>
[0186] (1) shot blasting: a test piece (metal material) was
subjected to a shot blasting treatment for 5 minutes with the use
of shot balls of .phi.0.5 mm (from SUS).
[0187] (2) water washing: the test piece subjected to shot blasting
was immersed for 90 seconds in tap water warmed to 60.degree.
C.
[0188] (3) lubrication treatment (contact step): the test piece
washed with the water was immersed for 30 seconds in the
lubricating coating agent for metal materials (see Table 1), warmed
to 60.degree. C.
[0189] (4) drying: the test piece subjected to the lubrication
treatment was dried for 3 minutes at room temperature
(blowing).
[0190] <Step C (Oil-Based Lubricating Coating Agent)>
[0191] (1) degreasing: a test piece (metal material) was immersed
for 10 minutes in a commercially available degreasing agent
(registered trademark: FINECLEANER E6400 from Nihon Parkerizing
Co., Ltd., concentration: 20 g/L) warmed to 60.degree. C.
[0192] (2) water rinsing: the degreased test piece was immersed for
10 seconds in tap water warmed to 60.degree. C.
[0193] (3) drying: the test piece rinsed with the water was dried
for 3 minutes at 80.degree. C.
[0194] (4) lubrication treatment (contact step): the dried test
piece was immersed for 30 seconds in the lubricating coating agent
for metal materials (see Table 2) at room temperature.
[0195] <Step D (Powder-Based Lubricating Coating Agent)>
[0196] (1) shot blasting: a test piece (metal material) was
subjected to a shot blasting treatment for 5 minutes with the use
of shot balls of .phi.0.5 mm (from SUS).
[0197] (2) water rinsing: the test piece subjected to shot blasting
was immersed for 90 seconds in tap water warmed to 60.degree.
C.
[0198] (3) drying: the test piece rinsed with the water was dried
for 3 minutes at 80.degree. C.
[0199] (4) lubrication treatment (contact step): to the dried test
piece, the lubricating coating agent for metal materials (see Table
3) with the solid lubricant dispersed in the base component (C-8)
as a binder was applied with the use of an air gun for
electrostatic powder coating so as to achieve a predetermined
coating amount.
[0200] (5) drying: the test piece subjected to the lubrication
treatment was dried for 3 minutes at 150.degree. C.
[0201] <Step E (Phosphate+Lubrication)>
[0202] (1) degreasing: a test piece (metal material) was immersed
for 10 minutes in a commercially available degreasing agent
(registered trademark: FINECLEANER E6400 from Nihon Parkerizing
Co., Ltd., concentration: 20 g/L) warmed to 60.degree. C.
[0203] (2) water rinsing: the degreased test piece was immersed for
30 seconds in tap water at room temperature.
[0204] (3) chemical conversion treatment (chemical conversion
treatment step): the test piece rinsed with the water was immersed
for 10 minutes in a commercially available phosphate treatment
solution (registered trademark: PALBOND 181X from Nihon Parkerizing
Co., Ltd., concentration: 90 g/L) warmed to 80.degree. C.
[0205] (4) water rinsing: the test piece subjected to the chemical
conversion treatment was immersed for 30 seconds in tap water
warmed to 60.degree. C.
[0206] (5) lubrication treatment (contact step): the test piece
washed with the water was immersed for 30 seconds in the
lubricating coating agent for metal materials (see Table 1), warmed
to 60.degree. C.
[0207] (6) drying: the test piece subjected to the lubrication
treatment was dried for 3 minutes at 80.degree. C.
[0208] Table 1 shows test standards for the water-based lubricating
coating agents for metal materials.
