[Designation of Document] SPECIFICATION
[Title of the hivention] SURFACE-TREATED METAL MATERIAL AND
AQUEOUS METAL SURFACE-TREATMENT AGENT
[Technical Field]
[0001]
The present invention relates to a metal material subjected to a chromate-free
surface treatment which has excellent corrosion resistance, heat resistance, antifingerprint
properties, electrical conductivity, paintability and black shaving resistance
during processing, and an aqueous metal surface-treatment agent used for the relevant
surface treatment. More specifically, the present invention relates to a metal material
subjected to a chromate-free surface treatment which can retain excellent corrosion
resistance without being affected by the alkaline degreasing, bending and punching
that are conducted when the surface-treated metal material is processed into a stamped
article and in addition, has excellent heat resistance, anti-fingerprint properties,
electrical conductivity, paintability and black shaving resistance during processing, and
an aqueous metal surface-treatment agent used for the relevant surface treatment.
Priority is claimed on Japanese Patent Application No. 2011-100126, filed on
April 27,2011, and the content of which is incorporated herein by reference.
[Background Art]
[0002]
As a technology which has excellent adhesion to the surface of a metal
material and imparts corrosion resistance, anti-fingerprint properties, or the like on the
surface of the metal material, the following methods have been generally known and
put in practice: a method in which a chromate treatment is carried out on the surface of
a metal material by use of a treatment solution containing chromic acid, dichromic acid
- 1 -
or salt thereof as a main component, a method in which a phosphate treatment is
carried out, a method in which a treatment is carried out by use of a silane coupling
agent alone, a method in which an organic-resin film treatment is carried out, or the
like.
[0003]
As a technology using mainly inorganic components, Patent Document 1 cites
a metal surface-treatment agent containing a vanadium compound and a metal
compound which includes at least one metal selected fi-om a group consisting of
zirconium, titanium, molybdenum, tungsten, manganese and cerium.
[0004]
On the other hand, as a technology using mainly a silane coupling agent.
Patent Document 2 discloses the treatment of a metal sheet by use of an aqueous
solution containing low concentration of organic functional silanes and a cross-linking
agent to obtain a temporary anticorrosive effect. A method is disclosed in which a
cross-linking agent establishes cross-links between organic functional silanes to form a
dense siloxane film.
[0005]
In addition, Patent Document 3 discloses a non-chrome based surface-treated
metal sheet which has excellent corrosion resistance, and in addition, excellent antifingerprint
properties, blackening resistance and paint adhesion and a method of
manufacturing the same, when a surface treatment agent is used which contains a
specific resin compound (A), a cationic urethane resin (B) having at least one cationic
functional group selected from a group consisting of primary to tertiary amino groups
and quaternary ammonium base, one or more types of silane coupling agents (C)
having a specific reactive functional group and a specific acid compound (E), and has
amounts of the cationic urethane resin (B) and the silane coupling agents (C) within a
predetermined range.
[0006]
Furthermore, Patent Document 4 discloses a technology in which silane
coupling agents are used as main components, a treatment solution with a specific pH
is prepared from a treatment agent which includes a silane coupling agent I having a
specific functional group A and a silane coupling agent II having a different functional
group B which can react with the functional group A, and the surface of a metal
material is coated with the treatment solution, heated and dried to form a film which
includes reaction products of the silane coupling agents I and II.
[0007]
In addition. Patent Document 5 discloses a technology which uses a surface
treatment agent for a metal material containing a compound having two or more
functional groups with specific structures as (a) components and at least one compound
selected from a group consisting of an organic acid, phosphoric acid and fluoride
complex as a (b) component, and having a molecular weight of 100-30,000 per
functional group in the (a) component, and has excellent corrosion resistance.
[0008]
However, the technologies in Patent Documents 1 to 3 do not have all of
sufficient corrosion resistance, heat resistance, anti-fingerprint properties, electrical
conductivity, paintability and black shaving resistance during processing, and still have
problems when it comes to practical uses. In addition, the technologies in Patent
Documents 4 to 5 use silane coupling agents as main components and mix a plurality
of silane coupling agents for use. However, hydrolysis and condensation of a silane
coupling agent, and reactivity of an organic functional group and effects obtained
thereby are not sufficiently examined, and a technology is not disclosed in which the
properties of a plurality of silane coupling agents are sufficiently controlled.
[0009]
Furthermore, Patent Document 6 discloses a chromate-free surface-treated
metal material which has a composite film formed thereon containing each component
when the surface of a metal material is coated with an aqueous metal surface-treatment
agent containing an organic silicon compound (W) obtained by mixing two types of
silane coupling agents with specific structures at specific mass ratio and a specific
inhibitor, and the surface-treated metal material is dried. The technology is an
excellent technology which has been put into practice as a surface-treated metal sheet
subjected to a chromate-free surface treatment which has excellent corrosion resistance,
heat resistance, anti-fingerprint properties, electrical conductivity, paintability and
black shaving resistance during processing. However, a surface-treated metal sheet is
required to have a high-performance composite film.
[Prior Art Document]
[Patent Document]
[0010]
[Patent Document 1] Japanese Unexamined Patent Application, First
Publication No. 2002-30460
[Patent Document 2] United States Patent No. 5,292,549 Specification
[Patent Document 3] Japanese Unexamined Patent Application, First
Publication No. 2003-105562
[Patent Document 4] Japanese Unexamined Patent Application, First
Publication No. H8-73775
[Patent Document 5] Japanese Unexamined Patent Application, First
- 4 -
Publication No. 2001-49453
[Patent Document 6] Japanese Unexamined Patent Application, First
Publication No. 2007-051365
[Disclosure of the Invention]
[Problem that the Invention is to solve]
[0011]
The present invention solves the problems with the related art and provides a
metal material subjected to a chromate-free surface treatment which is excellent in
terms of corrosion resistance, heat resistance, anti-fingerprint properties, electrical
conductivity, paintability and black shaving resistance during processing and an
aqueous metal surface-treatment agent used for the relevant surface treatment. More
specifically, the present invention relates to a metal material subjected to a chromatefree
surface treatment which can retain excellent corrosion resistance without being
affected by the alkaline degreasing, bending and punching that are conducted when the
surface-treated metal material is processed into a stamped article, and in addition, has
excellent heat resistance, anti-fingerprint properties, electrical conductivity, paintability
and black shaving resistance during processing, and an aqueous metal surfacetreatment
agent used for the relevant surface treatment.
[Means for Solving the Problems]
[0012]
The present invention has been completed upon intensive examinations that
the inventors have repeatedly conducted to solve the above-described problems. In
the present invention, a surface-treated metal material includes a composite film
formed on a surface of a metal material and is subjected to a chromate-free surface
treatment, the composite film including, as a film forming component, an organic
- 5 -
silicon compound (W) with a specific structure; as inhibitor components, at least one
metal compound (X) selected from a group consisting of a titanium compound and a
zirconium compound; a phosphate compound (Y); and a fluorine compound (Z), all of
which are essential components, and each component of the composite film has a
specific percent. The surface-treated metal material has excellent corrosion resistance,
heat resistance, anti-fingerprint properties, electrical conductivity, paintability and
black shaving resistance during processing, and can retain excellent corrosion
resistance without being affected by the alkaline degreasing, bending and punching
that are conducted when a surface-treated metal material is processed into a stamped
article.
[0013]
According to an aspect of the present invention, a surface-treated metal
material has a composite film on a surface of the metal material. The composite film
includes: as a film forming component, (i) an organic silicon compound (W) having
cyclic siloxane bonds in the structure thereof; as inhibitor components, (ii) at least one
metal compound (X) selected from a group consisting of a titanium compound and a
zirconium compound; (iii) a phosphate compound (Y); and (iv) a fluorine compound
(Z). In each of the components of the composite film, the ratio of XsAVs is fi^om 0.06
to 0.16, where Ws is the solid mass of Si derived from the organic silicon compound
(W) and Xs is the solid mass of at least one metal component selected from a group
consisting of Ti and Zr included in the metal compound (X); the ratio of YsAVs is from
0.15 to 0.31, where Ws is the solid mass of Si derived from the organic silicon
compound (W) and Ys is a solid mass of P derived from the phosphate compound (Y);
the ratio of Zs/ Ws is from 0.08 to 0.50, where Ws is the solid mass of Si derived from
the organic silicon compound (W) and Zs is the solid mass of F derived from the
%
fluorine compound (Z); and, in the composite film, the amount of an organic resin with
a mean molecular weight equal to or greater than 3,000 is limited to less than 10
mass% of the total weight of the film.
[0014]
In addition, the abundance of cyclic siloxane bonds and chain siloxane bonds
of the organic silicon compound (W) is preferably the ratio of W1AV2 ranging from 1.0
to 2.0, where Wi is an absorbance of from 1,090 to 1,100 cm'^ indicating the cyclic
siloxane bond by the FT-IR reflection method and Wz is an absorbance of fi^om 1,030
to 1,040 cm"' indicating the chain siloxane bond.
