DESCRIPTION
TITLE OF INVENTION
METAL SURFACE TREATMENT AGENT FOR ZINC-PLATED STEEL
MATERIAL, COATING METHOD, AND COATED STEEL MATERIAL
TECHNICAL FIELD
[0001]
The present invention relates to a metal snrface treatment agent for a zinc-plated steel
material, a coating method using the metal snrface treatment agent, and a coated steel material.
BACKGROUND ART
[0002]
Conventionally, zinc-plated steel materials, etc. have been generally subjected to rust
preventive treatment by chromate using a hexavalent chromium salt, and the resultant has
been coated, as required, with an organic resin in order to impart fingerprint resistance·,
scratch resistance, etc. thereto, and thereafter, fmther overcoated with various paints.
[0003]
In recent years, amid emergence of environmental problems, there are moves to legally
restrict or prohibit chromate treatment, which has been conventionally applied to steel
materials. Cln·omate-treated layers have high corrosion resistance and paint adhesiveness by
themselves. If this chromate treatment cannot be conducted, these performances will
drastically deteriorate. Thus, it has been required to form a rust preventive layer having
good corrosion resistance and paint adhesiveness without conducting cln·omate treatment.
[0004]
PTL 1 describes a coated steel sheet characterized in that the coated steel sheet has a
coating film which is formed by combining ethylene-unsaturated carboxylic acid copolymer
resin particles (A) having an average particle size of20 to 100 nm and containing a silanol
group and/or alkoxysilyl group, silicone oxide pmticles (B) having an average particle size of
5 to 50 nm, and an organic titanium compound (C) and that the amount of the coating film is
0.5 to 3 g/m2
. However, although the above-described coating film improves the substrate
adhesiveness and press oil resistance, finther improvement in the tape-peeling resistance is
required.
[0005]
2
PTL 2 describes a surface-treated metal sheet characterized in that the metal sheet is
formed by applying a treatment solution containing an organic resin, a silane coupling agent,
and a solid humectant in a lithium silicate aqueous solution having an Si02/Li20 ratio (molar
ratio) of 18 to 33 to a surface of the metal sheet followed by drying. However, the abovedescribed
metal sheet has the problem of poor alkali resistance.
[0006]
PTL 3 describes a surface-treated metal sheet in which a surface treatment coating film
is formed on a metal sheet or a metal-plated sheet, characterized in that the surface treatment
film contains Si and Li such that Si/Li (molar ratio) reaches 36 to 66 as well as substantially
contains no Cr. However, the above-described metal sheet has the problem of inferior tapepeeling
resistance.
[0007]
PTL 4 describes a surface treatment solution for zinc-plated metal materials,
characterized by containing, in an aqueous medium, lithium silicate having an Si/Li molar
ratio in the range of 1 to 4, and also containing 5 to 50 parts by mass of a silane coupling
agent, 0.2 to 10 parts by mass (as vanadium metal) of a vanadium compound, 0.2 to 10 parts
by mass (as titanium metal) of a titanium compound, and 0.01 to 10 parts by mass of wax,
each based on 100 parts by mass of the lithium silicate. However, the above-described
surface treatment solution for zinc-plated metal materials has insufficient alkali resistance.
CITATION LIST
PATENT LITERATURE
[0008]
PTL 1: JP 4922295 B
PTL 2: JP-A-11-58599
PTL 3: JP-A-2000-45078
PTL 4: JP-A-2010-37584
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0009]
In view of the above-described situation, an object of the present invention is to
provide a metal surface treatment agent for a zinc-plated steel material having improved press
oil resistance, substrate adhesiveness, tape-peeling resistance, paint adhesiveness, resistance
3
of a processed part to corrosion, alkali resistance, and ablation resistance, a coating method
using the metal surface treatment agent, and a coated steel material.
[0010]
Here, the tape-peeling resistance means that, in the case of transporting coils or
processed articles of steel material by sea mail, even if the coils or articles are fixed with
highly adhesive tape and subjected to high temperature and high humidity conditions, a
coating film on the coils or articles will not come off on peeling the tape off. The ablation
resistance refers to resistance against abrasion flaws that may be caused by fretting in the case
of transpot1ing coils or processed mticles of steel material.
SOLUTION TO PROBLEM
[0011]
The present inventors have intensively studied to find that a metal surface treatment
agent for a zinc-plated steel material which comprises a specific organic resin pat1icles (A),
silicon oxide patticles (B), lithium silicate (C), an organic titanium compound (D), and an
epoxy-group containing compound (E), develops excellent press oil resistance, substrate
adhesiveness, tape-peeling resistance, paint adhesiveness, resistance of a processed part to
corrosion, alkali resistance, and ablation resistance in which the total number of moles of
silicon, calculated in terms of SiOz, contained in the silicon oxide particles (B) and the lithium
silicate (C) is 40 to 70 times the number of moles of elemental lithium, calculated in terms of
Li02, contained in the lithium silicate (C), and in which the ratio of the mass of the lithium
silicate (C) relative to the mass of elemental titanium contained in the organic titanium
compound (D) is 0.2 to 200, having completed the present invention.
[0012]
Specifically, the present invention provides the following [I] to [7].
[I] A metal surface treatment agent for a zinc-plated steel material comprising organic resin
pmticles (A), silicon oxide patticles (B), lithium silicate (C), an organic titanium compound
(D), and an epoxy-group containing compound (E),
wherein the organic resin particles (A) are resin particles which is prepared by
modifying a base resin with a silane coupling agent (A-1) and a multifunctional epoxy-group
containing compound (A-2) and the organic resin particles (A) have a silanol group and/or an
alkoxysilyl group, and the total number of moles of elemental silicon, calculated in terms of
Si02, contained in the silicon oxide particles (B) and the lithium silicate (C) is 40 to 70 times
the number of moles of elemental lithium, calculated in terms of LizO, contained in the
lithium silicate (C),
4
wherein based on the total mass of the solid content of the metal surface treatment
agent, the mass of the solid content of the organic resin particles (A) is 20 to 70% by mass,
the content of the silicon oxide particles (B) is I 0 to 50% by mass, the content of the lithium
silicate (C) is 1 to I 0% by mass, the content of the organic titanium compound (D) is, in terms
of elemental titanium, 0.05 to 5% by mass, and the content of the epoxy-group containing
compound (E) is 0.2 to I 0% by mass, and
wherein the ratio of the mass of the lithium silicate (C) relative to the mass of
elemental titanium contained in the organic titanium compound (D) is 0.2 to 200.
[2] The metal surface treatment agent for a zinc-plated steel material according to the above
[I], wherein the ratio of the mass of the total amount of the silane coupling agent (A-1)
relative to the sum of the mass of elemental titanium contained in the organic titanium
compound (D) and the mass of the lithium silicate (C) is 0.01 to 13.
(3] The metal surface treatment agent for a zinc-plated steel material according to the above
[I] or [2], comprising 0.1 to 10% by mass of a niobium compound (F) based on the total mass
of the solid content of the metal surface treatment agent.
[4] The metal surface treatment agent for a zinc-plated steel material according to any one of
the above [I] to [3], comprising 0.1 to 10% by mass of a phosphate compound (G), in terms
of elemental phosphorous, based on the total mass of the solid content of the metal surface
treatment agent.
(5] The metal surface treatment agent for a zinc-plated steel material according to any one of
the above [1] to [4], wherein the organic resin particles (A) are obtained by blending a silane
coupling agent (A-1) in a propmtion of 1 to 20% by mass based on the mass of the solid
content of the base resin and allowing the blend to react.
[6] The metal surface treatment agent for a zinc-plated steel material according to any one of
the above [1] to (5], wherein the organic resin pmticles (A) are obtained by blending a
multifunctional epoxy-group containing compound (A-2) in a proportion of 1 to 20% by mass
based on the mass of the solid content of the base resin and allowing the blend to react.
[7] The metal surface treatment agent for a zinc-plated steel material according to any one of
the above [1] to [6],
wherein the total number of moles of elemental silicon, calculated in terms of Si02,
contained in the silicon oxide particles (B) and the lithium silicate (C) is 50 to 65 times the
number of moles of elemental lithium, calculated in terms ofLi20, contained in the lithium
silicate (C).
5
[8] A method for coating a zinc-plated steel material, comprising a step of applying the metal
surface treatment agent for a zinc-plated steel material according to any one of the above [I]
to [7] to a surface of the zinc-plated steel material to form a coating film.
[9] A coated steel material obtained by the method for coating a zinc-plated steel material
according to the above [8].
ADVANTAGEOUS EFFECTS OF INVENTION
[0013]
According to the present invention, it is possible to provide a metal surface treatment
agent for a zinc-plated steel material having improved press oil resistance, substrate
adhesiveness, tape-peeling resistance, paint adhesiveness, resistance of a processed part to
corrosion, alkali resistance, and ablation resistance, a coating method using the metal surface
treatment agent, and a coated steel material.
DESCRIPTION OF EMBODIMENTS
[0014]
Hereinbelow, the present invention will be described in detail, but the present
invention is not limited by the following embodiments.
[0015]
[Metal surface treatment agent for a zinc-plated steel material]
The metal surface treatment agent for a zinc-plated steel material of the present
invention is a metal surface treatment agent for a zinc-plated steel material comprising
organic resin particles (A), silicon oxide particles (B), lithium silicate (C), an organic titanium
compound (D), and an epoxy-group containing compound (E), wherein the organic resin
particles (A) are resin particles which are modified by a silane coupling agent (A-1) and a
multifunctional epoxy-group containing compound (A-2) and have a silanol group and/or an
alkoxysilyl group, and the total number of moles of elemental silicon, calculated in terms of
SiOz, contained in the silicon oxide pmiicles (B) and the lithium silicate (C) is 40 to 70 times
the number of moles of elemental lithium, calculated in terms of Li20, contained in the
lithium silicate (C), wherein based on the total mass ofthe solid content of the metal surface
treatment agent, the mass of the solid content of the organic resin particles (A) is 20 to 70%
by mass, the content of the silicon oxide particles (B) is 10 to 50% by mass, the content of the
lithium silicate (C) is I to 10% by mass, the content of the organic titanium compound (D) is,
in terms of elemental titanium, 0.05 to 5% by mass, and the content of the epoxy-group
containing compound (E) is 0.2 to 10% by mass, and wherein the ratio of the mass of the
6
lithium silicate (C) relative to the mass of elemental titanium contained in the organic
titanium compound (D) is 0.2 to 200.
Accordingly, the metal surface treatment agent for a zinc-plated steel material of the
present invention has excellent performance in any of press oil resistance, substrate
adhesiveness, tape-peeling resistance, paint adhesiveness, resistance of a processed part to
corrosion, alkali resistance, and ablation resistance.
[0016]