TABLE-US-00001 TABLE 1 composition of lubricating coating agent for
metal material (1000 g in total) solid lubricant base component
layered lipophilic inclusion blending solid content blending clay
lubricating amount amount concentration base amount mineral
component (mass %) (g) (mass %) component (g) Example 1 A-1 B-12
4.3 100 50 B-12 95 Example 2 A-2 B-12 5.0 100 50 B-12 95 Example 3
A-3 B-12 8.0 100 50 B-12 95 Example 4 A-4 B-12 8.2 100 50 B-12 95
Example 5 A-5 B-12 8.2 100 50 B-12 95 Example 6 A-6 B-12 8.1 100 50
B-12 95 Example 7 A-7 B-12 8.1 100 50 B-12 95 Example 8 A-8 B-12
8.1 100 50 B-12 95 Example 9 A-9 B-12 6.4 100 50 B-12 95 Example 10
A-10 B-12 5.1 100 50 B-12 95 Example 11 A-11 B-12 4.1 100 50 B-12
95 Example 12 A-12 B-12 8.2 100 50 B-12 95 Example 13 A-13 B-12 8.1
100 50 B-12 95 Example 14 A-14 B-12 8.1 100 50 B-12 95 Example 15
A-15 B-12 8.0 100 50 B-12 95 Example 16 A-16 B-12 7.8 100 50 B-12
95 Example 17 A-17 B-12 6.7 100 50 B-12 95 Example 18 A-18 B-12 4.8
100 50 B-12 95 Example 19 A-5 B-1 8.2 100 50 B-12 95 Example 20 A-5
B-2 8.2 100 50 B-12 95 Example 21 A-5 B-3 7.2 100 50 B-12 95
Example 22 A-5 B-4 4.9 100 50 B-12 95 Example 23 A-5 B-5 8.2 100 50
B-12 95 Example 24 A-5 B-6 8.1 100 50 B-12 95 Example 25 A-5 B-7
8.0 100 50 B-12 95 Example 26 A-5 B-8 8.0 100 50 B-12 95 Example 27
A-5 B-9 8.1 100 50 B-12 95 Example 28 A-5 B-10 8.1 100 50 B-12 95
Example 29 A-5 B-11 8.0 100 50 B-12 95 Example 30 A-5 B-13 8.0 100
50 B-12 95 Example 31 A-5 B-14 8.1 100 50 B-12 95 Example 32 A-5
B-12 8.2 100 50 C-1 95 Example 33 A-5 B-12 8.2 100 50 C-2 95
Example 34 A-5 B-12 8.2 100 50 C-3 95 Example 35 A-5 B-12 8.2 100
50 C-4 95 Example 36 A-5 B-12 8.2 100 50 C-5 95 Example 37 A-5 B-12
8.2 100 50 C-6 95 Example 38 A-5 B-12 8.2 100 50 C-7 237.5 Example
39 A-5 B-12 8.2 40 20 B-12 155 Example 40 A-5 B-12 8.2 10 5 B-12
185 Example 41 A-5 B-12 8.2 6 3 B-12 189 Example 42 A-5 B-12 8.2
13.5 50 B-12 12.83 Example 43 A-5 B-12 8.2 15 50 B-12 14.25 Example
44 A-5 B-12 8.2 60 50 B-12 57 Example 45 A-5 B-12 8.2 200 50 B-12
190 Example 46 A-5 B-12 8.2 100 50 B-12 95 Example 47 A-5 B-12 8.2
100 50 B-12 95 composition of lubricating coating agent for metal
material (1000 g in total) surfactant water total solid blending
blending content coating amount amount concentration treatment
amount surfactant (g) (g) (mass %) method (g/m.sup.2) parameter
Example 1 D-1 5 800 20 Step A 10 water Example 2 D-1 5 800 20 Step
A 10 contact Example 3 D-1 5 800 20 Step A 10 angle Example 4 D-1 5
800 20 Step A 10 Example 5 D-1 5 800 20 Step A 10 Mohs Example 6
D-1 5 800 20 Step A 10 hardness Example 7 D-1 5 800 20 Step A 10
average Example 8 D-1 5 800 20 Step A 10 particle size Example 9
D-1 5 800 20 Step A 10 Example 10 D-1 5 800 20 Step A 10 Example 11
D-1 5 800 20 Step A 10 Example 12 D-1 5 800 20 Step A 10 aspect
ratio Example 13 D-1 5 800 20 Step A 10 Example 14 D-1 5 800 20
Step A 10 Example 15 D-1 5 800 20 Step A 10 Example 16 D-1 5 800 20
Step A 10 Example 17 D-1 5 800 20 Step A 10 Example 18 D-1 5 800 20
Step A 10 Example 19 D-1 5 800 20 Step A 10 lipophilic Example 20
D-1 5 800 20 Step A 10 lubricating Example 21 D-1 5 800 20 Step A
10 component Example 22 D-1 5 800 20 Step A 10 Example 23 D-1 5 800
20 Step A 10 Example 24 D-1 5 800 20 Step A 10 Example 25 D-1 5 800
20 Step A 10 Example 26 D-1 5 800 20 Step A 10 Example 27 D-1 5 800
20 Step A 10 Example 28 D-1 5 800 20 Step A 10 Example 29 D-1 5 800
20 Step A 10 Example 30 D-1 5 800 20 Step A 10 Example 31 D-1 5 800
20 Step A 10 Example 32 D-1 5 800 20 Step A 10 base Example 33 D-1
5 800 20 Step A 10 component Example 34 D-1 5 800 20 Step A 10
Example 35 D-1 5 800 20 Step A 10 Example 36 D-1 5 800 20 Step A 10
Example 37 D-1 5 800 20 Step A 10 Example 38 D-1 5 657.5 20 Step A
10 Example 39 D-1 5 800 20 Step A 10 solid Example 40 D-1 5 800 20
Step A 10 lubricant Example 41 D-1 5 800 20 Step A 10 concentration
Example 42 D-1 0.68 973 2.7 Step A 0.4 coating Example 43 D-1 0.75
970 3 Step A 0.5 amount Example 44 D-1 3 880 12 Step A 5 Example 45
D-1 10 600 40 Step A 40 Example 46 D-1 5 800 20 Step B 10 treatment
Example 47 D-1 5 800 20 Step E 10 step
[0209] Table 2 shows test standards for the oil-based lubricating
coating agents for metal materials.