[0015]
It is preferable that the film forming component of the composite film does
not preferably contain an organic resin of which a mean molecular weight is equal to or
greater than 3,000.
[0016]
The film forming component of the composite film is preferably composed of
only the organic silicon compound (W).
[0017]
The metal compound (X) and the fluorine compound (Z) are preferably at
least one fluoro compound selected from a group consisting of titanium hydrofluoric
acid and zirconium hydrofluoric acid.
[0018]
When an interlayer resistance coefficient of the surface-treated metal material
is measured by a JIS C2550-4: 2011-Amethod where the total area of 10 pieces of
contact electrodes is 1,000 mm^, the coefficient is preferably less than 200 Qmm^ in
terms of excellence of electrical conductivity.
- 7 -
[0019]
Furthermore, it is preferable that the composite film contains, as a component
(C), at least one cobalt compound selected from a group consisting of cobalt sulphate,
cobalt nitrate and cobalt carbonate at a ratio of CsAVs ranging from 0.03 to 0.08, where
Ws is the solid mass of Si derived from the organic silicon compound (W) and Cs is
the solid mass of Co derived from the cobalt compound (C).
[0020]
In addition, the metal material is preferably a zinc-plated steel sheet.
[0021]
In addition, according to another aspect of the present invention, an aqueous
metal surface-treatment agent includes; (i) an organic silicon compound (W) having
cyclic siloxane bonds in the structure thereof; (ii) at least one metal compound (X)
selected from a group consisting of a titanium compound and a zirconium compound;
(iii) a phosphate compound (Y); and (iv) a fluorine compound (Z). In each of the
components of the aqueous metal surface-treatment agent, the ratio of XsAVs is from
0.06 to 0.16, where Ws is the solid mass of Si derived from the organic silicon
compound (W) and Xs is the solid mass of at least one metal component selected from
a group consisting of Ti and Zr included in the metal compound (X); the ratio of YsAVs
is from 0.15 to 0.31, where Ws is the solid mass of Si derived from the organic silicon
compound (W) and Ys is a solid mass of P derived from the phosphate compound (Y);
the ratio of Zs/ Ws is from 0.08 to 0.50, where Ws is the solid mass of Si derived from
the organic silicon compound (W) and Zs is a solid mass of F derived from the fluorine
compound (Z), and the amount of an organic resin of which a mean molecular weight
is equal to or greater than 3,000 is limited to less than 10 mass% of the total mass of
the solids.
- 8
[0022]
The organic silicon compound (W) of the aqueous metal surface-treatment
agent is obtained by mixing a silane coupling agent A containing at least one amino
group per molecule and a silane coupling agent B containing at least one glycidyl
group per molecule at a solid mass ratio A/B ranging from 0.5 to 1.7. It is preferable
that the organic silicon compound (W) contains, per molecule, two or more functional
groups (a) represented by a formula -SiR^R^R^ and one or more hydrophilic fiinctional
groups (b) which have at least one selected from a group consisting of a hydroxyl
group (when a functional group (a) includes a hydroxyl group, the hydroxyl group
included in the functional group (a) is discrete) and an amino group, where the R^', R^
and R^ are an alkoxy group or a hydroxyl group independently of one another, at least
one of the R^', R^ and R^ is an alkoxy group, and the mean molecular weight of the
organic silicon compound (W) is from 1,000 to 10,000.
[0023]
The metal compound (X) and the fluorine compound (Z) are preferably at
least one fluoro compound selected from a group consisting of titanium hydrofluoric
acid and zirconium hydrofluoric acid.
[0024]
In addition, it is preferable that a surface-treated metal material is coated with
an aqueous metal surface-treatment agent on a surface of the metal material and is
dried, and a composite film has a weight of from 0.05 to 2.0 g/m^ after drying is
completed.
[Advantage of the Invention]
[0025]
The surface-treated metal material and the aqueous metal surface-treatment
agent of the present invention can retain excellent corrosion resistance without being
affected by the alkaline degreasing, bending and punching that are conducted when the
surface-treated metal material is processed into a stamped article, and in addition, is
excellent in terms of heat resistance, anti-fingerprint property, electrical conductivity,
paintability and black shaving resistance during processing.
[Best Mode for Carrying Out the Invention]
[0026]
In the present invention, an applicable metal material is not particularly
specified. For example, iron, an iron-based alloy, aluminum, an aluminum-based
alloy, copper, a copper-based alloy and the like are cited, and, as necessary, a metal
material which has plating on the surface thereof can be used. Above all, in the
present invention, the most preferable material is a zinc-plated steel sheet. A
galvanized steel sheet, a zinc-nickel plated steel sheet, a zinc-iron plated steel sheet, a
zinc-chromium plated steel sheet, a zinc-aluminum plated steel sheet, a zinc-titanium
plated steel sheet, a zinc-magnesium plated steel sheet, a zinc-manganese plated steel
sheet, a zinc-aluminum-magnesium plated steel sheet, a zinc-aluminum-magnesiumsilicon
plated steel sheet and the like are cited as a zinc-plated steel sheet.
Furthermore, a zinc-plated steel sheet can be used of which the plating layer contains,
as a different metal element or impurities, a small amount of cobalt, molybdenum,
tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead,
bismuth, antimony, tin, copper, cadmium, arsenic or the like, or has an inorganic
substance such as silica, alumina and titania dispersed therein. Furthermore, the
above-described plating can be used in combination with other types of plating. For
example, a multilayer of plating is applicable in which the above-described plating is
combined with iron plating, iron-phosphorous plating, nickel plating, cobalt plating or
- 10 -
the like. A plating method is not particularly specified, and any widely known
method, such as an electro plating method, a hot dip plating method, a vapor
deposition plating method, a dispersion plating method, a vacuum plating method and
the like may be used.
[0027]
An organic silicon compound (W) is an essential component as a film forming
component of an aqueous metal surface-treatment agent used for a chromate-free
surface-treated metal material of the present invention, and has cyclic siloxane bonds
in the structure thereof Herein, the "cyclic siloxane bond" indicates a cyclic
structure which has a configuration of continuous Si-O-Si bonds, is configured with
only Si-0 bonds and has a number of the Si-0 repetition units of 3 to 8. On the other
hand, the "chain siloxane bond" indicates a structure which has a configuration of
continuous Si-O-Si bonds, is configured with only Si-0 bonds, has a number of the Si-
O repetition units of 3 to 8 and does not have the cyclic structures. When the organic
silicon compound (W) does not contain cyclic siloxane bonds in the structure thereof, a
apparent degree of cross-linking of a film is decreased, decomposition of a film due to
alkali or heat generated during processing or cohesive failure of a film due to
processing load is not restrained, a coarse film is formed, and thus, the excellent
corrosion resistance of the present invention can be not retained. In addition, the heat
resistance and black shaving resistance during processing, which are the effects of the
present invention, are inferior. Herein, "black shaving resistance during processing"
indicates resistance to a phenomenon that, when a metal material is subjected to
processing such as press working, the surface of the metal material strongly slides
against a press die or the like, and black sludge-like substance is formed from a film
covering the surface of the metal material, is fixed and accumulated, thereby impairing
- 11 -
the appearance thereof
[0028]
An organic silicon compound (W), which is an essential component as a film
forming component of an aqueous metal surface-treatment agent used for a chromatefree
surface-treated metal material of the present invention, is obtained by mixing a
silane coupling agent (A) containing at least one amino group per molecule and a
silane coupling agent (B) containing at least one glycidyl group per molecule at a solid
mass ratio [(A)/(B)] ranging from 0.5 to 1.7. It is preferable that an organic silicon
compound (W) obtained in this way contain, per molecule, two or more functional
groups (a) represented by a formula -SiR^R^R^ (wherein, R^', R^ and R^ each represent
an alkoxy group or a hydroxyl group independently of one another, and at least one of
R^', R^ and R^ represents an alkoxy group) and one or more hydrophilic functional
groups (b) which have at least one selected from a group consisting of a hydroxyl
group (when a functional group (a) includes a hydroxyl group, the hydroxyl group
included in the functional group (a) is discrete) and an amino group, and the mean
molecular weight of an organic silicon compound (W) is from 1,000 to 10,000.
[0029]
The solid mass ratio [(A)/(B)] of a silane coupling agent (A) and a silane
coupling agent (B) is preferably from 0.5 to 1.7, in which the silane coupling agent (A)
has at least one amino group per molecule and the silane coupling agent (B) has at least
one glycidyl group per molecule, and is more preferably from 0.6 to 1.5. When the
solid mass ratio [(A)/(B)] is from 0.5 to 1.7, an efficient and stable organic silicon
compound of the present invention is produced, and a film can be formed which has
excellent corrosion resistance, heat resistance, anti-fingerprint properties, electrical
conductivity, paintability and black shaving resistance during processing.