The organic resin particles (A) used in the present invention are resin patticles which
are prepared by modifying a base resin with a silane coupling agent (A-1) and a
multifunctional epoxy-group containing compound (A-2) and have a silanol group and/or an
alkoxysilyl group.
Examples of the base resin include, but are not particularly limited to, water dispersed
acrylic resins prepared by dispersing a copolymer resin of ethylene and an unsaturated
carboxylic acid, such as acrylic acid, methacrylic acid and maleic anhydride (for example,
ethylene-methacrylic acid copolymer) in water by neu!ralizing with an alkali metal hydroxide,
such as sodium hydroxide and potassium hydroxide, or ammonia water or organic amines ;
water dispersed polyurethane resins prepared by reacting an isocyanate group-containing
compound, a polyol, a low molecular weight polyol, and a compound containing an active
hydrogen group and a hydrophilic group in order to produce a polyurethane prepolymer, and
subsequently, by neutralizing the above-described hydrophilic group with a neutralizing agent
of the polyurethane prepolymer.
Examples of the organic resin patticles (A) include acrylic resin particles having a
silanol group and/or an alkoxysilyl group obtained by allowing a silane coupling agent (A-1)
and a multifunctional epoxy-group containing compound (A-2) described below to act on
these dispersed resin solutions, or polyurethane resin particles having a silanol group and/or
an alkoxysilyl group. Of these, acrylic resin particles obtained by allowing a silane coupling
agent (A-1) and a multifi.mctional epoxy-group containing compound (A-2), etc. described
below to act on a water dispersed resin solution of an ethylene-methacrylic acid copolymer
neutralized with base are preferred from the viewpoints of being capable ofthe
micropatticulate of particles forming a high-performance coating film.
[0017]
For example, in the case where the above-described ethylene-methacrylic acid
copolymer resin is used as the base resin, the base resin preferably comprises ethylene in a
content of 90 to 70% by mass and methacrylic acid in a content of I 0 to 30% by mass.
7
Although the base resin may contain other monomers as required, the amount of the
monomer used is preferably I 0% by mass or less. In use of the above-described ethylenemethacrylic
acid copolymer resin, it is possible to produce the resin by a known method such
as polymerization by an apparatus for producing high pressure low-density polyethylene, etc.
As for the amount of the base resin blended, it is preferable to react 80% by mass or
more of the base resin, based on the mass of the solid content of the organic resin particles
(A). It is more preferable to react the base resin in a range of 90% by mass or more, based
on the mass of the solid content of the organic resin particles.
[00 18]
The organic resin particles (A) have a silanol group and/or an alkoxysilyl group.
Since the organic resin pmiicles (A) have the above-described functional group, it is capable
of causing reaction with silicon oxide pmiicles (B) or an organic titanium compound (D) so as
to form a coating film. As a result, it is capable of improving the substrate adhesiveness,
press oil resistance, etc. Examples of the alkoxysilyl group in the above-described
alkoxysilyl group include, but are not particularly limited to, a trimethoxysilyl group, a
dimethoxysilyl group, a methoxysilyl group, a triethoxysilyl group, a diethoxysilyl group, and
an ethoxysilyl groups. The above-described functional group can be obtained by reacting a
silane coupling agent (A-1 ), etc. described below with a water dispersion of the abovedescribed
base resin.
[0019]
(Silane coupling agent (A-1))
Examples of the silane coupling agent (A-1) used in the organic resin particles (A)
include epoxy group-containing silane compounds such as 3-
glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-
glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane; amino group-containing silane compounds such as y(
2-aminoethyl)aminopropyltrimethoxysilane, y-(2-aminoethyl)aminopropyltriethoxysilane, y(
2-aminoethyl)aminopropylmethyldimethoxysilane, y-(2-
aminoethyl)aminopropylmethyldiethoxysilane, y-aminopropyltrimethoxysilane, yaminopropyltriethoxysilane,
y-aminopropylethoxysilane, N-[2-(vinylbenzylamino)ethyl]-3-
aminopropyltrimethoxysilane, and N-phenyl-y-aminopropyltrimethoxysilane; mercapto
group-containing silane compounds such as y-mercaptopropyltrimethoxysilane, ymercaptopropylmethyldimethoxysilane,
y-mercaptopropyltriethoxysilane, andymercaptopropylmethyldiethoxysilane;
vinyltrimethoxysilane, vinyltriethoxysilane, ymethacryloxypropylmethyldimethoxysilane,
y-methacryloxypropyltrimethoxysilane, y8
mcthacryloxypropylmethyldiethoxysilane, and y-methacryloxypropyltriethoxysilanc, and
epoxy group-containing silane compounds arc preferred. These may be used alone, or two
or more of these may be used in combination.
As for the amount blended, the silane coupling agent (A-I) is preferably blended in a
proportion of 1 to 20% by mass based on 100% by mass of the solid content of the base resin
and allowed to react. It is more preferable to react the silane coupling agent (A-1) in a range
of 1 to 10% by mass, based on I 00% by mass of the solid content of the base resin. When
the amount of the silane coupling agent (A-1) blended is 1% by mass or more, a coating film
to be formed on the surface of the steel material is excellent in alkali resistance, solvent
resistance, and paint adhesiveness, etc. When the amount of the silane coupling agent (A-1)
is 20% by mass or less, the hydrophilicity of the coating film may become appropriate, the
corrosion resistance may become good, and the solution stability of the metal surface
treatment agent used for forming a coating film may become good.
[0020]
(Multifunctional epoxy-group containing compound (A-2))
Examples of the multifunctional epoxy-group containing compound (A-2) used in the
organic resin pmticles (A) include sorbitol polyglycidyl ether,
pentaerythritolpolyglycidylether, glycerolpolyglycidylether, diglycerolpolyglycidylether,
propyleneglycoldiglycidylether, triglycidyltris(2-hydroxyethyl) isocyanurate, bisphenol A
glycidylether, and hydrogenated bisphenol A glycidylether. These may be used alone, or
two or more of these may be used in combination. Using the multifunctional epoxy-group
containing compound (A-2) increases the affinity with an organic resin, and thus may be
advantageous for increasing the paint film adhesiveness when the coating film is overcoated
with an overcoat paint.
Here, the multifunctional epoxy-group containing compound (A-2) includes no epoxy
group-containing silane compound.
As for the amount blended, it is preferable to react 1 to 20% by mass of the
multifunctional epoxy-group containing compound (A-2), based on 100% by mass of the
solid content of the base resin. It is more preferable to react the multifunctional epoxy-group
containing compound (A-2) in a range of I to I 0 % by mass or more, based on 100% by mass
of the solid content of the base resin. When the amount of the multifimctional epoxy-group
containing compound (A-2) blended is 1% by mass or more, a coating film to be formed on
the surface of the steel material is excellent in alkali resistance, solvent resistance, paint
adhesiveness, etc. When the amount of the multifunctional epoxy-group containing
compound (A-2) is 20% by mass or less, the hydrophilicity of the coating film may become
:')
9
appropriate, the corrosion resistance may become good, and the solution stability of the metal
surface treatment agent used for forming a coating fihn may become good.
[0021]
Resin particles of the organic resin particles (A) preferably has an average particle size
of 20 to I 00 nm. Here, the average particle size can be measured by a particle size
measuring apparatus using dynamic light scattering, such as FPAR-1000 (manufactured by
Otsuka Electronics Co., Ltd.). The average particle size value is a cumulant average patticle
size obtained by measuring at a solution temperature of 25°C after diluting a water dispersion
of the resin particles (A) with ion exchange water to a concentration appropriate for
measurement by the above-described apparatus. When the average particle size by the
method is 20 mn or more, the viscosity and hydrophilicity become appropriate, and
workability, corrosion resistance, etc. become satisfactory. When the average particle size is
1 00 nm or less, the substrate adhesiveness, press oil resistance, etc. become satisfactory in
respect of the coating film performance.
[0022]
The organic resin particles (A) are contained in a content of20 to 70% by mass based
on the total mass of the solid content of the metal surface treatment agent. When the content
of the organic resin particles (A) is less than 20% by mass, it is not possible to achieve
sufficient performance of a paint film, in particular, resistance of a processed part to corrosion.
From the viewpoint of exerting the effect of the present invention satisfactorily by adjusting
the balance with the content of other ingredients, the content of the organic resin particles (A)
is within 70% by mass. For the similar reason, the content of the organic resin particles (A)
is preferably 30 to 65% by mass, more preferably 40 to 60% by mass, based on the total mass
of the solid content of the metal surface treatment agent.
The content ofthe organic resin pmticles (A) can be also calculated from the amount
blended when each raw material is blended.
[0023]

The silicon oxide particles (B) used in the present invention preferably has a number
average particle size of the primary particles of 5 to 50 mn, more preferably 5 to 20 nm, and
can be selected from colloidal silica, fumed silica, etc. as appropriate. The number average
pmticle size of the primary particles of the silicon oxide pmticles (B) can be determined by
electron microscopy observation. Specific examples of the silicon oxide particles (B)
include SNOWTEXN, SNOWTEX C (manufactured byNissan Chemical Industries, Ltd.),
ADELITE AT-20N, AT-20A (manufactured by ADEKA CORPORATION), Cataloid S-20L,
10
and Cataloid SA (manufactured by JGC Catalysts and Chemicals Ltd.). These may be used
alone, or two or more of these may be used in combination.
The silicon oxide particles (B) are contained in a content of l 0 to 50% by mass based
on the total mass of the solid content of the metal surface treatment agent. When the content
is less than l 0% by mass, it is not possible to achieve sufficient performance of a paint film,
in particular, substrate adhesiveness and tape-peeling resistance. For exerting the effect of
the present invention satisfactorily by adjusting the balance with the content of other
ingredients, the content is 50% by mass or less. For the similar reason, the content of the
silicon oxide particles (B) is preferably 15 to 45% by mass, more preferably 20 to 40% by
mass, based on the total mass of the solid content of the metal smface treatment agent.
The content of the silicon oxide particles (B) can be also calculated from the amount
blended when each raw material is blended.
[0024]