TABLE-US-00002 TABLE 2 composition of lubricating coating agent for
metal material (1000 g in total) solid lubricant base component
total soild layered lipophilic inclusion blending solid content
blending content coating clay lubricating amount amount
concentration base amount concentration treatment amount mineral
component (mass %) (g) (mass %) component (g) (mass %) method
(g/cm.sup.2) parameter Example 48 A-1 B-12 4.3 300 30 B-12 700 100
Step C 25 water Example 49 A-2 B-12 5.0 300 30 B-12 700 100 Step C
25 contact Example 50 A-3 B-12 8.0 300 30 B-12 700 100 Step C 25
angle Example 51 A-4 B-12 8.2 300 30 B-12 700 100 Step C 25 Example
52 A-5 B-12 8.2 300 30 B-12 700 100 Step C 25 Mohs Example 53 A-6
B-12 8.1 300 30 B-12 700 100 Step C 25 hardness Example 54 A-7 B-12
8.1 300 30 B-12 700 100 Step C 25 average Example 55 A-8 B-12 8.1
300 30 B-12 700 100 Step C 25 particle Example 56 A-9 B-12 6.4 300
30 B-12 700 100 Step C 25 size Example 57 A-10 B-12 5.1 300 30 B-12
700 100 Step C 25 Example 58 A-11 B-12 4.1 300 30 B-12 700 100 Step
C 25 Example 59 A-12 B-12 8.2 300 30 B-12 700 100 Step C 25 aspect
Example 60 A-13 B-12 8.1 300 30 B-12 700 100 Step C 25 ratio
Example 61 A-14 B-12 8.1 300 30 B-12 700 100 Step C 25 Example 62
A-15 B-12 8.0 300 30 B-12 700 100 Step C 25 Example 63 A-16 B-12
7.8 300 30 B-12 700 100 Step C 25 Example 64 A-17 B-12 6.7 300 30
B-12 700 100 Step C 25 Example 65 A-18 B-12 4.8 300 30 B-12 700 100
Step C 25 Example 66 A-5 B-1 8.2 300 30 B-12 700 100 Step C 25
lipophilic Example 67 A-5 B-2 8.2 300 30 B-12 700 100 Step C 25
lubricating Example 68 A-5 B-3 7.2 300 30 B-12 700 100 Step C 25
component Example 69 A-5 B-4 4.9 300 30 B-12 700 100 Step C 25
Example 70 A-5 B-5 8.2 300 30 B-12 700 100 Step C 25 Example 71 A-5
B-6 8.1 300 30 B-12 700 100 Step C 25 Example 72 A-5 B-7 8.0 300 30
B-12 700 100 Step C 25 Example 73 A-5 B-8 8.0 300 30 B-12 700 100
Step C 25 Example 74 A-5 B-9 8.1 300 30 B-12 700 100 Step C 25
Example 75 A-5 B-10 8.1 300 30 B-12 700 100 Step C 25 Example 76
A-5 B-11 8.0 300 30 B-12 700 100 Step C 25 Example 77 A-5 B-13 8.0
300 30 B-12 700 100 Step C 25 Example 78 A-5 B-14 8.1 300 30 B-12
700 100 Step C 25 Example 79 A-5 B-12 8.2 200 20 B-12 800 100 Step
C 25 solid Example 80 A-5 B-12 8.2 50 5 B-12 950 100 Step C 25
lubricant Example 81 A-5 B-12 8.2 30 3 B-12 970 100 Step C 25
concentration
[0210] Table 3 shows test standards for the powder-based
lubricating coating agents for metal materials.