12
Furthermore, when the ratio [(A)/(B)] is in a preferable range of from 0.6 to 1.5, the
corrosion resistance can be further improved.
[0030]
The silane coupling agent (A) is not particularly specified. However, 3-
aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane or the like are exemplary
examples. Examples of the silane coupling agent (B) include 3-
glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.
[0031]
In addition, an organic silicon compound of the present invention preferably
contains, per molecule, two or more functional groups (a) represented by a formula
-SIR'R^R^ (wherein, R^', R^ and R^ each represent an alkoxy group or a hydroxyl
group independently of one another, and at least one of R^', R^ and R^ represents an
alkoxy group). When two or more of the functional groups (a) described above are
included per molecule, it is possible to regularly and densely arrange silicon-containing
portions and organic substance portions in a film, and to obtain the excellent film
which has heat resistance, electrical conductivity and black shaving resistance during
processing usually exhibited by an inorganic film, and the anti-fingerprint properties
and paintability usually exhibited by an organic film.
[0032]
In addition, an organic silicon compound of the present invention preferably
contains one or more hydrophilic functional groups (b) which have at least one
selected from a group consisting of a hydroxyl group (when a functional group (a)
includes a hydroxyl group, the hydroxyl group included in the fiinctional group (a) is
discrete) and an amino group. In addition, the mean molecular weight is preferably
from 1,000 to 10,000, and is more preferably from 1,300 to 6,000. Herein, the
13
molecular weight is not particularly specified. However, the molecular weight can be
measured by use of any measurement of a direct measurement by TOF-MS method or
a conversion measurement by a chromatographic method. When the mean molecular
weight is in a range from 1,000 to 10,000, the water resistance of a formed film is wellbalanced
with the dissolution stability or dispersion stability of the organic silicon
compound.
[0033]
In addition, the abundance of cyclic siloxane bonds and chain siloxane bonds
of the organic silicon compound (W) can be measured by a reflection method using
Fourier transform infi^ared spectrophotometer (FT-IR). The ratio of [W1AV2] is
preferably from 1.0 to 2.0, where (Wi) is an absorbance of from 1,090 to 1,100 cm'^
indicating the cyclic siloxane bond and (W2) is an absorbance of from 1,030 to 1,040
cm'^ indicating the chain siloxane bond. Furthermore, the ratio [W1AV2] is more
preferably from 1.2 to 1.8. When the ratio [W1AV2] is in a range from 1.0 to 2.0, the
excellent barrier properties and resistance to alkali or heat which are exhibited by the
cyclic siloxane bond, and pliability due to the chain siloxane bond are obtained.
Accordingly, a film can retain excellent corrosion resistance without being affected by
the alkaline degreasing, bending and punching that are conducted when the surfacetreated
metal material is processed into a stamped article, and in addition, a film can be
formed which has excellent heat resistance, anti-fingerprint properties, electrical
conductivity, paintability and black shaving resistance during processing.
[0034]
In addition, the method of manufacturing an organic silicon compound (W) of
the present invention is not particularly specified. However, a method is cited where
the silane coupling agent (A) and the silane coupling agent (B) are sequentially added
- 14 -
to water adjusted to a pH 4, and the resuhant solution is agitated for a predetermined
time. Herein, when the silane coupling agent (A) is added, the aqueous solution
generates heat. For this reason, water is cooled in advance, continues to be cooled for
a predetermined time, and the organic silicon compound (W) is manufactured in a
certain temperature range, thereby allowing control of the abundance of cyclic silane
bonds and chain silane bonds in the organic silicon compound (W). Specifically,
when the temperature is controlled to be in a range from 15 to 30°C, it is preferable
because the ratio [W1AV2] become from 1.0 to 2.0. However, when the temperature
is increased to a temperature higher than 30°C, the percentage of the cyclic siloxane
bond being produced becomes insufficient, the ratio [W1AV2] becomes less than 1.0,
and thus, the barrier properties and corrosion resistance are deteriorated. Accordingly,
a temperature higher than 30°C is not preferable. In addition, when the temperature is
lower than 15°C, the percentage of the cyclic siloxane bond being produced becomes
excessive, the ratio [W1AV2] becomes more than 2.0, and thus, the film becomes too
brittle and the workability is deteriorated. Accordingly, a temperature lower than
15°C is not preferable.
[0035]
An aqueous metal surface-treatment agent of the present invention necessarily
contains, as an inhibitor component, at least one metal compound (X) selected from a
group consisting of a titanium compound and a zirconium compound. A titanium
compound is not particularly specified. However, titanium hydrofluoric acid,
titanium ammonium fluoride, titanium sulfate, titanium oxysulfate, potassium titanium
oxide oxalate or the like are exemplary examples. Above all, titanium hydrofluoric
acid is more preferable. When titanium hydrofluoric acid is used, better corrosion
resistance or paintability can be obtained.
- 15 -
[0036]
The zirconium compound is not particularly specified. However, zirconium
hydrofluoric acid, zirconium ammonium fluoride, zirconium sulfate, zirconium
oxychloride, zirconium nitrate, zirconium acetate or the like are exemplary examples.
Zirconium hydrofluoric acid is the most preferable. When zirconium hydrofluoric
acid is used, better corrosion resistance or paintability can be obtained.
[0037]
In addition, in regard to a blending quantity of a metal compound (X) which is
an essential component of the present invention, the solid mass ratio [(Xs)/(Ws)] is
necessarily from 0.06 to 0.16, where (Ws) is the solid mass of Si derived from an
organic silicon compound (W), and (Xs) is the solid mass of at least one metal
component selected from a group consisting of Ti and Zr included in the metal
compound (X). The solid mass ratio [(Xs)/(Ws)] is preferably from 0.07 to 0.14, and
is more preferably from 0.08 to 0.13. When the solid mass ratio [(Xs)/(Ws)] is less
than 0.06, where (Ws) is a solid mass of Si derived from the organic silicon compound
(W) and (Xs) is a solid mass of at least one metal component selected from a group
consisting of Ti and Zr included in the metal compound (X), the effect of the metal
compound (X) is not exhibited, the removing of oxide film from the surface of a metal
material or reactivity between an organic silicon material (W) of the present invention
and the surface of a metal material to be treated is deteriorated, the adhesion and
barrier effects of a formed composite film are deteriorated, and thus, the overall
performance is insufficient. Accordingly, a solid mass ratio [(Xs)/(Ws)] less than
0.06 is not preferable. On the other hand, when the solid mass ratio [(Xs)/(Ws)]
exceeds 0.16, a reaction film is excessively formed on the surface of a metal material
to be treated due to a metal compound (X), and thus, the electrical conductivity is
- 16 -
remarkably deteriorated. Accordingly, a solid mass ratio [(Xs)/(Ws)] exceeding 0.16
is not preferable.
[0038]
In addition, an aqueous metal surface-treatment agent of the present invention
necessarily contains a phosphate compound (Y) as an inhibitor component. The
phosphate compound (Y) is not particularly specified. However, phosphoric acid,
ammonium phosphate, potassium phosphate, sodium phosphate or the like are
exemplary examples. Phosphoric acid is the most preferable. When phosphoric
acid is used, better corrosion resistance can be obtained.
[0039]
In regard to a blending quantity of a phosphate compound (Y) which is an
essential component of the present invention, the solid mass ratio [(Ys)/(Ws)] is
necessarily from 0.15 to 0.31, where (Ws) is a solid mass of Si derived from an organic
silicon compound (W) and (Ys) is a solid mass of P derived from a phosphate
compound (Y). The solid mass ratio [(Ys)/(Ws)] is preferably from 0.16 to 0.28, and
is more preferably from 0.18 to 0.25. When a solid mass ratio [(Ys)/(Ws)] is less than
0.15, where (Ws) is the solid mass of Si derived from the organic silicon compound
(W) and (Ys) is a solid mass of P derived from a phosphate compound (Y), the eluting
inhibitor effect of a phosphate compound (Y) is not obtained, and thus, a solid mass
ratio [(Ys)/(Ws)] less than 0.15 is not preferable. On the contrary, when the solid
mass ratio [(Ys)/(Ws)] exceeds 0.31, the film is remarkably water-soluble, and thus, a
solid mass ratio [(Ys)/(Ws)] exceeding 0.31 is not preferable.
[0040]
In addition, an aqueous metal surface-treatment agent of the present invention
necessarily contains a fluorine compound (Z) as an inhibitor component. The fluoric
- 17 -
compound (Z) is not particularly specified. However, fluoride such as hydrofluoric
acid, hydrofluoboric acid, hydrosilicofluoric acid and water soluble salts thereof and a
fluoride salt complex are exemplary examples. Hydrofluoric acid is the most
preferable. When hydrofluoric acid is used, better corrosion resistance and
paintability can be obtained.