The lithium silicate (C) used in the present invention is a salt composed of a lithium
oxide and silicon dioxide and represented by the general formula LhO·nSi02. According to
a value of n, which represents a molar ratio between lithium oxide and silicon dioxide,
examples include lithium otihosilicate (Li4Si04 (Liz0·0.5Si0z: n = 0.5)), lithium metasilicate
(LizSiOJ (LizO·SiOz: n = 1)), hexalithium orthodisilicate (Li6Si201 (Liz0·2/3Si0z:n = 2/3)),
Li4Sh0t6 (Liz0·3.5Si0z: n = 3.5), Li4Si902o (Liz0·4.5Si0z: n = 4.5), and L4Si,s0Jz
(Liz0·7.5Si0z: n = 7.5). The lithium silicate (C) also may be a hydrate thereof, for example.
The lithium silicate (C) may be used as a lithium silicate aqueous solution, for example.
In such a case, the solid content ofthe aqueous solution is, for example, I to 50% by mass,
preferably 2 to 40% by mass. The lithium silicate (C) has a different water solubility
depending on a value of n, which is a molar ratio between lithium oxide and silicon dioxide.
For example, a lithium silicate having n of2 to 5 is water-soluble, but a lithium silicate
having n of 6 to I 0 is watet-insoluble.
Examples of such a lithium silicate (C) include Lithium silicate 35 (lithium silicate
aqueous solution, SiOz/LhO (molar ratio)= 3.5), Lithium silicate 45 (lithium silicate aqueous
solution, Si02/Lh0 (molar ratio) = 4.5), and Lithium silicate 75 (lithium silicate aqueous
solution, Si02/Liz0 (molar ratio)= 7.5) (all manufactured by Nissan Chemical Industries,
Ltd.). These may be used alone, or two or more of these may be used in combination.
It is considered that the lithium silicate (C) forms pseudo-crosslinking by ionic
crosslinking with the silicon oxide particles (B) to thereby form a coating film excellent in
tape adhesion resistance.
11
The lithium silicate (C) is contained in a content of 1 to 10% by mass based on the
total mass of the solid content of the metal surface treatment agent. When the content of the
lithium silicate (C) is less than 1% by mass, the tape-peeling resistance becomes
unsatisfactory. From the viewpoint of exerting the effect of the present invention
satisfactorily by adjusting the balance with the content of other ingredients, the content is
10% by mass or less. For the similar reason, the content of the lithium silicate (C) is
preferably 1 to 7% by mass, more preferably I to 5% by mass, based on the total mass of the
solid content of the metal surface treatment agent.
The content of the lithium silicate (C) can be also calculated from the amount blended
when each raw material is blended.
[0025]
The total number of moles of elemental silicon, calculated in terms of Si02, contained
in the silicon oxide particles (B) and the lithium silicate (C) is 40 to 70 times the number of
moles of elemental lithium, calculated in terms ofLhO, contained in the lithium silicate (C)
(hereinafter, simply also referred to as "the molar ratio of Si02 to LhO is 40 to 70"). When
the molar ratio of Si02 to LhO is less than 40, sufficient performance of a paint film cannot
be obtained, and in particular, the alkali resistance is decreased. In contrast, when the molar
ratio exceeds 70, the tape-peeling resistance is inferior. For the similar reason, the molar
ratio of Si02 to Li20 is preferably 50 to 65, more preferably 50 to 60.
[0026]
As described above, in the metal surface treatment agent for a zinc-plated steel
material of the present invention, a ratio of the mass oflithium silicate (C) relative to the mass
of elemental titanium contained in the organic titanium compound (D) is0.2 to 200. When
the mass ratio is less than 0.2, the press oil resistance and the tape-peeling resistance
deteriorate. When the mass ratio exceeds 200, the alkaline degreasing ability deteriorates.
For the similar reason, the ratio of the mass of the lithium silicate (C) relative to the mass of
elemental titanium contained in the organic titanium compound (D) is preferably 0.5 to 17,
more preferably 1.5 to 17.
In the metal surface treatment agent for a zinc-plated steel material of the present
invention, a ratio of the mass of the total amount of the silane coupling agent (A-1) relative to
the sum of the mass of the elemental titanium contained in the organic titanium compound
(D) and the mass of the lithium silicate (C) is preferably 0.01 to 13. When the mass ratio is
in the range ofO.Ol to 13, the tape-peeling resistance and the alkali resistance are improved,
and the press oil resistance and the resistance of a processed pmt to corrosion are also
improved. For the similar reason, the ratio of the mass of the silane coupling agent (A-1)
II
~
12
relative to the sum of the mass of the elemental titanium contained in the organic titanium
compound (D) and the mass of the lithium silicate (C) is more preferably 0.1 to 13, stillmore
preferably 0.35 to 0.65.
[0027)

Specific examples of the organic titanium compound (D) used in the present invention
include di propoxy -bis( tri ethano laminato )titanium, dipropoxy -bis( diethanolaminato )titanium,
dibutoxy-bis(triethanolaminato )titanium, dibutoxy-bis ( diethanolaminato )titanium,
dipropoxy-bis( acetylacetonato )titanium, dibutoxy-bis( acetylacetonato )titanium, dihydroxybis(
lactato )titanium monoammonium salt, dihydroxy-bis(lactato )titanium diammonium salt,
propanedioxytitanium-bis(ethyl acetoacetate), oxotitaniumbis(monoammonium oxalate), and
isopropyltri(N-amidoethyl-aminoethyl)titanate. One of these may be alone, or two or more
of these may be used in combination.
The organic titanium compound (D) is contained in a content of 0.05 to 5% by mass, in
terms of elemental titanium, based on the total mass of the solid content of the metal surface
treatment agent. When the content of the organic titanium compound (D) is less than 0.05%
by mass, it is not possible to achieve sufficient performance of a paint film. From the
viewpoint of exerting the effect of the present invention satisfactorily by adjusting the balance
with the content of other ingredients, the content is within 5% by mass. For the similar
reason, the content of the organic titanium compound (D) is more prefel'ably 0.1 to 2% by
mass, more preferably 0.3 to I% by mass, in terms of elemental titanium, based on the total
mass of the solid content of the metal surface treatment agent.
The content of the organic titanium compound (D) can be also calculated from the
amount blended when each raw material is blended.
[0028]

The epoxy-group containing compound (E) used in the present invention is preferably,
but not particularly limited to, a multifunctional epoxy resin. Because the amount of the raw
material used can be reduced, the compound (E) is preferably as multifunctional as possible,
preferably trifunctional or more, stillmore preferably tetrafunctional or more. Also, from
the viewpoint of controlling change in the viscosity due to reaction with the organic resin
particles (A) and from the viewpoint of the handleability of the resulting metal treatment
agent, the compound (E) is preferably trifunctional to pentafunctional, for example. As a
specific example, the aforementioned multifunctional epoxy-group containing compound (A-
2) can be used as an epoxy-group containing compound.
13
The epoxy-group containing compound (E) reacts with the organic resin particles (A)
and forms a highly-crosslinked coating film on forming a coating film to thereby improve, in
particular, the press oil resistance.
The epoxy-group containing compound (E) is contained in a content of 0.2 to I 0% by
mass based on the total mass of the solid content of the metal surface treatment agent. When
the content of the epoxy-group containing compound (E) is less than 20% by mass, it is not
possible to achieve sufficient performance of a paint film, in pmiicular, sufficient press oil
resistance. From the viewpoint of exerting the effect of the present invention satisfactorily
by adjusting the balance with the content of other ingredients, the content is I 0 % by mass or
less. For similar reason, the content of the epoxy-group containing compound (E) is
preferably I to 8% by mass, more preferably 2 to 7% by mass, based on the total mass of the
solid content of the metal surface treatment agent.
The content of the epoxy-group containing compound (E) can be also calculated fi·om
the amount blended when each raw material is blended.
[0029]

The metal surface treatment agent for a zinc-plated steel material of the present
invention preferably contains a niobium compound (F) in addition to (A) to (E) mentioned
above.
The niobium compound (F) is contained in a content of preferably 0.1 to 10% by mass
based on the total mass of the solid content of the metal surface treatment agent. When the
content of the niobium compound (F) is within the range of0.1 to 10% by mass, the metal
surface treatment agent provides excellent resistance of a processed part to corrosion. For
the similar reason, the content of the niobium compound (F) is more preferably 0.2 to 5% by
mass, stillmore preferably 0.5 to 2% by mass, based on the total mass of the solid content of
the metal surface treatment agent.
[0030]
The niobium compound (F) is not particularly limited, and conventionally known
niobium-containing compounds can be used. Examples include niobium oxide, niobic acid
and salts thereof, fluoroniobates, and fluorooxoniobates. Of these, niobium oxide is
preferable from the viewpoint of improving the corrosion resistance.
[0031]
The niobium oxide is preferably niobium oxide particles. This makes it possible to
form a coating film into which the niobium oxide particles are incorporated, enabling the
corrosion resistance to be fmiher improved.
14
[0032]
The niobium oxide particles refer to an oxide of niobium dispersed in a microparticle
state in water, and for example, may be those in which niobium oxide are not formed strictly
and which is an amorphous, intermediate state between niobium hydroxide and niobium oxide.
[0033]
As niobium oxide pmiicles added to the metal surface treatment agent to be used for
forming a coating film, niobium oxide particles produced in accordance with a known method
can be used. Examples of the niobium oxide particles include, but are not par(icularly
limited to, those produced in accordance with the known methods disclosed in JP-A-6-321543,
JP-A-8-143314, JP-A-8-325018 A, etc. Niobium oxide sol and niobium oxide sluny
commercially available from Taki Chemical Co., Ltd. also can be used.
[0034]
The average particle size of the niobium oxide particles is preferably 2 nm to 10 11m,
more preferably 2 nn1 to I 11m. A smaller average particle size is more preferably because a
coating film comprising a more stable and compact niobium oxide is formed and thus a tust
preventing property can be stably imparted to an object to be treated. The average particle
size of the niobium oxide pmiicles can be determined using a laser light diffraction scattering
type microtrac HRA pmiicle size distribution meter (manufactured by HONEYWELL Inc.
etc.), as a volume average particle size, which is a particle size at which the accumulated
volume reached 50%.
[0035]