TABLE-US-00003 TABLE 3 composition of lubricating coating agent for
metal material (1000 g in total) solid lubricant base component
total soild layered lipophilic inclusion blending solid content
blending content coating clay lubricating amount amount
concentration base amount concentration treatment amount mineral
component (mass %) (g) (mass %) component (g) (mass %) method
(g/cm.sup.2) parameter Example 82 A-1 B-12 4.3 700 70 C-8 300 100
Step D 10 water Example 83 A-2 B-12 5.0 700 70 C-8 300 100 Step D
10 contact Example 84 A-3 B-12 8.0 700 70 C-8 300 100 Step D 10
angle Example 85 A-4 B-12 8.2 700 70 C-8 300 100 Step D 10 Example
86 A-5 B-12 8.2 700 70 C-8 300 100 Step D 10 Mohs Example 87 A-6
B-12 8.1 700 70 C-8 300 100 Step D 10 hardness Example 88 A-7 B-12
8.1 700 70 C-8 300 100 Step D 10 average Example 89 A-8 B-12 8.1
700 70 C-8 300 100 Step D 10 particle Example 90 A-9 B-12 6.4 700
70 C-8 300 100 Step D 10 size Example 91 A-10 B-12 5.1 700 70 C-8
300 100 Step D 10 Example 92 A-11 B-12 4.1 700 70 C-8 300 100 Step
D 10 Example 93 A-12 B-12 8.2 700 70 C-8 300 100 Step D 10 aspect
Example 94 A- 13 B-12 8.1 700 70 C-8 300 100 Step D 10 ratio
Example 95 A-14 B-12 8.1 700 70 C-8 300 100 Step D 10 Example 96
A-15 B-12 8.0 700 70 C-8 300 100 Step D 10 Example 97 A-16 B-12 7.8
700 70 C-8 300 100 Step D 10 Example 98 A-17 B-12 6.7 700 70 C-8
300 100 Step D 10 Example 99 A-18 B-12 4.8 700 70 C-8 300 100 Step
D 10 Example 100 A-5 B-1 8.2 700 70 C-8 300 100 Step D 10
lipophilic Example 101 A-5 B-2 8.2 700 70 C-8 300 100 Step D 10
lubricating Example 102 A-5 B-3 7.2 700 70 C-8 300 100 Step D 10
component Example 103 A-5 B-4 4.9 700 70 C-8 300 100 Step D 10
Example 104 A- 5 B-5 8.2 700 70 C-8 300 100 Step D 10 Example 105
A-5 B-6 8.1 700 70 C-8 300 100 Step D 10 Example 106 A-5 B-7 8.0
700 70 C-8 300 100 Step D 10 Example 107 A-5 B-8 8.0 700 70 C-8 300
100 Step D 10 Example 108 A-5 B-9 8.1 700 70 C-8 300 100 Step D 10
Example 109 A-5 B-10 8.1 700 70 C-8 300 100 Step D 10 Example 110
A-5 B-11 8.0 700 70 C-8 300 100 Step D 10 Example 111 A-5 B-13 8.0
700 70 C-8 300 100 Step D 10 Example 112 A-5 B-14 8.1 700 70 C-8
300 100 Step D 10 Example 113 A-5 B-12 8.2 700 70 C-8 300 100 Step
D 0.5 coating Example 114 A-5 B-12 8.2 700 70 C-8 300 100 Step D 5
amount Example 115 A-5 B-12 8.2 700 70 C-8 300 100 Step D 40
Example 116 A-5 B-12 8.2 30 3 C-8 970 100 Step D 10 solid Example
117 A-5 B-12 8.2 50 5 C-8 950 100 Step D 10 content Example 118 A-5
B-12 8.2 300 30 C-8 700 100 Step D 10 concentration
Comparative Example 1
[0211] <Zinc Phosphate Treatment+Reactive Soap Treatment>
[0212] (1) degreasing: a test piece (metal material) was immersed
for 10 minutes in a commercially available degreasing agent
(registered trademark: FINECLEANER E6400 from Nihon Parkerizing
Co., Ltd., concentration: 20 g/L) warmed to 60.degree. C.
[0213] (2) water rinsing: the degreased test piece was immersed for
30 seconds in tap water at room temperature.
[0214] (3) phosphate treatment: the test piece rinsed with the
water was immersed for 10 minutes in a commercially available
phosphate treatment solution (registered trademark: PALBOND 181X
from Nihon Parkerizing Co., Ltd., concentration: 90 g/L) warmed to
80.degree. C.