In addition, when hydrofluoric acid is used, titanium hydrofluoric acid or
zirconium hydrofluoric acid can be more preferably used as the above-described metal
compound (X). In this case, better corrosion resistance or paintability can be
obtained.
[[0041]
In regard to a blending quantity of a fluorine compound (Z) which is an
essential component of the present invention, the solid mass ratio [(Zs)/(Ws)] is
necessarily fi-om 0.08 to 0.50, where (Ws) is the solid mass of Si derived from an
organic silicon compound (W) and (Zs) is the solid mass of F derived from a fluorine
compound (Z). The solid mass ratio [(Zs)/(Ws)] is preferably from 0.10 to 0.40, and
is more preferably from 0.15 to 0.30. When the solid mass ratio [(Zs)/(Ws)] is less
than 0.08 where (Ws) is the solid mass of Si derived from the organic silicon
compound (W) and (Zs) is a solid mass of F derived from a fluorine compound (Z), a
sufficient corrosion resistance is not obtained, and thus, a solid mass ratio [(Zs)/(Ws)]
less than 0.08 is not preferable. On the other hand, when the solid mass ratio
[(Zs)/(Ws)] exceeds 0.50, the film is remarkably water-soluble, and thus, a solid mass
ratio [(Zs)/(Ws)] exceeding 0.50 is not preferable.
[0042]
In addition, in an aqueous metal surface-treatment agent of the present
invention, an organic resin having a mean molecular weight of equal.to or greater than
- 18 -
3,000 as a film forming component is necessarily limited to less than 10 mass% of the
total solid content (that is, a total film weight) of the aqueous metal surface-treatment
agent. Herein, the "organic resin" indicates both a natural resin and a synthetic resin,
and is not particularly specified. Specifically, rosin, natural rubber or the like taken
from a plant is cited as a natural resin, and phenolic resin, epoxy resin, melamine resin,
urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, thermosetting
polyimide resin, acrylic resin, or the like is cited as a synthetic resin. The resin is
either dispersed or water-soluble in an aqueous system. An organic resin does not
include an organic silicon compound (W) in the present invention. The "mean
molecular weight of equal to or greater than 3,000" is defined because the molecular
weights of a natural resin such as rosin or natural rubber and a synthetic resin such as
phenolic resin are generally equal to or greater than 3,000. The mean molecular
weight of a resin is not particularly specified. The molecular weight can be measured
using a direct measurement method such as a TOF-MS method or a conversion
measurement method such as a chromatographic method. When an aqueous metal
surface-treatment agent of the present invention contains an organic resin of equal to or
more than 10 mass% of the total solid content of the aqueous metal surface-treatment
agent, and the contained organic resin has a mean molecular weight of equal to or
greater than 3,000, an extremely degradation occurs especially in black shaving
resistance and electrical conductivity, and it is not preferable that the amount of
organic resin contained therein be equal to or more than 10 mass% of the total solid
content. In addition, since the organic resin does not improve an excellent corrosion
resistance of an aqueous metal surface-treatment agent of the present invention, the
addition thereof is not required.
[0043]
- 19 -
Furthermore, an aqueous metal surface-treatment agent of the present
invention preferably contains, as a component (C), at least one cobalt compound
selected from a group consisting of cobah sulphate, cobalt nitrate and cobalt carbonate
in a film. The solid mass ratio of a component (C) [(Cs)/(Ws)] preferably ranges from
0.03 to 0.08, where Ws is the solid mass of Si derived from the organic silicon
compound (W) and Cs is a solid mass of Co derived from a cobalt compound (C).
The solid mass ratio [(Cs)/(Ws)] is more preferably from 0.04 to 0.07, and is most
preferably fi-om 0.05 to 0.06. When the solid mass ratio [(Cs)/(Ws)] is from 0.03 to
0.08, where (Ws) is the solid mass of Si derived from the organic silicon compound
(W) and (Cs) is a solid mass of Co derived from a cobalt compound (C), oxygendeficient
corrosion can be restrained without deteriorating the corrosion resistance,
which is an effect of Co, and thus, a solid mass ratio [(Cs)/(Ws)] ranging from 0.03 to
0.08 is preferable.
[0044]
In addition, an aqueous metal surface-treatment agent of the present invention
can contain a vanadium compound. The vanadium compound (V) is not particularly
specified. However, vanadium pentoxide V2O5, meta vanadic acid HVO3, ammonium
metavanadate, sodium metavanadate, vanadium oxyfrichloride VOCI3, vandadium
trioxide V2O3, vanadium dioxide VO2, vanadium oxysulfate VOSO4, vanadium
oxyacetylacetonate VO(OC(=CH2)CH2COCH3)2, vanadium acetylacetonate
V(OC((=CH2)CH2COCH3)3, vanadium trichloride VCI3, phosphovanadomolybdic acid,
and the like are exemplary examples thereof In addition, a tetravalent to divalent
vanadium compound can be used, which is reduced from a pentavalent vanadium
compound by an organic compound having at least one functional group selected from
a group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, primary, to
- 20 -
tertiary amino groups, an amide group, a phosphate group and a phosphonic acid group.
[0045]
In addition, in regard to a blending quantity of a vanadium compound, the
solid mass ratio [(Vs)/(Ws)] is preferably from 0.12 to 0.25, where (Ws) is a solid mass
of Si derived from an organic silicon compound (W) and (Vs) is the solid mass of V
derived from a vanadium compound. The solid mass ratio [(Vs)/(Ws)] is more
preferably from 0.14 to 0.22, and is the most preferably from 0.15 to 0.20. The
vanadium compound has an effect on not only improvement of corrosion resistance but
also the raising of the performance of a film obtained by an aqueous metal surfacetreatment
agent of the present invention due to reaction of the vanadium compound
with the organic silicon compound (W), formation of compound thereof with a
phosphate compound (Y) and the like.
[0046]
It is preferable that a surface-treated metal material of the present invention be
coated with the aqueous metal surface-treatment agent, and be dried until a
temperature reaches a temperature higher than 50°C and lower than 250°C, and the
weight of a film be from 0.05 to 2.0 g/m^ after drying is completed. In regard to a
drying temperature, the target temperature is preferably higher than 50°C and lower
than 250°C, is more preferably from 70°C to 150°C, and the most preferably from
100°C to 140°C. When the target temperature is equal to or lower than 50°C, a
solvent of the aqueous metal surface-treatment agent does not completely volatilize,
and thus, a target temperature equal to or less than 50°C is not preferable. On the
other hand, when the target temperature is equal to or higher than 250°C, a portion of
organic chains of a film formed by the aqueous metal surface-treatment agent are
decomposed, and thus, a target temperature equal to.or higher.than 250°C is not
- 21 -
preferable. The mass of a film is preferably from 0.05 to 2.0 g/m^, is more preferably
from 0.2 to 1.0 g/m^, and is the most preferably from 0.3 to 0.6 g/m^. When the mass
of a film is less than 0.05 g/m^, the surface of the metal material cannot be coated, and
thus, corrosion resistance is remarkably deteriorated. Accordingly, the mass of a film
less than 0.05 g/m^ is not preferable. On the other hand, when the mass of a film is
more than 2.0 g/m^, black shaving resistance during processing is deteriorated, and
thus, a mass of the film more than 2.0 g/m^ is not preferable.
[0047]
In an aqueous metal surface-treatment agent used in the present invention, a
leveling agent, a water-soluble solvent, a metal stabilizer, an etching inhibitor, a pH
adjuster or the like can be used to improve paintability within a limit that the effects of
the present invention are not impaired. A leveling agent includes a polyethylene
oxide or polypropylene oxide adduct, an acetylene glycol compound or the like as a
nonionic or a cationic surfactant. Alcohols such as ethanol, isopropyl alcohol, t-butyl
alcohol and propylene glycol, cellosolves such as ethylene glycol monobutyl ether and
ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, and
ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are cited as
water-soluble solvents. Chelate compounds such as EDTA and DTPA are cited as
metal stabilizers. Amine compounds such as ethylene diamine, triethylene pentamine,
guanidine and pyrimidine are cited as etching inhibitors. In particular, a metal
stabilizer having two or more amino groups per molecule is effective, and is more
preferable. Organic acids such as acetic acid and lactic acid, inorganic acids such as
hydrofluoric acid, ammonium salt, amines or like are cited as pH adjusters.
[0048]
A surface-treated metal material of the present invention can retain excellent
- 22 -
«
corrosion resistance without being affected by the alkaline degreasing, bending and
punching that are conducted when the surface-treated metal material is processed into a
stamped article, and in addition, is excellent in terms of heat resistance, anti-fingerprint
propertie, electrical conductivity, paintability and black shaving resistance during
processing. The reasons for this are assumed to be as follows, but the present
invention is not bound thereby.