The metal surface treatment agent for a zinc-plated steel material of the present
invention preferably contains a phosphate compound (G) in addition to (A) to (E) or (A) to
(F) described above. Examples of the phosphate compound (G) include phosphoric acids
such as otihophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid,
and tetraphosphoric acid, and phosphates such as triammonium phosphate, ammonium
phosphate dibasic, trisodium phosphate and disodium hydrogenphosphate. These may be
used alone, or two or more of these may be used in combination.
Whe1,1 the phosphate compound (G) is used, the phosphate ion forms a phosphate layer
on the surface of a metal base to passivate the metal, enabling a rust preventing property to be
improved.
The phosphate compound (G) is contained in a content of preferably 0.1 to 10% by
mass, in terms of elemental phosphorous, based on the total mass of the solid content of the
metal surface treatment agent. When the content of the phosphate compound (G) is within
15
the range of 0.1 to 10% by mass, the metal smface treatment agent provides excellent
resistance of a processed pa1t to corrosion. For the similar reason, the content of the
phosphate compound (G) is more preferably 0.2 to 5% by mass, still more preferably 0.5 to
2% by mass, in terms of elemental phosphorous, based on the total mass of the solid content
of the metal surface treatment agent.
The content of the phosphate compound (G) can be also calculated from the amount
blended when each raw material is blended.
[0036]
The phosphate compound (G) and the niobium compound (F) are combined to enable a
coating film which is, in particular, excellent in resistance of a processed part to corrosion to
be formed. The ratio of the mass of phosphate compound (G), in terms of elemental
phosphorous, to the mass of the niobium compound (F) is preferably 0.01 to 100, more
preferably 0.03 to 10, still more preferably 0.03 to 4.
[0037]

The metal surface treatment agent for a zinc-plated steel material of the present
invention may contain water in addition to (A) to (E), (A) to (F), or (A) to (G) described
above.
[0038]

The metal surface treatment agent for a zinc-plated steel material of the present
invention may contain other ingredients other than (A) to (G) described above and water.
For example, wax, a lubricant, and a pigment may be blended. As the wax, for example,
hydrocarbon waxes such as paraffin, microcrystalline, and polyolefin, and conventionally
known waxes such as derivatives thereof can be used. Examples of the derivatives described
above include carboxylated polyolefin and chlorinated polyolefin. As the lubricant, for
example, conventionally known lubricants such as fluorine-based, hydrocarbon-based, fatty
acid amide-based, ester-based, alcohol-based, metallic soap-based, and inorganic lubricants,
etc. can be used. As the pigment, various coloring pigments, for example, inorganic
pigments such as titanium oxide (Ti02), zinc oxide (ZnO), calcium carbonate (CaC03),
barium sulfate (BaS04), alumina (AhOJ), kaolin clay, carbon black, and iron oxide (Fe203,
Fe30 4), organic pigments, etc. can be used. Also, as an anti-rust agent, for example,
thiocarbonyl compounds and guanidine compounds described in JP 492295 B can be used.
[0039]
(Method for producing a metal surface treatment agent for a zinc-plated steel material)
16
The metal surface treatment agent for a zinc-plated steel material of the present
invention can be produced by blending the silicon oxide particles (B), the lithium silicate (C),
the organic titanium compound (D), and the epoxy-group containing compound (E) in a water
dispersion including resin pmiicles of the organic resin particles (A) dispersed therein to
prepare the metal surface treatment agent and nuihcrmore, blending one or more selected
from the niobium compound (F), the phosphate compound (G), water and other ingredients as
required.
[0040]
[Method for coating zinc-plated steel material]
The method for coating a zinc-plated steel material of the present invention is
characterized in that the metal surface treatment agent for a zinc-plated steel material of the
present invention is applied to a surface of the zinc-plated steel material to form a coating film.
Thus, the method for coating a zinc-plated steel material of the present invention has excellent
performance in any of press oil resistance, substrate adhesiveness, tape-peeling resistance,
paint adhesiveness, resistance of a processed part to corrosion, alkali resistance, and ablation
resistance.
[0041]
The coating film is one in a state where the organic resin particles (A), the silicon
oxide pmiicles (B), the organic titanium compound (D), and the epoxy-group containing
compound (E) are bound to one another. In other words, the coating film in a state where
the functional groups of the organic resin pmiicles (A), the nmctional groups on the surface of
the silicon oxide particles (B), and the functional groups of the organic titanium compound
(D) and the epoxy-group containing compound (E) form bonds to be combined.
Additionally, it is considered that the silicon oxide particles (B) and the lithium silicate
(C) are ionic-crosslinked to form pseudo-crosslinking in the coating film.
[0042]
The bonds are mainly formed by reaction among the Si-OR groups and/or Si-OH
groups of the organic resin particles (A), the Si-OH groups on the surface of the silicon oxide
particles (B), and the Ti-OR' groups and/or Ti-01-1 groups of the organic titanium compound
(D). It is considered that the bonds are Si-0-Si bonds, Si-0-Ti-0-Si bonds, etc. These
bonds can provide an advantageous effect by which the organic resin pmiicles and the
inorganic particles form chemically robust bonds. Additionally, it is considered that the
carboxylic acid groups of the organic resin pmiicles (A) and the epoxy groups of the epoxygroup
containing compound (E) are crosslinked to form a more robust coating film to thereby
improve the press oil resistance, etc. Here, the above-described R is a substituent derived
17
from the aforementioned silane coupling agent (A-1), and the above-described R' is a
substituent derived from the aforementioned organic titanium compound (D).
Fmthennore, it is considered that the silicon oxide particles (B) and the lithium silicate
(C) form pscudo-crosslinking by ionic crosslinking as aforementioned to thereby form a
coating film excellent in tape adhesion resistance.
The particle size of the organic resin particles (A) is in the specific range, and therefore,
bonds among the above-described pmticles are formed at a high density in the coating film.
Accordingly, the coating film becomes chemically stable, and highly homogeneous in the
microscopic sense. l-Ienee, it is assmned that the metal surface treatment agent for a zincplated
steel material of the present invention is provided with a particularly significant effect.
In producing a metal surface treatment agent for coating zinc-plated steel material, the
order for adding each of the above-described ingredients is not particularly limited, but, for
example, the method for producing a metal surface treatment agent for a zinc-plated steel
material described above can be used.
[0043]
For the metal surface treatment agent for a zinc-plated steel material, a solvent or a
leveling agent can be used for forming a more uniform and smooth coating film. The
solvent or leveling agent is not particularly limited as long as it is one generally used in paints.
Examples include hydrophilic solvents such as alcohol-based, ketone-based, ester-based, and
ether-based solvents, and leveling agents such as silicone-based leveling agents.
[0044]
A coating film with the metal surface treatment agent can be formed by applying the
metal surface treatment agent to a surface of the steel material. To coat zinc-coated steel or
non-coated steel, for example, the metal surface treatment agent is applied to an object to be
coated, which has been degreased as required. The coating method is not particularly
limited, and roll coat, air spray, airless spray, inm1ersion, etc., which are commonly used, are
employed as appropriate. To enhance the curability of the coating film, the object to be
coated is preferably preheated, or, after coating, the object coated is preferably thermally
dried. The peak metal temperature (PMT) on the steel sheet, which is an indicator of the
heating temperature for the object to be coated is preferably 20 to 250°C, more preferably 50
to 220°C. When the heating temperature is 50°C or more, the moisture content evaporates at
a higher rate, and sufficient film formability can be achieved. Thus, the solvent resistance
and alkali resistance are improved. In contrast, when the heating temperature is 250°C or
less, pyrolysis of the resin becomes difficult to occur to thereby improve the solvent
18
resistance and alkali resistance and also prevent a deterioration in the appearance by
yellowing.
Also, the metal surface treatment agent for a zinc-plated steel material of the present
invention can form a coating film having a sufficiently excellent performance by evaporation
of the moisture content even under low temperature conditions of around room temperature
(20°C).
Drying time in case of thermal drying after coating is preferably I second to 5 minutes.
[0045]
[Coated steel material]
The coated steel material of the present invention can be obtained by coating a steel
material with the metal surface treatment agent for a zinc-plated steel material of the present
invention. The coated steel material also can be obtained by the method for coating a zincplated
steel material characteristic of applying the metal surface treatment agent for a zincplated
steel material of the present invention to a surface of the zinc-plated steel material to
form a coating film. Thus, the coated steel material of the present invention has excellent
performance in any of press oil resistance, substrate adhesiveness, tape-peeling resistance,
paint adhesiveness, resistance of a processed pm1 to corrosion, alkali resistance, and ablation
resistance.
[0046]
In the coated steel material, the amount of the coating film is preferably 0.1 to 3 g/m2
,
more preferably 0.5 to 1.5 g/m2
• When the above-described amount of the coating film is
0.1 g/m2 or more, the corrosion resistance is improved. When the above-described amount
of the coating film is 3 g/m2 or less, the substrate adhesiveness can be prevented from
decreasing.
[0047]
The coated steel material of the present invention can be used after a paint film is
formed by applying an overcoat paint on the coating film. Examples of the overcoat paint
include paints composed of acrylic resin, acrylic-modified alkyd resin, epoxy resin, urethane
resin, melamine resin, phthalic acid resin, amino resin, polyester resin, vinyl chloride resin,
etc.
[0048]
The thickness of the paint film of the overcoat paint is determined depending on the
application ofthe anti-rust metal product, the type of the overcoat paint used, etc., and is not
particularly limited. The thickness of the paint film of the overcoat paint is usually 5 to 300
Jlm, more preferably 10 to 200 Jllll. A paint film of the overcoat paint can be formed by
19
applying, thermally dried, and curing an overcoat paint on a coating film formed with the
metal surface treatment agent for a zinc-plated steel material. The drying time and
temperature are adjusted as appropriate depending on the type of the overcoat paint to be
applied, the thickness of the paint film, etc. Usually, the drying temperature is preferably 50
to 250°C, and the drying time is preferably 5 minutes to an hour. The method for applying
the overcoat paint can be conducted by a conventionally known method, depending on the
form of the paint.
[0049]
Examples of the steel material used in the present invention include zinc-based plated
steel materials such as zinc-plated steel materials, zinc-nickel-plated steel materials, zinc-ironplated
steel materials, zinc-chromium-plated steel materials, zinc-aluminum-plated steel
materials, zinc-titanium-plated steel materials, zinc-magnesium-plated steel materials, zincmanganese-
plated steel materials, zinc-aluminum-magnesium-plated steel materials, zincaluminum-
magnesium-silicone-plated steel materials, etc., and these plated layers containing,
as a small amount of a different elemental metal or an impurity, cobalt, molybdenum,
tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth,
antimony, tin, copper, cadmium, arsenic, etc. and those in which an inorganic substance snch
as silica, alumina, or titania is dispersed. Furthermore, the present invention is applicable to
multilayer plating, which is a combination of the plating as above with other type of plating,
such as iron plating, iron-phosphorous plating, nickel plating, and cobalt plating.
Fmihermore, the present invention is also applicable to aluminum or aluminum-based alloy
plating. The plating is not particularly limited, and any of known methods of electroplating,
hot-dip plating, deposition plating, dispersal plating, vacuum plating, etc.
EXAMPLES
[0050]
Hereinbelow, the present invention will described in detail by Examples, but the
present invention is not limited to the following Examples. In the following description, all
of the percentages for representation of the concentrations are expressed in% by mass, unless
specifically indicated.
[0051]