[0215] (4) water rinsing: the test piece subjected to the phosphate
treatment was immersed for 30 seconds in tap water at room
temperature.
[0216] (5) reactive soap treatment: the test piece rinsed with the
water was immersed for 5 minutes in a commercially available
reactive soap treatment solution (registered trademark: PALUBE 235
from Nihon Parkerizing Co., Ltd., concentration: 70 g/L) warmed to
80.degree. C.
[0217] (6) drying: the test piece subjected to the reactive soap
treatment was dried for 3 minutes at 80.degree. C.
Comparative Example 2
[0218] The water-based lubricant (Patent Literature 1: JP 3517522
B2) listed below was prepared, and applied to a test piece by the
method in accordance with the step A such that the dried coating
amount was 10 g/m.sup.2.
[0219] <Water-Based Lubricant>
[0220] sodium tetraborate: 10.0 weight %
[0221] calcium stearate: 5.0 weight %
[0222] palm oil: 5.0 weight %
[0223] polyoxyethylene alkyl ether: 1.0 weight %
[0224] balance: water
Comparative Example 3
[0225] The following water-based lubricating coating agent was
prepared with the use of the talc (A-5) including no lipophilic
lubricating component. The agent was applied to a test piece by the
method in accordance with the step A such that the dried coating
amount was 10 g/m.sup.2.
[0226] <Water-Based Lubricant>
[0227] solid lubricant: A-5 100 g
[0228] base component: C-1 95 g
[0229] surfactant: D-1 5 g
[0230] water: 800 g
Comparative Example 4
[0231] The following oil-based lubricant including no solid
lubricant was used and applied to a test piece in accordance with
the step C such that the coating amount was 25 g/m.sup.2.
[0232] <Oil-Based Lubricant>
[0233] base component: B-10 1000 g
Comparative Example 5
[0234] The following powder-based lubricating coating agent was
prepared with the use of the talc (A-5) including no lipophilic
lubricating component. The agent was applied to a test piece by the
method in accordance with the step D such that the dried coating
amount was 10 g/m.sup.2.
[0235] <Powder-Based Lubricant>
[0236] solid lubricant: A-5 700 g
[0237] base component: C-8 300 g
Comparative Example 6
[0238] The following water-based lubricating coating agent was
prepared with the use of molybdenum disulfide. The agent was
applied to a test piece by the method in accordance with the step A
such that the dried coating amount was 10 g/m.sup.2.
[0239] <Water-Based Lubricant>
[0240] solid lubricant: A-19 (molybdenum disulfide) 100 g
[0241] base component: B-10 95 g
[0242] surfactant: D-1 5 g
[0243] water: 800 g
[0244] [Evaluation Method]
[0245] Effects of the lubricating coating agent for metal materials
according to the present invention were verified by the following
evaluations. It is to be noted that among the examples and the
comparative examples, at the standard of using the oil or the
extreme-pressure agent as a base component for a lubricating
coating and a binder component, no slidability test (Bowden test)
was carried out, because the standard is not suitable for the
intended use as sliding coatings.
[0246] (1) lubricity (forgeability, wire drawability, tube
drawability, slidability)
[0247] (2) corrosion resistance
[0248] (3) operability
[0249] (4) appearance
[0250] [Forgeability Test]
[0251] <Spike Test>
[0252] test material: S45C material (25 mm.phi..times.30 mm)
subjected to spheroidizing annealing
[0253] test method: Test was carried out in accordance with the
invention in JP 3227721 B2 for the evaluation. The lubricating
coatings following protrusions of the test pieces were evaluated
visually. In this test, in order to confirm whether the lubricity
was decreased or not due to re-absorption of moisture by the
lubricating coating, the lubricity was compared between a case of
completely drying the lubricating coating under the condition of
80.degree. C. for 3 minutes and a case of moisture absorption by
the lubricating coating under the condition of 30.degree. C. and
relative humidity 80% for 5 hours after the complete drying. Here
are evaluation criteria. It is to be noted that the level B or
higher corresponds to a practical level.