[0049]
A film formed by an aqueous metal surface-treatment agent used in the
present invention is mainly formed by an organic silicon compound. First, it is
assumed that, when a portion of the organic silicon compounds is concentrated due to
drying or the like, the organic silicon compounds react with each other and form a
continuous film, and a -Si-OH group, which is produced by the hydrolyzing of the
portion of the organic silicon compounds, forms Si-O-M bonds (M: metal element in
the surface of a material to be coated) with respect to the surface of a metal, thereby
exhibiting a remarkable barrier effect and obtaining corrosion resistance. In addition,
since a dense film can be formed, the film can be thin and electrical conductivity is
improved.
On the other hand, a film formed by an aqueous metal surface-treatment agent
of the present invention is formed on the basis of silicon, and silicon and organic
chains are regularly arranged in the structure thereof In addition, since the organic
chains are relatively short, silicon-containing portions and organic substance portions,
that is, an inorganic substance and an organic substance, are regularly and densely
arranged in extremely minute areas of a film. For this reason, it is assumed that a
new film can be formed which has the heat resistance, electrical conductivity and black
shaving resistance during processing usually exhibited by an inorganiciilm andlhe
- 23 -
anti-fmgerprint properties and paintability usually exhibited by an organic film. It is
assumed that, when the abundance of cyclic siloxane bonds and chain siloxane bonds
is adjusted, silicon and organic chains are regularly arranged, the distribution of the
cyclic and chain siloxane bonds is controlled as a surface treatment film, and cyclic
siloxane bond portions and chain siloxane bond portions are arranged in a sea-island
form, thereby being able to have an extremely excellent performance of such a film.
[0050]
When, as inhibitor components, at least one metal compound (X) selected
from a group consisting of a titanium compound and a zirconium compound, a
phosphate compound (Y), and a fluorine compound (Z) are complexed in a base film
as such a film forming component, the corrosion resistance is improved. The
compounds are present as dense precipitation films in an interface between a base film
and a metal to be treated, and the precipitation films exhibit an excellent barrier efifect
against corrosive factors. Furthermore, a portion of the compounds remain as an
eluting inhibitor even in the base film and also has an effect of repairing a film defect
portion.
It is particularly preferable in view of corrosion resistance that titanium
hydrofluoric acid and/or zirconium hydrofluoric acid corresponding to both of at least
one metal compound (X) selected from a group consisting of a titanium compound and
a zirconium compound and a fluorine compound (Z) are used as inhibitor components
to be added to an aqueous metal surface-treatment agent as in the embodiments of the
present invention. The corrosion resistance-exhibiting mechanism is assumed to be
as follows. When the surface of a metal material is coated with an aqueous metal
surface-treatment agent, the pH is increased very near the surface of the metal material
to be treated by etching reaction, a portion of F is dissociated, and a dense metal oxide-
- 24 -
0
based film and/or a metal hydroxide-based film (at least one compound selected from a
group consisting of a titanium compound and a zirconium compound) is formed. In
addition, the dissociated F forms a composite compound film (F compound) with the
organic silicon compound or the metal material to be treated. The film, as described
above, exhibits excellent barrier effects against corrosion factors. It is assumed that a
composite film of the present invention, which is made based on such a corrosion
resistance-exhibiting mechanism, exhibits heat resistance, anti-fingerprint property,
electrical conductivity, paintability, black shaving resistance during processing, and
excellent corrosion resistance.
[Example]
[0051]
Hereinafter, the present invention will be specifically described with reference
to Examples and Comparative Examples. However, the present invention is not
limited thereto. The preparation of a test sheet. Examples and Comparative Examples,
and a method of coating a surface treatment agent for a metal material will be
described below.
[0052]
Preparation of Test Sheets
(1) Test Materials
The commercially available materials described below were used.
Electrolytic zinc-plated steel sheet (EG): sheet thickness = 0.8 mm, amount of
plating = 20/20 (g/m^)
Hot-dip galvanized steel sheet (GI): sheet thickness = 0.8 mm, amount of
plating = 90/90 (g/m^)
Electrogalvanized-12% nickel plating (ZL): sheet thickness = 0.8 mm, amount
25
H^'
ofplating-20/20 (g/m^)
Hot-dip zinc-11% aluminum-3% magnesium-0.2% silicon plating (SD): sheet
thickness = 0.8 mm, amount of plating = 60/60 (g/m^)
where "amount of plating" indicates a weight (g) per unit area (1 m^).
[0053]
(2) Degreasing Treatment
A silicate-based alkali degreasing agent "FINECLEANER 4336"
(manufactured by Nihon Parkerizing Co., Ltd.) was sprayed on a material for two
minutes on condition that a concentration is 20 g/L and a temperature is 60°C, was
washed with pure water for 30 seconds and was dried to obtain a test sheet.
[0054]
Silane coupling agents used in the Examples and Comparative Examples are
illustrated in Table 1; synthetic organic silicon compounds (W) are illustrated in Table
2; cobalt compounds (C) are illustrated in Table 3; and blending of the Examples and
Comparative Examples used in the tests are illustrated in Tables 4 to 5.
[0055]
[A method of Adjusting Organic Silicon Compounds Wl to W13]
Silane coupling agents (A) and silane coupling agents (B) illustrated in Table
1 were sequentially added to ion-exchanged water adjusted to pH 4 and a
predetermined temperature, the resultant solution was agitated for a predetermined
time while being controlled at a predetermined temperature, and thus, the organic
silicon compounds Wl to W13 illustrated in Table 2 were obtained.
[0056]
[A method of Adjusting Organic Silicon Compound W14 for Comparison]
The silane coupling agents (A) and the silane coupling agents (B) illustrated
- 26 -
in Table 1 were sequentially added to ion-exchanged water adjusted to pH 4, the
resultant solution was agitated for a predetermined time without a temperature control
(cooling), and thus, an organic silicon compound W14 for the comparison illustrated in
Table 2 was obtained.
[0057]
[Organic Silicon Compounds W15 to W17 for Comparison]
Organic silicon compounds according to Examples 1,3 and 5 of Japanese
Unexamined Patent Application, First Publication No. 2007-51365 were adjusted by
use of adjustment methods of the publication to obtain organic silicon compounds W15
to W17 for the comparison.
[0058]
[Urethane Resin for Comparison]
Polyether polyol (synthetic components: tetramethylene glycol and ethylene
glycol, molecular weight 1,500) (150 parts by mass), 6 parts by mass of
trimethylolpropane, 24 parts by mass of N-methyl-N, N-diethanolamine, 94 parts by
mass of isophorone diisocyanate and 135 parts by mass of methyl ethyl ketone were
put into a reaction vessel and subjected to reaction for 1 hour while a temperature was
maintained at 70°C to 75°C to produce urethane prepolymer. Subsequently, 15 parts
by mass of dimethyl sulfate was put into the reaction vessel and subjected to reaction
for 30 to 60 minutes at 50°C to 60°C to produce cationic urethane prepolymer.
Subsequently, 576 parts by mass of water was put into the reaction vessel, the mixture
was uniformly emulsified, and methyl ethyl ketone was recovered to obtain watersoluble
cationic urethane resin. The mean molecular weight of the obtained urethane
resin was measured to be 100,000 by use of a chromatographic method according to
TOF-MS.
27
[0059]
[Acrylic Resin for Comparison]
Styrene (25 parts by mass), 25 parts by mass of butyl acrylate, 20 parts by
mass of acrylonitrile, 15 parts by mass of acrylic acid, 10 parts by mass of
hydroxyethyl acrylate and 5 parts by mass of N-methylol acrylamide were
copolymerized in an reaction vessel to form acrylic resin. The produced acrylic resin
(300 parts by mass), 700 parts by mass of water and 0.5 parts by mass of
polyoxyethylene-based emulsifier were mixed and forcibly emulsified by use of an
agitator. A mean molecular weight of the obtained acrylic resin was measured to be
50,000 by use of a chromatographic method according to TOF-MS.
[0060]
[Phenol Resin for Comparison]
Phenol (1 mole) and 0.3 g of p-toluenesulfonic acid as a catalyst were put into
a 1,000-ml flask provided with a reflux condenser, the internal temperature was
increased to 100°C, 0.85 moles of aqueous formaldehyde solution was added over 1
hour, and the mixture was subjected to reaction under reflux for 2 hours at 100°C.
Thereafter, the reaction vessel was cooled in water and turbidity of an aqueous layer to
be split into an upper layer disappeared, the aqueous layer was removed by decantation,
the mixture was heated and agitated to a temperature of 170 to 175°C to remove
unreacted contents and water. Next, after the temperature was decreased to 100°C
and polycondensate was completely dissolved by adding 234 g of butyl cellosolve, 234
g of pure water was added, 1 mole of diethanolamine was added when the temperature
in the system was decreased to 50°C, and 1 mole of aqueous formaldehyde solution
was dropped into the system over approximately 1 hour at 50°C. Furthermore, the
temperature was increased to 80°C, the mixture continued to be subjected to reaction
- 28 -
while being agitated for approximately 3 hours to obtain cationic phenol-based
polycondensate. The mean molecular weight of the obtained phenol resin was
measured to be 6,000 by use of a chromatographic method according to TOF-MS.