(Production of resin particles (a-1 ))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
20
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.69% of hydrogenated bisphenol A diglycidyl ether (product name: SR-HBA,
manufactured by SAKAMOTO YAKUHINKOGYO CO., LTD) and 1.15% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane (product name: KBM-303, manufactured by ShinEtsu
Chemical Co., Ltd.) were further added and allowed to react at 85°C for 2 hours to
thereby obtain a water dispersion of resin particles (a-1) having a silanol group and/or
methoxysilyl group, wherein the dispersion had a solid content of 24%. The average pmiicle
size of the resin particles (a-1) measured by a particle size measuring apparatus using
dynamic light scattering, FPAR-1 000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0052]

(Production of resin particles (a-2))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.69% of hydrogenated bisphenol A diglycidyl ether and 0.29% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were further added and allowed to react at 85°C for 2
hours to thereby obtain a water dispersion of resin particles (a-2) having a silanol group
and/or methoxysilyl group, wherein the dispersion had a solid content of24%. The average
patiicle size of the resin pmiicles (a-2) measnred by a particle size measuring apparatus using
dynamic light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0053]

(Production of resin particles (a-3))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.69% ofhydrogenated bisphenol A diglycidyl ether and 5.75% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were futiher added and allowed to react at 85°C for 2
hours to thereby obtain a water dispersion of resin particles (a-3) having a silanol group
21
and/or methoxysilyl group, wherein the dispersion had a solid content of24%. The average
particle size of the resin particles (a-3) measured by a particle size measuring apparatus using
dynamic light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0054]

(Production of resin particles (a-4))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred ·at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.23% of hydrogenated bisphenol A diglycidyl ether and 1.15% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were further added and allowed to react at 85°C for 2
hours to thereby obtain a water dispersion of resin particles (a-4) having a silanol group
and/or methoxysilyl group, wherein the dispersion had a solid content of24%. The average
particle size of the resin pat1icles (a-4) measured by a pat1icle size measuring apparatus using
dynamic light scattering, FP AR-1 000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0055]

(Production of resin particles (a-5))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 4.6% of hydrogenated bisphenol A diglycidyl ether and 1.15% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were fm1her added and allowed to react at 85°C for 2
hours to thereby obtain a water dispersion of resin pm1icles (a-5) having a silanol group
and/or methoxysilyl group, wherein the dispersion had a solid content of24%. The average
particle size of the resin particles (a-5) measured by a pat1icle size measuring apparatus using
dynamic light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0056]

(Production of resin particles ( a-6))
22
In a reaction vessel, to an aqueous urethane resin (product name: Adeka Bontighter
HUX-320, manufactured by Adeka Corporation)(solid content is 30%), 0.90% of
hydrogenated bisphenol A diglycidyl ether, and 1.50% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were added and allowed to react at 85°C for 2 hours
to thereby obtain a water dispersion of resin particles (a-6) having a silanol group and/or
methoxysilyl group, wherein the dispersion had a solid content of24%. The average particle
size of the resin particles (a-6) measured by a particle size measuring apparatus using
dynamic light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0057]

(Production of resin particles (a-7))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.69% of hydrogenated bisphenol A diglycidyl ether and 1.15% ofyglycidoxypropyltrimethoxysilane
(product name: KBM-403, manufactured by Shin-Etsu
Chemical Co., Ltd.) were fiuther added and allowed to react at 85°C for 2 hours to thereby
obtain a water dispersion of resin particles (a-7) having a silanol group and/or methoxysilyl
group, wherein the dispersion had a solid content of24%. The average particle size of the
resin particles ( a-7) measured by a particle size measuring apparatus using dynamic light
scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70 nm.
[0058]

(Production of resin patticles (a-8))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 5.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.69% of sorbitol polyglycidyl ether (product name: Denacol EX-614B
manufactured byNagase ChemteX Corporation) and 1.15% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were finther added and allowed to react at 85°C for 2
hours to thereby obtain a water dispersion of resin particles (a-8) having a silanol group
and/or methoxysilyl group, wherein the dispersion had a solid content of24%. The average
23
particle size of the resin particles (a-8) measured by a particle size measuring apparatus using
dynamic light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70
nm.
[0059]

(Production of resin particles (b))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 4.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of23%. To this water dispersed resin
solution, 0.69% of hydrogenated bisphenol A diglycidyl ether and 1.15% of2-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane were further added and allowed to react at 85°C for 2
hours to thereby obtain a water dispersion of resin particles (b) having a silanol group and/or
methoxysilyl group, wherein the dispersion had a solid content of24%. The average particle
size of the resin pmiicles (b) measured by a particle size measuring apparatus using dynamic
light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 100 nm.
[0060]

(Production of resin particles (c))
To a reaction vessel, an ethylene-methacrylic acid copolymer resin (ethylene content is
80% and methacrylic acid content is 20%), 4.6% of sodium hydroxide based on the resin, and
deionized water were added and stirred at 95°C for 6 hours to thereby obtain a water
dispersed resin solution having a solid content of 23%. To this water dispersed resin
solution, 0.69% of hydrogenated bisphenol A diglycidyl ether was further added and allowed
to react at 85°C for 2 hours to thereby obtain a water dispersion of resin particles (c) having a
solid content of24%. In Production Example 10, no silane coupling agent was added. The
average particle size of the resin particles (c) measured by a particle size measuring apparatus
using dynamic light scattering, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.)
was I I 0 nm.
[0061]
The resin patiicles obtained in Production Examples I to I 0 are shown in Table I
below.
[0062]
24
Table 1
Water-soluble
multifunctional
Base resin Silane coupling agent epoxy-group
(A-1) containing
Resin compound
particles (A-2
Amount Amount Amount
Resin
blended Product blended Product blended
[%by name [%by name [%by
mass] mass] mass]
Production a-1 lonomer A 100 KBM303 4 SR-HBA Example 1 3
Production a-2 lonomer A 100 KBM303 1 SR-HBA 3 Example 2
Production a-3 lonomer A 100 KBM303 20 SR-HBA 3 Example 3
Production a-4 lonomer A 100 KBM303 4 SR-HBA 1
Example 4
Production a-5 lonomer A 100 KBM303 4 SR-HBA 20 Example 5
Production a-6 Urethane 100 KBM303 4 SR-HBA 3 Example 6
Production a-7 lonomer A 100 KBM403 4 SR-HBA 3 Example 7
Production a-8 lonomer A 100 KBM303 4 EX-6148 3 Example 8
Production
Example 9 b lonomer B 100 KBM303 4 SR-HBA 3
Production
Example c lonomerB 100 - - SR-HBA 3
10
Note:
Ionomer A (patiicles diameter: 70mm) ethylenemethacrylic acid copolymer resin
(methacrylic acid content: 20% by mass, neutralization degree% by NaOH: 60%)
Ionomer B (patiicles diameter: 1 OOnun) ethylenemethacrylic acid copolymer resin
(methacrylic acid content: 20% by mass, neutralization degree% by NaOH: 50%)
Urethane; HUX-320
KBM303; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
KBM403; y-glycidoxypropyltrimethoxysilane
SR-I-IBA; Hydrogenated bisphenol A diglycidyl ether
EX614B; Sorbitol polyglycidyl ether
[0063]
Average
particle
size
[nm]
70
70
70
70
70
70
70
70
100
110
25
In Examples I to 32 and Comparative Examples I to 23 described below, the
following raw materials and materials and water as the solvent were used to prepare metal
smface treatment agents.
Silicon oxide patiicles; product name AT-20A manufactured by ADEKA
CORPORATION, average particle size 12 mn
Lithium silicate; product name Lithium silicate 35 manufactured by Nippon Chemical
Industrial CO., LTD.
Organic titanium compound; product name T -50,
dipropoxybis(acetylacetonato )titanium manufactured by Nippon Soda Co., Ltd.
Epoxy-group containing compound; product name SR-HBA, manufactured by
SAKAMOTO YAKUHIN KOGYO CO., LTD
Niobium compound; product name BIRAL Nb-G6000, manufactured by Taki
Chemical Co., Ltd., average particle size 15 nm
Phosphate compound; raw material name trisodium phosphate (anhydride)
Other raw materials; carbodiimide (product name CARBODILITE SV-02
manufactured by Nisshinbo Chemical Inc.), melamine resin (product name CYMEL 385,
manufactured by Cytec Industries Japan LLC.), WAX (product name Hitech E-6000S,
manufactured by Toho Chemical Co., Ltd., compound name; polyethylene dispersion)
[0064]
(Zinc-plated steel sheet)
Electrolytic zinc-coated steel sheets "NS ZINKOTE (registered trademark)"
manufactured by NIPPON STEEL & SUMITOMO METAL CORPORATION (referred to as
EG hereinafter), hot-dip zinc plated steel sheets "NS SIL VERZINC (registered trademark)"
manufactured by NIPPON STEEL & SUMITOMO METAL CORPORATION (referred to as
GI hereinafter), zinc-aluminum-magnesium-silicone alloy-plated steel sheets "SUPERDYMA
(registered trademark)" manufactured by NIPPON STEEL & SUMITOMO METAL
CORPORATION (referred to as SD hereinafter), zinc-aluminum alloy-plated steel sheets
"Galvalume steel sheet (registered trademark)" manufactured by NIPPON STEEL &
SUMIKIN COATED SHEET CORPORATION (referred to as GL hereinafter), zinc-nickel
alloy-plated steel sheets "NS Zinclite (registered trademark)" manufactured by NIPPON
STEEL & SUMITOMO METAL CORPORATION (referred to as ZL hereinafter), and zincaluminum-
magnesium alloy-plated steel sheets "ZAM (registered trademark)" manufactured
by Nisshin Steel Co., Ltd. were used as base sheets. Base sheets used had a thickness of 0.6
mm. The EG used had an amount of plated on one surface of20 g/m2
. The GI, SD, GL,
and ZAM used had amount of plated on one surface of 60 g/m2
• The ZL had an amount of
26
plated on one surface of20g/m2
, and the amount of nickel in the plated layer was 12% by
mass.
[0065]