[0254] evaluation criteria:
[0255] S: the coating which followed fully to the protrusion tip
(almost no metallic luster)
[0256] A: the coating which followed to the protrusion tip
[0257] B: the coating which followed to the protrusion top
[0258] C: the coating which followed to the protrusion center
[0259] D: the coating which followed to the protrusion bottom
[0260] [Wire Drawability Test]
[0261] test material: S45C, .phi.3.0 mm, 50000 mm in length
[0262] test method: wire drawing was made under the condition of a
reduction of area from 5 to 20% with the use of an R die The
limited reduction of area capable of stable wire drawing without
any scratch or chatter was evaluated in accordance with the
following evaluation criteria. It is to be noted that the level B
or higher corresponds to a practical level.
[0263] evaluation criteria:
[0264] S: limited reduction of area of 23% or more
[0265] A: limited reduction of area of 20% or more and less than
23%
[0266] B: limited reduction of area of 15% or more and less than
20%
[0267] C: limited reduction of area of 10% or more and less than
15%
[0268] D: limited reduction of area of less than 10%
[0269] [Tube Drawability Test]
[0270] test material: STKM17A, .phi.25.4 mm.times.2.5 mmt, 2000 mm
in length
[0271] test method: Test was carried out under the condition of
tube drawing speed 20 m/min with the use of an R die and a
cylindrical plug in a draw bench The limited reduction of area
capable of stable tube drawing without any scratch or chatter was
evaluated in accordance with the following evaluation criteria. It
is to be noted that the level B or higher corresponds to a
practical level.
[0272] evaluation criteria:
[0273] S: limited reduction of area of 53% or more
[0274] A: limited reduction of area of 50% or more and less than
53%
[0275] B: limited reduction of area of 45% or more and less than
50%
[0276] C: limited reduction of area of 40% or more and less than
45%
[0277] D: limited reduction of area of less than 40%
[0278] [Slidability Test]
[0279] <Bowden Test>
[0280] test material: SPCC-SD, 70 mm.times.150 mm.times.0.8
mint
[0281] test method: a Bowden test was carried out mainly as
performance evaluation of sliding coatings (in the case of a
water-soluble inorganic salt, a water-soluble organic salt, or a
water-based resin for the base component of the lubricating
coating). This test is carried out by sliding a plate test piece
with the lubricating coating formed, with the test piece in contact
with a steel ball under constant load, and measuring the friction
coefficient and the sliding frequency. When the coating was
fractured, and then seizured, the friction coefficient reached
0.25, and thus, the slidability was evaluated with the sliding
frequency achieved until the friction coefficient reached 0.25. It
is to be noted that the level B or higher corresponds to a
practical level in the following evaluation criteria.
[0282] test conditions:
[0283] load: 50 N
[0284] indenter: 10 mm.phi. SUJ2 steel ball
[0285] sliding speed: 10 mm/s
[0286] test temperature: 60.degree. C.
[0287] evaluation criteria:
[0288] S: 250 times or more
[0289] A: 200 times or more, and less than 250 times
[0290] B: 150 times or more, and less than 200 times
[0291] C: 100 times or more, and less than 150 times
[0292] D: less than 100 times
[0293] [Comprehensive Evaluation of Lubricity]
[0294] The respective evaluation results for forgeability, wire
drawability, tube drawability, and slidability were scored as
follows, and the average value was regarded as a comprehensive
evaluation result for lubricity. It is to be noted that whether the
lubricity was practical or not was determined by the performance of
B or higher (score of 3 or higher) in each lubricity evaluation and
the average value of 3.0 or higher for the scores.
S=5,A=4,B=3,C=2,D=1
[0295] [Corrosion Resistance Test]
[0296] test material: SPCC-SD, 70 mm.times.150 mm.times.0.8 mmt
[0297] test method: for the corrosion resistance test, the plate
test piece with the lubricating coating formed was left for 1 month
in the plant in the Hiratsuka district, and evaluated with the rust
area ratio. In the plant, the average temperature was 27.6.degree.
C., and the average humidity was 75%. It is to be noted that the
level B or higher corresponds to a practical level in the following
evaluation criteria.
[0298] evaluation criteria:
[0299] A: rust area ratio of less than 1%
[0300] B: rust area ratio of 1% or more and less than 10%
[0301] C: rust area ratio of 10% or more and less than 30%
[0302] D: rust area ratio of 30% or more and less than 80%
[0303] [Operability Evaluation]
[0304] The performance of line operation was evaluated by a
treatment load test (sludge generation test). In this test, with
respect to 1 L of the lubricating coating agent, a test plate
(SPCC-SD: 70 mm.times.150 mm.times.0.8 mmt) was continuously
treated until reaching a treatment load of 0.3 m.sup.2, and
evaluated with the presence or absence of sludge generated. It is
to be noted that the level B or higher corresponds to a practical
level in the following evaluation criteria.