[0061]
[Epoxy Resin for Comparison]
Bisphenol A polypropylene oxide 2 mole adduct (180 parts by mass) was put
into a reaction vessel, heated and agitated. Boron trifluoride diethylether complex
(0.9 parts by mass) was added as a catalyst, 27 parts by mass of 2-ethylhexyl
monoglycidyl ether (epoxy equivalent 198) was dropped thereto over 1 hour at 60°C to
70°C, the mixture was aged for 1.5 hours as it was, and additionally subjected to
reaction. After disappearance of oxirane rings in the system was confirmed by
hydrochloric acid absorption, boron trifluoride ethylether complex was deactivated
with 3 parts by mass of 48 mass% sodium hydroxide. While 370 parts by mass of
epichlorohydrin and 1.4 parts by mass of tetramethylammonium chloride were added,
epichlorohydrin was refluxed under reduced pressure at 50°C to 60°C, 109 parts by
mass of 48 mass% sodium hydroxide was dropped, the produced hydroxyl group was
refluxed and dehydrated. After the completion of droppage, the dehydration reaction
was progressed while refluxing and dehydration were performed for 3 hours. The
produced sodium chloride was removed by filtration. Excessive epichlorohydrin was
distilled under reduced pressure. The obtained resin had expoxy equivalent 283,
viscosity 1,725 mPas (25°C) and total chlorine content 0.4 mass%. The obtained
epoxy resin (300 parts by mass) and 700 parts by mass of water were mixed, 3.0 parts
by mass of polyoxyethylene emulsifier was added, and the mixture was forcibly
emulsified with an agitator. The mean molecular weight of the obtained epoxy resin
was measured to be 12,000 by use of a chromatographic method according to TOF-MS.
- 29 -
[0062]
[Table 1]
Al
A2
Bl
B2
Silane Coupling Agent
3-aniinopropyltrimethoxysilane
3-aminopropyltriethoxysilane
3 -gly cidoxypropyltrimethoxy silane
3-glycidoxypropyltriethoxysilane
30
m-
[0063]
[Table 2]
W-l
W-2
W-3
W-4
W-5
W-6
W-7
W-8
W-9
W-10
W-11
W-12
W-13
W-14
W-15
W-16
W-17
Silane Coupling Agent
A
Al
Al
Al
A2
A2
A2
A2
A2
Al
Al
Al
Al
Al
A2
Al
Al
Al
B
Bl
Bl
Bl
Bl
Bl
Bl
Bl
Bl
B2
B2
B2
B2
B2
Bl
B2
B2
B2
Ratio
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0,7
0.5
0.6
1.0
1.5
1.7
0.7
0.5
1.0
1.5
Number Of
Functional
Group (A)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Molecular
Weight
1500
1000
10000
2000
2000
2000
2000
2000
3000
3000
3000
3000
3000
2000
3000
3000
3000
Cyclic Siloxane
Existing/Non-
Existing
existing
existing
existing
existing
existing
existing
existing
existing
existing
existing
existing
existing
existing
non-existing
non-existing
non-existing
non-existing
W1AV2
1.3
1.2
1.4
1.5
1.8
1.2
0.5
2.3
1.9
1.3
1.8
1.7
1.7
0
0
0
0
Temperature During
Manufacturing
Start
Temperature
15
15
15
15
10
5
5
1
20
20
20
20
20
25
25
25
25
Maximum
Temperature
20
21
20
19
18
22
43
12
25
28
27
25
24
65
46
52
61
Remarks
Without temperature control
(cooling)
Organic silicon compound
(W) of Example 1 of Japanese
Unexamined Patent
Application, First Publication
No. 2007-51365
Organic silicon compound
(W) of Example 3 of Japanese
Unexamined Patent
Application, First Publication
No. 2007-51365
Organic silicon compound
(W) of Example 5 of Japanese
- 31 -
Unexamined Patent
Application, First Publication
No. 2007-51365
[0064]
[Table 3]
Cl
C2
C3
Cobalt compound (C)
Cobalt Nitrate
Cobalt Sulphate
Cobalt Carbonate
32 -
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u.
p
X
•'H
S£XH
K'^H
[0066]
[Table 5]
Ex.50
Ex.51
Ex.52
Ex.53
Ex.54
Ex.55
Ex.56
Ex. 57
Ex.58
Ex.59
Ex. 60
Ex.61
Ex.62
Ex.63
Ex.64
Ex.65
Ex. 66
Ex.67
Ex.68
Ex.69
Ex. 70
Ex.71
Ex.72
Comp.
Ex. 1
Blending
Organic
Silicon
Compound
(W)
W-10
W-10
w-10
W-IO
w-10
W-IO
w-10
W-10
w-10
W-10
w-10
w-10
w-10
w-10
W-6
W-6
w-6
W-8
W-8
W-8
W-7
W-7
W-7
W-14
Ti Or Zr Compound (X), Fluorine
Compound (Z)
Type
HsZrFfi
H,ZrF6
HoZrFs
HiZrFs
HjZrFe
H2ZrF6
HjZrFs
HjZrFs
HjTiFs
HzTiFe
H2TiF6
HzTiFs
HjTiFs
HjTiFs
HjZrFs
HjZrFe
HjZrFs
HiTiFs
ftTiFs
HjTiFs
HjZrFs
HjZrFe
HjZrFe
HoTiFfi
(X,)/(W,)
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
0.10
(Z.)/(WO
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.28
0.28
0.28
0.28
0.28
0.28
0.15
0.15
0.15
0.28
0.28
0.28
0.15
0.15
0.15
0.28
Phosphate
(Y)
Type
H3PO4
H3PO4
HjPO,
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
H3PO4
Compound
(Ys)/(W,)
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.18
0.18
0.18
0.18
0.18
0.18
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.20
0.20
Cobalt Compound (C)
Type
CI
C2
C3
CI
CI
CI
CI
CI
CI
CI
CI
(C,)/(W,)
0.05
0.05
0.05
0.03
0.04
0.06
0.07
0.08
0.05
0.05
0.05
V
Compound
VO-AA
V/Si=0.12
VO-AA
V/Si=0.14
VO-AA
V/Si=0.15
VO-AA
V/Si=0.20
VO-AA
V/Si=0.22
VO-AA
V/Si=0.25
VO-AA
V/Si=0.15
VO-AA
V/Si=0.15
VO-AA
V/Si=0.15
Organic Resin
Type Amount
Conditions
Material
EG
EG
EG
EG
EG
EG
EG
EG
EG
EG
EG
EG
EG
EG
Gl
Gl
GI
ZL
ZL
ZL
SD
SD
SD
EG
Amount
of a Film
g/m'
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
PMT
°C
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
- 35 -
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A=white rust is less than 3% of total area and black rust is not generated
B=the incidences of white rust and black rust are less than 3% of the total area
C=the incidences of white rust and black rust are equal to or more than 3% of
the total area and less than 10%
I>=the incidences of white rust and black rust are equal to or more than 10%
of the total area and less than 30%
E=the incidences of white rust and black rust are equal to or more than 30%
ofthe total area
[0068]
2. SST processed portion test
After a central portion of a rectangular test specimen of 70 mm x 150 mm
(flat sheet) having end surfaces sealed with tapes was extruded for Erichsen test (7 mm
extrusion), the test specimen was subjected to salt spray test for 72 hours according to
JIS Z 2371 and observed for the incidence of rust in extruded portion.

A=the incidence of rust is less than 5% of total area
B=the incidence of rust is equal to or more than 5% and less than 10% ofthe
- 38 -
total area
C=the incidence of rust is equal to or more than 10% and less than 20% of the
total area
D=the incidence of rust is equal to or more than 20% and less than 30% of the
total area
E=the incidence of rust is equal to or more than 30% of the total area
[0069]
3. SST flat portion test after degreasing
A rectangular test specimen of 70 mm x 150 mm was subjected to dipping
treatment for 2 minutes by use of a caustic soda-based alkali degreasing agent
FINECLEANER L4460 (manufactured by Nihon Parkerizing Co., Ltd.) on condition
that a concentration is 20 g/L of FINECLEANER L4460A agent and 12 g/L of
FINECLEANER L4460B agent, and a temperature is 60°C. The test specimen was
washed with pure water for 30 seconds and dried. The test specimen had end surfaces
sealed with tape, was subjected to salt spray test for 72 hours according to JIS Z 2371,
and was observed for the incidence of rust.

B=the incidence of rust is less than 10% of the total area
C=the incidence of rust is equal to or more than 10% and less than 20% of the
total area
D=the incidence of rust is equal to or more than 20% and less than 30% of the
total area
E=the incidence of rust is equal to or more than 30% of the total area
[0070]
4. SST end surface test after punching
- 39 -
#
A rectangular test specimen of 70 mm x 150 mm had 5 holes (each of 10 mm
diameter) opened by the punching tool at the center thereof, was subjected to a salt
spray test for 72 hours according to JIS Z 2371 and the rust widths of 5 end surfaces
were observed.