(Preparation of a metal surface treatment agent for a zinc-plated steel material)
To a water dispersion of the above-described resin particles (a- I), silicon oxide
particles (B), lithium silicate (C), an organic titanium compound (D), an epoxy-group
containing compound (E), a niobium compound (F), and a phosphate compound (G) were
blended in accordance with the formulas in Table 2 to thereby prepare a metal surface
treatment agent for a zinc-plated steel material.
(Production of a test sheet)
Each zinc-plated steel sheet was degreased by spraying with an alkali degreasing agent
(SURFCLEANER !55 manufactured by Nippon Paint Co., Ltd.) at 60°C for 2 minutes, then
rinsed with water, and dried by hot air. After cooling, the above-described metal surface
treatment agent was applied onto this degreased steel sheet with a bar coater so as to achieve
an amount of the dry coating film of lg/m2
, and baked snch that the peak metal temperature
(PMT) on the steel sheet could be 150°C using a hot air dryer having an atmosphere
temperature of 500°C and the peak metal temperature (PMT) on the steel sheet could be 50°C
using a hot air dryer having an atmosphere temperature of200°C to produce a test sheet.
[0066]

The blends and blending conditions of the metal surface treatment agent for a zincplated
steel material and the production conditions for a test sheet shovm in Tables 2 and 3
were used to thereby prepare a metal surface treatment agent for a zinc-plated steel material
and produced a test sheet as in Example I.
[0067]
[Evaluation method]
The test sheets of Examples I to 32 and Comparative Examples I to 23 produced as
described above were evaluated as follows. Evaluation results are shown in Tables 2 and 3.
[0068]

After a test sheet was immersed in a press oil (G6318SK, produced by NIH ON
KOHSAKUYU CO., LTD) at room temperature for 24 hours, the test sheet was washed with
hexane and placed on a rubbing tester. After the test plate was rubbed reciprocatingly 10
27
times using absorbent cotton impregnated with ethanol under a load of0.5 kgf/cm2
, the state
of the coating film was evaluated in accordance with the following evaluation criteria.
[0069]
A: No rubbing mark is remained on the rubbed surface
B: Rubbing marks are slightly remained on the rubbed surface
C: White rubbing marks are remained on the rubbed surface
D: A portion of the rubbed surface comes off

A test sheet within an hour after painting was extmded by 8 mm from an Erichsen
Tester. Then, Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was
attached on the extruded portion, and then, Cellotape was forcedly peeled. After the test
sheet was impregnated with a methyl violet dye solution for 30 minutes, the state of the
coating film was evaluated in accordance with the following evaluation criteria.
[0070]
A: Substantially no peeling
B: Peeled area is less than 10%
C: Peeled area is 10% or more and less than 25%
D: Peeled area is 25% or more

Filament tape (manufactured by Hitachi Maxell, Ltd.) was attached on a test sheet,
which was left under conditions including 40°C and humidity of 80% for two weeks. Then,
the tape was forcedly peeled. The state of the coating film was evaluated in accordance with
the following evaluation criteria.
[0071]
A: Substantially no peeling
B: Substantially no peeling, but a trace of the tape remains
C: Peeled area of less than 50%
D: Peeled area of 50% or more

A melamine alkyd paint (product name: Organeo White manufactured by Nippon Paint
Co., LTD.) was applied onto a surface of the test sheet with a bar coater so as to achieve a dry
film thickness of 20 1-1m and baked at 130°C for 15 minutes to thereby produce a paint film
sheet. Then, after the paint film sheet was immersed in boiling water for 30 minutes, taken
out, and left for 24 hours, the paint film sheet was extruded by 7 nun from an Erichsen Tester.
Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was attached on the
28
extruded portion, and then, Cellotape was forcedly peeled. The state ofthe coating film was
evaluated in accordance with the following evaluation criteria.
[0072]
A: Substantially no peeling
B: Peeled area is less than I 0%
C: Peeled area is I 0% or more and less than 25%
D: Peeled area is 25% or more

The test sheet was extruded by 7 1nm from an Erichsen Tester. The edges and back
surface of the test sheet were sealed with tape and subject to the salt spray testing (SST)(JISZ-
2371). White rust occurrences after 72 hours were observed and evaluated in accordance
with the following evaluation criteria.
[0073]
A: No white rust occurred
B: Area where white rust occurred is less than 10%
C: Area where white rust occurred is 10% or more and less than 30%
D: Area where white rust occmTed is 30% or more

A test sheet was illllllersed in a 2% by mass aqueous solution of an alkali degreasing
agent (SURFCLEANER 155 manufactured by Nippon Paint Co., Ltd.) (pH 12.5) at 60°C with
stirring for two minutes. Then, the edges and back surface of the test sheet were sealed with
tape and subject to the salt spray testing(JIS-Z-2371). White rust occurrences after 72 hours
were observed and evaluated in accordance with the following evaluation criteria.
[0074]
A: No white rust occurred
B: Area where white rust occurred is less than I 0%
C: Area where white rust occurred is I 0% or more and less than 30%
D: Area where white rust occurred is 30% or more