[0305] evaluation criteria:
[0306] A: no sludge generated
[0307] B: sludge slightly generated (generation amount: less than 3
g/L)
[0308] C: sludge generated (generation amount: 3 g/L or more)
[0309] [Appearance Evaluation]
[0310] The L value was measured as appearance evaluation after the
formation of the lubricating coating.
[0311] test material: SPCC-SD, 70 mm.times.150 mm.times.0.8 mmt
[0312] measuring instrument: color computer SM-3 from Suga Test
Instruments Co., Ltd.
[0313] evaluation criteria: here are evaluation criteria. The
degree of blackness is higher as the L value is lower, which is
determined to mean a worse working environment. The level B or
higher corresponds to a practical level.
[0314] A: 70 or more
[0315] B: 50 or more, and less than 70
[0316] C: less than 50
[0317] Table 4 shows the evaluation results for the water-based
lubricating coating agents for metal materials.
TABLE-US-00004 TABLE 4 lubricity test forgeability (spike test)
comprehensive moisture wire tube evaluation of corrosion drying
absorption drawability drawability slidability lubricity resistance
operability appearance parameter Example 1 B B B B 3.0 B A A water
Example 2 A B A A 3.8 A A A contact angle Example 3 S A A A 4.3 A A
A Example 4 S A S A 4.5 A A A Example 5 S A S S 4.8 A A A Mohs
Example 6 A B B A 3.5 A A A hardness Example 7 S A S S 4.8 A A A
average Example 8 S A S S 4.8 A A A particle Example 9 S A S A 4.5
A A A size Example 10 A B A A 3.8 A A A Example 11 B B B B 3.0 B A
A Example 12 A B B B 3.3 A A A aspect Example 13 A B A A 3.8 A A A
ratio Example 14 S A S S 4.8 A A A Example 15 S A S S 4.8 A A A
Example 16 A B A A 3.8 A A A Example 17 A B B A 3.5 A A A Example
18 B B B B 3.0 B A A Example 19 S A A A 4.3 A A A lipophilic
Example 20 S A A A 4.3 A A A lubricating Example 21 A A A A 4.0 A A
A component Example 22 B B B B 3.0 B A A Example 23 S A A A 4.3 A A
A Example 24 S A A A 4.3 A A A Example 25 S A A A 4.3 A A A Example
26 S A A A 4.3 A A A Example 27 S A A A 4.3 A A A Example 28 S A A
A 4.3 A A A Example 29 S A S S 4.8 A A A Example 30 S A S S 4.8 A A
A Example 31 S A S S 4.8 A A A Example 32 S A A A A 4.2 A A A base
Example 33 S B S A A 4.2 A A A component Example 34 B A B B B 3.2 A
A A Example 35 S A S A A 4.4 A A A Example 36 B B B A B 3.2 A A A
Example 37 A B A A B 3.6 A A A Example 38 A B A A A 3.8 A A A
Example 39 S A S S 4.8 A A A Solid Example 40 A B A A 18 A A A
lubricant Example 41 B B B B 3.0 A A A concentration Example 42 B B
B B 3.0 B A A coating Example 43 A B A B 3.5 A A A amount Example
44 S A A A 4.3 A A A Example 45 S A S S 4.8 A A A Example 46 S A S
S 4.8 A A A treatment Example 47 S S S S 8.0 A A A step
[0318] Table 5 shows the evaluation results for the oil-based
lubricating coating agents for metal materials.
TABLE-US-00005 TABLE 5 lubricity test forgeability (spike test)
comprehensive moisture wire tube evaluation of corrosion drying
absorption drawability drawability lubricity resistance operability
appearance parameter Example 48 B B B B 3.0 B A A water Example 49
A B B A 3.5 A A A contact Example 50 S A A A 4.3 A A A angle
Example 51 S A S A 4.5 A A A Example 52 S S S A 4.8 A A A Mohs
Example 53 A B A A 3.8 A A A hardness Example 54 S S S A 4.8 A A A
average Example 55 S S S A 4.8 A A A particle Example 56 A B A A
3.8 A A A size Example 57 A B A B 3.5 A A A Example 58 B B B B 3.0
B A A Example 59 B B B B 3.0 A A A aspect Example 60 A B B A 3.5 A
A A ratio Example 61 S S S A 4.8 A A A Example 62 S S S A 4.8 A A A
Example 63 A B A A 3.8 A A A Eaxmple 64 A B A B 3.5 A A A Example
65 B B B B 3.0 B A A Example 66 S B A A 4.0 A A A lipophilic
Example 67 S B A A 4.0 A A A lubricating Example 68 A B B A 3.5 A A
A component Example 69 B B B B 3.0 B A A Example 70 S B A A 4.0 A A
A Example 71 S B A A 4.0 A A A Example 72 S B A A 4.0 A A A Example
73 S B A A 4.0 A A A Example 74 S e A A 4.0 A A A Example 75 S B A
A 4.0 A A A Example 76 S S S A 4.8 A A A Example 77 S S S A 4.8 A A
A Example 78 S S S A 4.8 A A A Example 79 S A S A 4.5 A A A solid
Example 80 A B B B 3.3 A A A lubricant Example 81 B B B B 3.0 A A A
concentration
[0319] Table 6 shows the evaluation results for the powder-based
lubricating coating agents for metal materials.