B=rust width (maximum out of 5 measurement positions) is smaller than 1
mm
C=rust width (maximum out of 5 measurement positions) is equal to or larger
than 1 mm and smaller than 2 mm
D=rust width (maximum out of 5 measurement positions) is equal to or larger
than 2 mm and smaller than 3 mm
E=rust width (maximum out of 5 measurement positions) is equal to or larger
than 3 mm
[0071]
5. Heat resistance test
A rectangular test specimen of 70 mm x 150 mm was heated in an oven for 2
hours at 200°C, had end surfaces sealed with tape, was subjected to a salt spray test for
48 hours according to JIS Z 2371 and observed for the incidence of rust.

B=the incidence of rust is less than 3% of the total area
C=the incidences of rust is equal to or more than 3% and less than 10% of
the total area
D=the incidences of rust is equal to or more than 10% and less than 30% of
the total area
E=the incidences of rust is equal to or more than 30% of the total area
[0072]
- 40 -
#
6. Anti-fingerprint properties test
A test specimen was coated with Vaseline, L values (lightness) were measured,
before and after Vaseline was coated, by use of a spectrophotometer (SC-T45
manufactured by Suga Test Instruments Co., Ltd.), and variation (AL) was calculated.

B=AL is less than 0.5
C=AL is equal to or more than 0.5 and less than 1.0
D=AL is equal to or more than 1.0 and less than 2.0
E=AL is equal to or more than 2.0
[0073]
7. Electrical conductivity test
An interlayer resistance coefficient was measured by JIS C2550-4: 2011-A
method on condition that a total area of 10 pieces of contact electrodes is 1,000 mm^

B=interlayer resistance is less than 100 Qmm^
C=interlayer resistance is equal to or more than 100 Qmm^ and less than 200
Qmm^
D=interlayer resistance is equal to or more than 200 Q-mm^ and less than 300
Qmm^
E=interlayer resistance is equal to or more than 300 Qmm^
[0074]
8. Paintability test
A test specimen was painted with melamine-alkyd based paint (amilac #1000
white manufactured by Kansai Paint Co., Ltd.) by use of a bar coater to have a film
thickness of 25 |am after baking and drying are completed, baked for 20 minutes at
41
#
120°C, scored in a grid (1 mm x 1 mm) pattern, and subjected to a tape peeling test.
Adhesion was evaluated based on the ratio of the number of remaining film grids on
the test specimen to the total number of film grids (the number of the remaining film
grids/the number of the total film grids (100 grids))

B=AL is less than 0.5
C=AL is equal to or more than 0.5 and less than 1.0
D=AL is equal to or more than 1.0 and less than 2.0
E=AL is equal to or more than 2.0
[0076]
10. SST test after deep drawing
After press oil attached to the stamped article obtained at the test 9 was
removed by use of hexane, the test specimen was subjected to salt spray test for 72
hours and observed for the incidence of rust on the side surfaces thereof

A^he incidence of rust is less than 5% of the total area
B=the incidence of rust is equal to or more than 5% and less than 10% of the
total area
C=the incidence of rust is equal to or more than 10% and less than 20% of the
total area
D=the incidence of rust is equal to or more than 20%) and less than 30% of the
total area
43
t
E=the incidence of rust is equal to or more than 30% of the total area
[0077]
Test results were illustrated in Tables 6 and 7. Accordingly, when Examples
01 to 13 and Comparative Examples 01 to 04 are compared to each other. Examples 01
to 13 use an organic silicon compound (W) according to the present invention and
show excellent performance in corrosion resistance in flat portion, corrosion resistance
in processed portion after deep drawing, corrosion resistance after degreasing and
corrosion resistance of end surfaces after punching, compared to Comparative
Example 01 (temperature is not controlled during manufacturing and cyclic siloxane
bonds are not contained) and Comparative Examples 02 to 04 (Examples of Patent
Literature, Japanese Unexamined Patent Application, First Publication No. 2007-
51365). In addition. Examples 01 to 06 have a more preferable amount of cyclic
siloxane bonds of an organic silicon compound (W), and partially or entirely show
excellent corrosion resistance compared to Examples 07 and 08. In addition, a
surface-treated steel sheet of the present invention shows excellent performance
regardless of the amount of film and peak metal temperature (PMT) compared to
Examples 14 to 24.
[0078]
According to comparisons between Examples 25 to 30 and Comparative
Examples 05 to 07, when a metal compound (X) is a titanium compound or a
zirconium compound, and the amount thereof is within a range of the present invention,
the corrosion resistance, electrical conductivity and paintability can be compatible with
each other. In addition, when a metal compound (X) is within a preferable range, any
metal compound (X) show a good performance in Examples 31 to 36. In addition,
according to comparisons between Examples 39 to 43 and Comparative Examples 08
- 44 -
•
and 09, when the amount of a fluorine compound (Z) is within a range of the present
invention, the corrosion resistance, electrical conductivity and paintability are
compatible with each other. Similarly, according to comparisons between Examples
44 to 49 and Comparative Examples 10 to 12, when the blending quantity of a
phosphate compound (Y) is within the range of the present invention, excellent
corrosion resistance, heat resistance, anti-fingerprint properteis and paintability are
compatible with each other. In addition, when a Co compound or a V compound is
contained in a composite film of the present invention, it is possible to obtain more
excellent corrosion resistance in a flat portion or processed portion without a
remarkable deterioration of performance in Examples 50 to 63. On the other hand,
according to Comparative Examples 13 to 18 containing an organic resin, when an
organic resin is contained in a composite film, electrical conductivity and black
shaving resistance, which are the effects of the present invention, are remarkably
deteriorated.
[0079]
In addition, according to comparisons between Examples 64 to 72 and
Comparative Examples 19 to 24, when a composite film of the present invention is
formed within a range of the present invention, the film is not affected by a material
itself, and any material of electrolytic zinc-plated steel sheet (EG), hot-dip galvanized
steel sheet (GI), electrogalvanized-12% nickel plating (ZL) and hot-dip zinc-11%
aluminum-3% magnesium-0.2% silicon plating (SD) show good performance.