A load of I 0 g/cm2 was applied on a test sheet via cardboard. An elliptic movement
of360 rounds/min was applied to the test sheet to allow ablation (wear scars) to occur at the
sliding portion. After the test was conducted for I 0 minutes, the surface of test sheet was
observed and evaluated in accordance with the following criteria.
A: Substantially no blackening
B: Less than I 0% of the area of the sliding portion blackened
[0075]
29
C: 10% or more and less than 30% of the area of the sliding portion blackened
D: 30% or more of the area of the sliding portion blackened
:=JJ
30
Table 2
Silicon Lithium g>§;
Epoxy-group Organic resin Nb ~ oxide silicate Organic titanium 2 containing compound Phosphate WAX I Coating film performance
(A) compound .\:l·- :a.s:J compound compound (B) (C) ,g =I- ~ ~- §~~ (E) (F) ~r: ~
.];;
Eo
"' ~ 0 sg .3 :§:§ "' ~ ~"' :§! ~1~ §:
g i!lg> ~ : ~:§ " " " " 0 ::;:i.S " " " " ~- * ~ 1 :;;; ·- ~ .Sl "!; E ~ i -g ] s i ~ 0·~ Oe.~ jl I I ] ] H !¥ .... c.. .8 8 ~ § PMT c :l'l ~ "' 0 ,g§: ,g ""'·- 11 0 1l "' ~ 1l
o!:l "" "" "" .I:! :k §: "" "" 0 -:ll ji -~ ~ ~ ~ ·" ·"' 0 0 0 0 § "'""' :g 0 0 0 § 0 ~
@,. "' i(J E1 -5·~ 1l c f'· ~r :1 ~ ~ ....: ... 6 "' ~ "' ~ -g ~ ~ ~ ~ ;g "' ·" ~ ·" c !j! !j! .Sl !j! .Sl ~ ~.-J ~ ·" "0 .5 ~ "' ~ c5l ~
~ 1l ~ ~ ·" El i(J <( <( <( <( £ <( <( <( £ <( "' '5 ~ j ~ " ,.s ~ a: c.. ,g
~ 1l :5 .!a B
[%by r;. by [%by [%by [%by r;. by [%by [%by rh by r;. by [%by [%by i(J" ~ -"
mass] mass] mass] [-) mass] mass] I-I [-) mass] mass] mass] mass] mass] mass] mass] c.. "~' /i'_ a::! :;;: ~
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG
5oo•c
1 HBA 150'C A A A A A A A 14s
Example a-2 55.6 27.8 2.1 57 5.1 0.58 3.6 0.13 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG
5oo·c
150'C A A A A A B A 2 HBA 14s
Example a-3 55.6 27.8 2.1 57 5.1 0.58 3.6 2.67 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 500'C
150'C A B A A B A A 3 HBA 14s
Example a-4 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 500'C
4 HBA 14s 150'C A A A B A A A
Example a-5 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 500'C
150'C A B A A B A A 5 HBA 14s
Example a-6 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 500'C
6 H8A 150'C A A A A A A B 14s
Example a-7 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 02 2.0 100.0 20.0 EG
5oo·c
7 H8A 150'C A A A A A A A 14s
Example a-8 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG
5oo•c
8 H8A 150'C A A A A A A A 14s
Example a-1 31.1 49.8 4.4 49 6.3 0.72 6.1 0.18 SR- 2.8 1.5 1.5 0.3 2.5 100.0 20.0 EG
5oo•c
9 H8A 150'C A 8 A B 8 8 A 14s
Example a-1 69.9 11.7 1.0 50 5.9 0.67 1.5 1.30 SR- 6.4 1.5 1.4 0.3 2.3 100.0 20.0 EG
5oo•c
10 H8A 150'C B A B A A A 8 14s
Example a-1 55.1 27.5 3.0 41 5.0 0.57 5.2 0.38 SR- 5.0 1.2 1.2 0.2 2.0 100.0 20.0 EG
5oo•c
11 H8A 150'C A A A A A A A 14s
Example a-1 55.8 27.9 1.7 69 5.1 0.58 2.9 0.63 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG
5oo·c
12 H8A 150'C A A A A A A A 14s
Example a-1 57.0 28.5 2.1 57 5.2 0.59 3.6 0.55 SR- 5.2 0.0 0.0 0.0 2.1 100.0 20.0 EG 500'C
13 ,_ 150'C A A A A 8 8 A L__ ___ H8A 14s
~11
31
Table 2 (continued)
Silicon Lithium .El :?8 Epoxy-group Organic resin Nb ~ Organic titanium containing Phosphate "E oxide silicate .!l ·- = Q) compound Wt-:X i Coating film performance
(A) 0 compound ~t: §IiI? compound compound ~~ (B) (C) = (F) !!1 "' Eo (E) ~:-
~~0 "'~ ~
~ ~§ ~ 1ig, tn"'§cu
""-~ § -ro ~d ~ "ll "ll "ll "ll s ;:j.S "ll "ll "ll §: "ll ~-
·~ -5~~ :§ ·- ~ 2 "2 E ~ ~ ~ !l
~ ~ "2 s "2 ~ c;.s ~ j ~ "2 H ~ ~
~ :§ !E .g§: .g ,.,._ 1i Q.
~ .8 s~§ PMT § ·~ 1 ~ ~ §
1l ..,
~ 0 ~ ·e~~ ~ 0 - ~ ]l rg ~ 1l c
"E "E "E § § "'"' ~ "E "E "E § "E ~
§.., "' "' :!L ~ ~ ~ "' ~£ r~-· -g ~ ~ ~ ~ "' .S!l ~ -~ -~ 0 ·~ c ·" ~ ~ -~ ~ "' ~ ~ 2 ~ "' ~ 2: .s 3i ..J 01 ~ "' 01 ! § ~ ·" ~ <( <( <( <( .: g "§ <( <( .: <( ::> '5 ._Eg:l = "'8 01 c ro .g 0: Q. (%by [%by [%by r;, by [%by [%by [%by [%by [%by [%by [%by [%by £ 1l :s .!~!2 ".8 76 -"'
1-1 1-1 [-] ~ 0': ~ ~
mass] mass] mass] mass] mass] mass] mass] mass] mass] mass] mass] mass] "' o::!L < <(
Example a-1 56.3 28.1 2.1 57 5.1 0.59 3.6 0.54 SR- 5.1 1.3 0.0 0.0 2.0 100.0 20.0 EG 500°C
150°C A A A A B B A
14 HBA 14s
Example a-1 56.3 28.1 2.1 57 5.1 0.59 3.6 0.54 SR- 5.1 0.0 1.3 0.2 2.0 100.0 20.0 EG 500°C
150°C A A A A B B A
15 HBA 14s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 02 2.0 100.0 20.0 Gl 500°C
150°C A A A A A A A
16 HBA 14s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 SD 500°C
150°C A A A A A A A
17 HBA 14s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 GL 500°C
150°C A A A A A A A
18 HBA 14s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 ZL 500°C
150°C A A A A A A A
19 HBA 14s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 ZAM 500°C 150°C A A A A A A A
20 HBA 14s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53
SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 2000C
50°C A A A A A A A
21 HBA 5s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 Gl
200°C
22 HBA 50°C A A A A A A A 5s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 so 200°C 50°C A A A A A A A
23 HBA 5s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 GL 2000C
50°C A A A A A A A
24 HBA 5s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 ZL 200°C
50°C A A A A A A A
25 HBA 5s
Example a-1 55.6 27.8 2.1 57 5.1 0.58 3.6 0.53 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG I 500oc 150°C A A A A A A A 26
........
HBA
. 14s
Table 2 (further continued)
:l:ll:E ~~
32
Silicon Lithium e: "c
Epoxy-group Nb Organic resin oxide silicate Organic titanium "" ~-- containing compound Phosphate WAX l!l Coating film performance
(A) compound (d. ~s compound compound (B) (C) :.>+ (F) ""' {! ,g "' (E) § ~- "' ~;=: :au ~. !§'E " .!> ~- ~~Q) §'Q;I= ;g ~ g, 0 E o ~ d1 §: 0 'll 'll 'll ::; 'll s ~ ~Jj .2 ~ 'll 'll 'll 'll ~ c-
~ I I s ~ ]j ·- c "' ~ ~ I ~ ~ H ~ "2(1}::.:
~ 1i
] c
"" ~s ·- ~ 0..
~ ~ 0 !!EQ) ~ 0 .e E 8:-:~ PMT
~ ~ - c 0.2 ..... ~ ~ 0 §~ ~ " " " § g>§!ll "' o·- ,g,e l:l " " " § " l!l ~ ·"' B l!l :g_ ~ "~ ~ ,g ~ :.:;;::::~ c ·" "' ~ !:!~ g ~ ~ ~ ~ 1 Ill e! l!l c
~ ~ ~ ~ "' "' ~ ~ "' ;g &: ~ -J ~.Q "' .5 j"" ::; 0 ~ ·" c -"' ~ '§ ~ g> 0 8 ~
Ill "" "" "" "" .s
~"" c.. "" "" "" .s "" "' " J!l 1l ]i i!l l l!l " "' '5 g ~ c 8 i!l c
~
"' 0 ,g
(%by [%by [%by r~o by [%by [%by [%by [%by [%by r;. by r~o by [%by ~ 2 :s .I!l£l?"-' 'ffi -"'
1-1 I-I 1-1 ~ ~ (f ~ ~
mass] mass] mass] mass] mass] mass] mass] mass] mass] mass] mass] mass] "' "':g_ <( ""
Example a-1 29.9 50.0 10.0 48 0.5 0.06 166.7 0.30 SR- 5.1 1.4 1.2 0.2 2.0 100.1 20.0 EG soo•c 27 HBA 14s 150'C A 8 B B B B A
Example a-1 55.1 27.8 5.0 52 2.6 0.30 16.7 0.42 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG SOO'C 150'C A A A A A A A 28 HBA 14s
Example a-1 62.0 10.0 1.0 44 17.5 2.00 0.5 0.83 SR- 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG soo·c 150'C 8 A B A B A B 29 HBA 14s
Example a-1 70.0 10.0 1.0 44 0.4 0.05 20.0 13.33 SR- 10.0 5.3 1.2 0.2 2.0 100.0 20.0 EG SOO'C 150'C B A 8 A 8 A 8 30 HBA 14s
Example a-1 68.0 10.0 1.0 44 0.8 0.09 11.4 12.50 SR- 10.0 5.3 2.9 0.5 2.0 100.0 20.0 EG SOO'C
31 HBA 14s 150'C A A A A A A 8
Example a-1 20.0 50.0 10.0 48 8.7 1.00 10.0 0.02 SR- 5.1 3.0 1.2 0.2 2.0 100.0 20.0 EG 500'C
32 HBA 14s 150'C A B B B B 8 A
Note:
* 1: Other than solid contents in metal surface treatment agent is _water
[0076]
:tm:tr: ;J
33
Table 3 .e•: §·-Fo' ~
Organic Silicon Uthium Organic ,.._ . ~ Epoxy-group Nb
Phosphate ~
resin(A) oxide silicate 0 titanium " lgi>';•5 containing compound compound WAX E " Coating film performance (B) (C) "•il compound ]•!I = 'i'Lo compound (E) (F) g ~ • .8 :9. s . ., 8< 1l ~;:
~
~ jg ~
c5 ji ~8 ~ -. ~~~
~ ~C) ~li' ~ !5 ~ PMT 1" 1" 1" 1" 0 "' .,~ 1" 1" 1" 1" '0 .• 1" 1" 1" ~ ;= ., 1" ~ 1" "- 1" ~ ! - ~ ;t>
~ § § '" I
.,
~ §e~
~ :§ :§ :§ ., ~ "" • :§ :§ i\2: :§ 8 ~ • "' * i • E ~ ~ l-' .s -~ -~ J j J j j ~ H. 101 ~" j J j ~ " ·E"l .!] -•~ "-~ ~ ., ~ ~ .0 .. " I 0 0 ..I:~ ~ ~ -~ - £ '5 ~ 'ii H ·" ~ 0 "' [%by r;~ by r;. by [%by [%by r~o by ~ -2
w~ by mass] [%by [%by r;~ by [%by [%by El ~ ~ ~ ~li. "ffi ::;:
mass] mass) mass] 1-1 mass] mass) I-I I-I mass] mass] mass] mass] mass] mass] 0.. ~ "- ~ ""
Comparative a-1 54.5 27.3 3.9 31 5.0 0.6 6.9 0.49 SR-HBA 5.0 1.2 1.2 0.2 2.0 100.0 20.0 EG soooc
Example 1 14s 150°C A A A A A D A
Comparative a-1 56.1 28.0 1.2 96 5.1 0.6 2.1 1.25 SR-HBA 5.1 1.3 1.2 0.2 2.0 100.0 20.0 EG soooc
Example 2 14s 150"C A A D A A A A
Comparative a-1 56.7 28.4 0.0 5.2 0.6 o.o 3.84 SR-HBA 5.2 1.3 1.3 0.2 2.0 100.0 20.0 EG 500°C
Example 3 1sooc A A D A A A A 14s
Comparative a-1 58.5 29.3 2.2 " 5.3 0.6 3.6 0.84 0.0 1.3 1.3 0.2 2.1 100.0 20.0 EG 5oo·c
Example 4 150'C D A D A A B A 14s
Comparative a-1 58.5 29.3 2.2 57 0.0 0.0 SR-HBA 5.3 1.3 1.3 0.2 2.1 100.0 20.0 EG 500°C
Example 5 150°C D A D A c c A ro ro
14s
Comparative a-1 55.6 27.8 2.1 57 5.1 0.6 3.6 0.84 SV-02 •2 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 500"C
Example 6 14s 150"C D A D A c c A
Comparative a-1 55.6 27.8 2.1 57 5.1 0.6 3.6 0.84 Cyme I 5.1 1.2 1.2 0.2 2.0 100.0 20.0 EG 5oo·c
Example 7 385 •3 150'C D A D A c c A 14s
Comparative a-1 70.0 9.0 1.0 40 8.0 0.9 1.1 1.46 SR-HBA 6.4 1.6 1.7 0.3 2.3 100.0 20.0 EG 500"C
Example 8 14s 150"C c A D A A A c
Comparative a-1 56.7 28.4 0.0 5.2 0.6 o.o 3.84 SR-HBA 5.2 1.3 1.3 0.2 2.0 100.0 20.0 Gl 5oo·c
Example 9 150"C A A D A A A A -
14s
Comparative a-1 56.7 28.4 0.0 5.2. 0.6 0.0 3.84 SR-HBA 5.2 1.3 1.3 0.2 2.0 100.0 20.0 SD
5oo•c
Example 10 1sooc A A D A A A A l4s
Comparative a-1 56.7 28.4 0.0 5.2 0.6 o.o 3.84 SR-HBA 5.2 1.3 1.3 0.2 2.0 100.0 20.0 GL 5oo·c
Example 11 150"C A A D A A A A 14s
Comparative a-1 56,7 28.4 0.0 5.2 0.6 0.0 3.84 SR-HSA 5.2 1.3 1.3 0.2 2.0 100.0 20.0 ZL
5oo·c
Example 12 14s 150"C A A D A A A A
Comparative a-1 56.7 28.4 0.0 5.2 0.6 o.o 3.84 SR-HBA 5.2 1.3 1.3 0.2 2.0 100.0 20.0 ZAM
50o•c
Example 13 150'C A A D A A A I A - ~-- --
. :m:a .:~
34
Table 3 (continued)
.s .r=
~ 15 ,__
§: _o
Nb ~ Organic Silicon Uthium Organic titanium Q ~§ Epoxy .group oxide silicate containing compound Phosphate WAX 11 _@ ~ resin(A) Coating film performance
(B) (C) ~ compound
~" :?:5 compound (E) (F) compound § ~ • '?lo § ·~ '5 8• "-g ~~ ~ ~ H ..
"' H ~~ " ·~ 'll 'll 'll ~ 'll §: :o- 'll 'll 'll [2: 'll £ " §1"1e.' PMT 1~ ~ .5 E
~ ~ ~ i L 'g I ;= ., I I 'g a. 'g ! I ~ ~ ~ IS
.ll :l! "' ~ .g ~ :l! ., :l! ~ :ii ~ ~ j j ~ • ~~ j i ~ i z~ "" .• .~ I I i ~ 0 I R ·"' ~ ~ • i ~ -g ~ !£ '@ :? .• '0 ·~ .<
~ 0 ::.:~ ~ 0 § t ~ a. :? '6 -@ '@ ~ § ·~" ~ 0
:!i ~ ~ ~ ."0£ i,g
[%by [%by f/o by [%by rio by [%by r~o by [%by f/o by rio by r;. by rio by 2 •• 0
mass] mass] mass] I· I mass] mass] [·) [·] mass] mass] mass] mass) mass) mass] mass] a. '" ~ a. H " 0:<
Comparative a-1 56.7 28.4 0.0 5.2 0,6 0.0 3.84 SR- 5.2 1.3 1.3 0.2 2.0 100.0 20.0 EG 200'C sooc A A D A A A A
Example 14 HBA 5s
Comparative a-1 56.7 28.4 0.0 5.2 0.6 0.0 3.84 SR- 5.2 1.3 1.3 0.2 2.0 100.0 20.0 Gl 200'C
Example 15 HBA 5s 50'C A A D A A A A
Comparative a-1 56.7 28.4 0.0 5.2 0.6 0.0 3.84 SR- 5.2 1.3 1.3 0.2 2.0 100.0 20.0 so 200°C sooc A A D A A A A Example 16 HBA 5s
Comparative a-1 56.7 28.4 0.0 5.2 0.6 0.0 3.84 SR- 5.2 1.3 1.3 0.2 2.0 100.0 20.0 Gl 2oooc
sooc A A D A A A A Example 17 HBA 5s
Comparative a-1 56.7 28.4 0.0 5.2 0.6 0.0 3.84 SR- 5.2 1.3 1.3 0.2 2.0 100.0 20.0 Zl 200'C sooc A A D A A A A Example 18 HBA 5s
Comparative a-1 56.7 28.4 0.0 5.2 0.6 0.0 3.84 SR- 5.2 1.3 1.3 0.2 2.0 100.0 20.0 ZAM
200'C
SO'C A A D A A A A
Example 19 HBA 5s
Comparative a-1 40.0 10.0 0.6 54 34.99 4.00 0.2 0.33 SR- 9.6 1.3 1.3 0.2 2.0 100.0 20.0 EG soooc
Example 20 HBA 150'C D B D B B B B 14s
Comparative a-1 23.4 50.0 12.0 41 5.1 0.6 20.7 0.19 SR- 5,0 1.3 1.3 0.2 2.0 100.0 20.0 EG 5oo·c
Example 21 HBA 150'C A B B B B D A 14s
Comparative a-1 35.7 10.0 0.5 84 39.4 4.50 0.1 0,27 SR- 9.9 1.3 1.3 0.2 2.0 100.0 20.0 EG 5oo·c
Example 22 HBA 14s 150°C D B D B B B B
Comparative a-1 30.0 50.0 12.0 41 0.4 0.05 240.0 0.10 SR- 3.0 1.3 1.3 0.2 2.0 100.0 20.0 EG 5oo·c
Example 23 HBA 14s ISO'C A B B B B D A
35
[0077]
As clear from Tables 2 and 3 above, the comparison between Examples I to 32 and
Comparative Examples I to 23 confirmed excellent effects of the metal surface treatment
agent for a zinc-plated steel material of the present invention in any of press oil resistance,
substrate adhesiveness, tape-peeling resistance, paint adhesiveness, resistance of a processed
part to corrosion, alkali resistance, and ablation resistance.
It was confirmed that, by use of the metal surface treatment agent for a zinc-plated
steel material, a coating method using the metal surface treatment agent, and coated steel
material of the present invention, excellent performance is developed in any of press oil
resistance, substrate adhesiveness, tape-peeling resistance, paint adhesiveness, resistance of a
processed part to corrosion, alkali resistance, and ablation resistance.
INDUSTRIAL APPLICABILITY
[0078]
The metal surface treatment agent for a zinc-plated steel material, a coating method
using the metal surface treatment agent, and coated steel material of the present invention can
be suitably used in automobiles, home appliances, building material products, etc.