TABLE-US-00006 TABLE 6 lubricity test forgeability (spike test)
comprehensive moisture wire tube evaluation of corrosion drying
absorption drawability drawability slidability lubricity resistance
operability appearance parameter Example 82 B B B B A 3.2 B A A
water Example 83 A B A A A 3.8 A A A contact Example 84 S A A A A
4.2 A A A angle Example 85 S A S A A 4.4 A A A Example 86 S A S S S
4.8 A A A Mohs Example 87 A A A A A 4.0 A A A hardness Example 88 S
A S S S 4.8 A A A average Example 89 S A S S S 4.8 A A A particle
Example 90 S A A A A 4.2 A A A size Example 91 A B A A A 3.8 A A A
Example 92 B B B B A 3.2 B A A Example 93 A B e B B 3.2 A A A
aspect Example 94 A B A A A 3.8 A A A ratio Example 95 S A S S S
4.8 A A A Example 96 S A S S S 4.8 A A A Example 97 S A S A A 4.4 A
A A Example 98 A A A A A 4.0 A A A Example 99 A B A B A 3.6 B A A
Example 100 A A A A A 4.0 A A A lipophilic Example 101 A A A A A
4.0 A A A lubricating Example 102 A B B B A 3.4 A A A component
Example 103 B B B B B 3.0 B A A Example 104 A A A A A 4.0 A A A
Example 105 A A A A A 4.0 A A A Example 106 A B A A A 3.8 A A A
Example 107 A B A B A 3.6 A A A Example 108 A B A B A 3.6 A A A
Example 109 A A A A A 4.0 A A A Example 110 S A S S S 4.8 A A A
Example 111 S A S S S 4.8 A A A Example 112 S A S S S 4.8 A A A
Example 113 B B B B B 3.0 A A A coating Example 114 A A A A A 4.0 A
A A amount Example 115 S A S S S 4.8 A A A Example 116 B B B B B
3.0 A A A solid Example 117 A B A A A 3.8 A A A lubricant Example
118 S A S S S 4.8 A A A concentration
[0320] Table 7 shows the evaluation results for comparative
examples.
TABLE-US-00007 TABLE 7 lubricity test forgeability (spike test)
comprehensive moisture wire tube evaluation of corrosion drying
absorption drawability drawability slidability lubricity resistance
operability appearance Comparative Example 1 S S S S S 5.0 A C B
Comparative Example 2 A C A A A 3.8 A A A Comparative Example 3 C C
D D C 1.6 C A A Comparative Example 4 D D D D 1.0 C A A Comparative
Example 5 C C C C C 2.0 C A A Comparative Example 6 S B A A 4.0 A A
C
[0321] As is clear from the evaluation results shown in Tables 4 to
6, the lubricating coating agents for metal materials according to
the examples of the present invention have achieved performance
equal to or higher than the practical level (rated as B or higher)
in all of the evaluation tests. In contrast, as for the comparative
examples in Table 7, comparative example 1 subjected to the
phosphate+reactive soap treatment has achieved lubricity at the
practical level, but operability rated as C. In addition,
comparative example 2 has achieved corrosion resistance,
operability, and an appearance at the practical levels, but
lubricity rated as C in the condition of moisture absorption.
comparative examples 3 to 5, the lubricants including no solid
lubricant according to the present invention, have failed to reach
the practical levels, with all of the lubricity tests and the
corrosion resistance rated as C or lower. comparative example 6 has
achieved excellent lubricity, corrosion resistance, and
operability, but the black appearance of the coating was rated as
C. From the foregoing results, the present invention can be
considered to have a greater deal of potential in industry, as
compared with the prior art.
* * * * *