45
•
[0080]
[Table 6]
Ex. 1
Ex.2
Ex.3
Ex.4
Ex.5
Ex.6
Ex.7
Ex.8
Ex.9
Ex. 10
Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15
Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex.20
Ex.21
Ex.22
Ex.23
Ex.24
Ex.25
Ex. 26
Ex.27
Ex.28
Ex.29
Ex.30
Ex.31
SST
Flat Portion
B
B
B
B
B
B
C
B
C
B
B
B
C
C
B
B
B
B
C
B
B
B
B
B
C
B
B
B
B
B
C
Processed Portion
Erichsen
B
B
B
B
B
B
B
C
C
B
B
B
C
C
B
B
B
B
C
B
B
B
B
B
C
B
B
B
B
B
C
Deep Drawing
B
B
B
B
B
B
B
C
C
B
B
B
C
C
B
B
B
B
C
B
B
B
B
C
C
B
B
B
B
C
C
After
Degreasing
B
B
B
B
B
B
C
B
B
B
B
B
C
C
C
B
B
B
C
C
B
B
B
B
C
B
B
B
B
B
C
Punching
End Surface
B
B
B
B
B
B
C
C
C
B
B
B
B
C
C
B
B
B
C
C
B
B
B
C
C
B
B
B
B
B
C
Heat
Resistance
B
B
B
B
B
B
B
B
B
B
B
B
C
B
B
B
B
C
B
B
B
B
B
B
C
B
B
B
B
B
C
Anti-
Fingerprint
Properties
B
C
B
B
B
B
C
B
B
B
B
B
C
C
C
B
B
B
C
B
B
B
B
B
C
B
B
B
B
B
C
Electrical
Conductivity
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
C
C
C
B
B
B
B
B
B
B
B
B
C
C
B
Paintability
B
B
B
B
B
B
B
C
B
B
B
B
B
B
B
B
B
B
C
B
B
B
B
C
C
B
B
B
C
C
C
Black
Shaving
Resistance
B
B
C
B
B
B
B
B
B
B
B
B
B
B
B
B
B
C
C
C
B
B
B
C
C
B
B
B
B
B
C
46
mmm^fimmmmmmmm
w^
Ex.32
Ex.33
Ex.34
Ex.35
Ex.36
Ex.37
Ex.38
Ex.39
Ex.40
Ex.41
Ex.42
Ex. 43
Ex.44
Ex.45
Ex.46
Ex.47
Ex.48
Ex.49
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
C
C
C
B
B
C
C
C
B
B
B
B
B
B
B
B
B
C
C
C
C
B
B
C
C
C
B
B
B
B
B
B
B
B
B
B
C
C
C
C
B
B
C
C
B
B
B
C
C
B
B
B
B
B
B
B
C
B
B
B
C
C
B
B
B
B
C
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
C
C
B
B
B
B
B
B
B
B
B
B
B
C
B
B
B
B
C
C
B
B
B
B
C
B
B
B
B
B
C
C
B
B
B
B
B
C
B
B
B
B
C
C
C
C
C
B
C
C
B
B
B
B
C
C
B
B
B
B
B
B
B
B
B
B
B
C
B
B
B
B
B
C
47
mn^ippni WliplWIWBBi
[0081]
[Table 7]
Ex.50
Ex.51
Ex.52
Ex.53
Ex.54
Ex.55
Ex.56
Ex.57
Ex.58
Ex.59
Ex, 60
Ex.61
Ex.62
Ex.63
Ex.64
Ex.65
Ex.66
Ex.67
Ex.68
Ex.69
Ex.70
E.X. 71
Ex.72
Comp. Ex. 1
Comp. Ex. 2
Comp. Ex. 3
Comp. Ex. 4
Comp. Ex, 5
Comp. Ex. 6
Comp, Ex. 7
Comp. Ex. 8
SST
Flat Portion
A
A
A
A
A
A
A
A
B
B
B
B
B
B
B
A
B
B
A
B
B
A
B
D
D
D
D
E
D
B
C
Processed Portion
Erichsen
B
B
B
B
B
B
B
B
A
A
A
A
A
A
B
B
A
B
B
A
B
B
A
C
C
D
D
E
E
B
C
Deep Drawing
B
B
B
B
B
B
B
B
B
B
A
A
A
A
B
B
A
B
B
A
B
B
A
D
D
D
D
E
E
E
C
After
Degreasing
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
D
E
E
E
E
E
B
D
Punching
End Surface
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
E
D
D
C
E
E
B
D
Heat
Resistance
B
B
B
B
B
B
B
B
B
B
B
B
C
C
B
B
B
B
B
B
B
B
B
B
B
B
B
D
C
B
C
Anti-
Fingerprint
Properties
B
B
B
B
B
B
B
C
B
B
B
B
B
C
B
B
B
B
B
B
B
B
B
B
B
B
B
D
C
B
B
Electrical
Conductivity
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
E
B
Paintability
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
E
D
E
D
Black
Shaving
Resistance
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
D
D
B
C
48
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[0082]
As described above, a metal material subjected to a chromate-free surface
treatment which forms a composite film of the present invention can retain corrosion
resistance, heat resistance, anti-fmgerprint properties, electrical conductivity,
paintability and black shaving resistance during processing, and more specifically, can
retain excellent corrosion resistance without being affected by the alkaline degreasing,
bending and punching that are conducted when the surface-treated metal material is
processed into a stamped article.
[Industrial Applicability]
[0083]
A surface-treated metal material and an aqueous metal surface-treatment agent
of the present invention can retain an excellent corrosion resistance without being
affected by the alkaline degreasing, bending and punching that are conducted when the
surface-treated metal material is processed into a stamped article, and in addition, are
excellent in terms of heat resistance, anti-fingerprint property, electrical conductivity,
paintability and black shaving resistance during processing. Consequently, the
present invention can be preferably used as a surface-treated metal material and an
aqueous metal surface-treatment agent.
- 50

[Designation of Document] CLAIMS
[Claim 1]
A surface-treated metal material comprising:
a composite film on a surface of a metal material, the composite film
comprising
as a film forming component, (i) an organic silicon compound (W) having
cyclic siloxane bonds in the structure thereof; and
as inhibitor components, (ii) at least one metal compound (X) selected from a
group consisting of a titanium compound and a zirconium compound, (iii) a phosphate
compound (Y), and (iv) a fluorine compound (Z);
wherein each of the components of the composite film has:
a ratio of XsAVs from 0.06 to 0.16, where Ws is a solid mass of Si derived
from the organic silicon compound (W) and Xs is a solid mass of at least one metal
component selected from a group consisting of Ti and Zr included in the metal
compound (X);
a ratio of YsAVs from 0.15 to 0.31, where Ws is the solid mass of Si derived
from the organic silicon compound (W) and Ys is a solid mass of P derived from the
phosphate compound (Y); and
a ratio of Zs/ Ws from 0.08 to 0.50, where Ws is the solid mass of Si derived
from the organic silicon compound (W) and Zs is a solid mass of F derived from the
fluorine compound (Z); and
wherein, in the composite film, the amount of an organic resin of which
a mean molecular weight is equal to or greater than 3,000 is limited to less tha
n 10 mass% of a total weight of the film.
[Claim 2]
- 51 -
•
The surface-treated metal material according to claim 1,
wherein an abundance of cyclic siloxane bonds and chain siloxane bonds of
the organic silicon compound (W) is a ratio of W1AV2 ranging from 1.0 to 2.0, where
Wi is an absorbance of from 1,090 to 1,100 cm"' indicating the cyclic siloxane bond
by the FT-IR reflection method and W2 is an absorbance of from 1,030 to 1,040 cm'
indicating the chain siloxane bond.
[Claim 3]
The surface-treated metal material according to claim 1 or 2,
wherein the film forming component does not contain an organic resin of
which a mean molecular weight is equal to or greater than 3,000.
[Claim 4]
The surface-treated metal material according to claim 1 or 2,
wherein the film forming component is composed of only the organic silicon
compound (W).
[Claim 5]
The surface-treated metal material according to claim 1 or 2,
wherein the metal compound (X) and the fluorine compound (Z) are at least
one fluoro compound selected from a group consisting of titanium hydrofluoric acid
and zirconium hydrofluoric acid.
[Claim 6]
The surface-treated metal material according to claim 1 or 2,
wherein when an interlayer resistance coefficient is measured by a JIS C2550-
4: 2011-A method where a total area of 10 pieces of contact electrodes is 1,000 mm^,
the coefficient is less than 200 Qmm^.
[Claim 7]
52
•
The surface-treated metal material according to claim 1 or 2,
wherein the composite film contains a cobalt compound (C) at a ratio of
CsAVs ranging from 0.03 to 0.08, where Ws is the solid mass of Si derived from the
organic silicon compound (W) and Cs is a solid mass of Co derived from the cobalt
compound (C).
[Claim 8]
The surface-treated metal material according to claim 1 or 2,
wherein the metal material is a zinc-plated steel sheet.
[Claim 9]
An aqueous metal surface-freatment agent comprising:
(i) an organic silicon compound (W) having cyclic siloxane bonds in the
structure thereof;
(ii) at least one metal compound (X) selected from a group consisting of a
titanium compound and a zirconium compound;
(iii) a phosphate compound (Y); and
(iv) a fluorine compound (Z),
wherein each of the components of the aqueous metal surface-treatment agent
has:
a ratio of XsAVs from 0.06 to 0.16, where Ws is a solid mass of Si derived
from the organic silicon compound (W) and Xs is a solid mass of at least one metal
component selected from a group consisting of Ti and Zr included in the metal
compound (X);
a ratio of YsAVs from 0.15 to 0.31, where Ws is the solid mass of Si derived
from the organic silicon compound (W) and Ys is a solid mass of P derived from the
phosphate compound (Y); and
- 53 -
• ^
a ratio of Zs/ Ws from 0.08 to 0.50, where Ws is the solid mass of Si derived
from the organic silicon compound (W) and Zs is a solid mass of F derived from the
fluorine compound (Z); and
wherein the amount of an organic resin of which a mean molecular weight is
equal to or greater than 3,000 is limited to less than 10 mass% of a total solid mass.
[Claim 10]
The aqueous metal surface-treatment agent according to claim 9,
wherein the organic silicon compound (W) is obtained by mixing a silane
coupling agent A containing at least one amino group per molecule and a silane
coupling agent B containing at least one glycidyl group per molecule at a solid mass
ratio A/B ranging from 0.5 to 1.7;
wherein the organic silicon compound (W) contains, per molecule, two or
more fiinctional groups (a) represented by a general formula -SIR'R^R^ and one or
more hydrophilic fiinctional groups (b) which have at least one selected from a group
consisting of a hydroxyl group and an amino group, where the R^ R^ and R'' are an
alkoxy group or a hydroxyl group independently on one another and at least one of the
R^ R^ and R^ is an alkoxy group; and
wherein a mean molecular weight of the organic silicon compound (W) is
from 1,000 to 10,000.
[Claim 11]
The aqueous metal surface-treatment agent according to claim 9 or claim 10,
wherein the metal compound (X) and the fluorine compound (Z) are at least
one fluoro compound selected from a group consisting of titanium hydrofluoric acid
and zirconium hydrofluoric acid.
[Claim 12]
54
A surface-treated metal material,
wherein a surface of a metal material is coated with the aqueous metal
surface-treatment agent according to claim 8 or 9 and is dried, and a composite film
has a weight of from 0.05 to 2.0 g/m^ after drying is completed.