CLAIMS
[Claim I]
A metal surface treatment agent for a zinc-plated steel material, comprising organic
resin particles (A), silicon oxide particles (B), lithium silicate (C), an organic titanium
compound (D), and an epoxy-group containing compound (E),
wherein the organic resin particles (A) are resin particles which are prepared by
modifying a base resin with a silane coupling agent (A-1) and a multifunctional epoxy-group
containing compound (A-2) and the organic resin pmiicles (A) have a silanol group and/or an
alkoxysilyl group, and the total number of moles of elemental silicon, calculated in terms of
Si02, contained in the silicon oxide patiicles (B) and the lithium silicate (C) is 40 to 70 times
the number of moles of elemental lithium, calculated in terms of Li20, contained in the
lithium silicate (C),
agent,
wherein, based on the total mass of the solid content of the metal surface treatment
the mass of the solid content of the organic resin particles (A) is 20 to 70% by mass,
the content of the silicon oxide particles (B) is 10 to 50% by mass,
the content of the lithium silicate (C) is I to I 0% by mass,
the content of the organic titanium compound (D) is, in terms of elemental titanium,
0.05 to 5% by mass, and
the content of the epoxy-group containing compound (E) is 0.2 to 10% by mass, and
wherein the ratio of the mass of the lithium silicate (C) relative to the mass of
elemental titanium contained in the organic titanium compound (D) is 0.2 to 200.
[Claim 2]
The metal surface treatment agent for a zinc-plated steel material according to claim I,
wherein the ratio of the mass of the silane coupling agent (A- I) to the sum of the mass of the
elemental titanium contained in the organic titanium compound (D) and the mass of the
lithium silicate (C) is 0.01 to 13.
[Claim 3]
The metal surface treatment agent for a zinc-plated steel material according to claim 1
or 2, comprising 0. I to 10% by mass of a niobium compound (F) based on the total mass of
the solid content of the metal surface treatment agent.
[Claim 4]
The metal surface treatment agent for a zinc-plated steel material according to any one
of claims I to 3, comprising 0.1 to 10% by mass of a phosphate compound (G), in terms of
37
elemental phosphorous, based on the total mass of the solid content of the metal surface
treatment agent.
[Claim 5]
The metal surface treatment agent for a zinc-plated steel material according to any one
of claims 1 to 4, wherein the organic resin particles (A) are obtained by blending the silane
coupling agent (A-1) in a proportion of 1 to 20% by mass based on the mass of the solid
content of the base resin and allowing the blend to react.
[Claim 6]
The metal surface treatment agent for a zinc-plated steel material according to any one
of claims I to 5, wherein the organic resin particles (A) are obtained by blending the
multifimctional epoxy-group containing compound (A-2) in a proportion of I to 20% by mass
based on the mass of the solid content of the base resin and allowing the blend to react.
[Claim 7]
The metal surface treatment agent for a zinc-plated steel material according to any one
of claims I to 6,
wherein the total number of moles of elemental silicon, calculated in terms of Si02,
contained in the silicon oxide particles (B) and the lithium silicate (C) is 50 to 65 times the
number of moles of elemental lithium, calculated in terms of LhO, contained in the lithium
silicate (C).
[Claim 8]
A method for coating a zinc-plated steel material, comprising a step of applying the
metal surface treatment agent for a zinc-plated ~tee! material according to any one of claims 1
to 7 to a surface of the zinc-plated steel material to form a coating film.
[Claim 9]
A coated steel material obtained by the method for coating a zinc-plated steel material
according to claim 8.