U.S. patent application number 14/677302 was filed with the patent office on 2015-07-30 for composition for metal surface treatment, metal surface treatment method, and metal material.
The applicant listed for this patent is Chemetall GmbH, NIPPON PAINT CO., LTD.. Invention is credited to Toshio Inbe, Thomas Kolberg.
Application Number | 20150211140 14/677302 |
Document ID | / |
Family ID | 38459118 |
Filed Date | 2015-07-30 |
United States Patent
Application |
20150211140 |
Kind Code |
A1 |
Inbe; Toshio ; et
al. |
July 30, 2015 |
Composition for Metal Surface Treatment, Metal Surface Treatment
Method, and Metal Material
Abstract
Disclosed is a composition for metal surface treatment which
enables to form a chemical conversion coating film which achieves
sufficient foundation surface concealment, coating adhesion and
corrosion resistance. Also disclosed is a method for treating the
surface of a metal material wherein such a composition for metal
surface treatment is used. Specifically disclosed is a metal
surface treatment composition used for a treatment of a metal
surface, which composition contains a zirconium compound and/or a
titanium compound, and a polyamine compound having a number average
molecular weight of not less than 150 but not more than 500,000.
The polyamine compound contains not less than 0.1 millimole but not
more than 17 millimoles of a primary and/or secondary amino group
per 1 g of the solid content, and the content of the zirconium
compound and/or titanium compound in the metal surface treatment
composition is not less than 10 ppm but not more than 10,000 ppm in
terms of metal elements. The mass ratio of the zirconium element
and/or titanium element contained in the zirconium compound and/or
titanium compound relative to the polyamine compound is not less
than 0.1 but not more than 100.
Inventors: |
Inbe; Toshio; (Tokyo,
JP) ; Kolberg; Thomas; (Heppenheim, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NIPPON PAINT CO., LTD.
Chemetall GmbH |
Osaka
Frankfurt am Main |
|
JP
DE |
|
|
Family ID: |
38459118 |
Appl. No.: |
14/677302 |
Filed: |
April 2, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13613544 |
Sep 13, 2012 |
9028667 |
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14677302 |
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12224635 |
Dec 1, 2008 |
8287662 |
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PCT/JP2007/053831 |
Feb 28, 2007 |
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13613544 |
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Current U.S.
Class: |
428/219 ;
148/247; 205/220; 428/418 |
Current CPC
Class: |
C25D 3/02 20130101; Y02T
50/60 20130101; Y02T 50/67 20130101; C25D 13/20 20130101; C23C
22/361 20130101; C09D 183/08 20130101; C23C 22/82 20130101; C25D
11/00 20130101; C23C 22/34 20130101; Y10T 428/273 20150115; C23C
22/48 20130101; C23C 22/83 20130101; Y10T 428/31529 20150401; Y10T
428/12472 20150115; C23C 22/02 20130101 |
International
Class: |
C25D 11/00 20060101
C25D011/00; C23C 22/82 20060101 C23C022/82; C23C 22/36 20060101
C23C022/36; C25D 13/20 20060101 C25D013/20; C25D 3/02 20060101
C25D003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 1, 2006 |
JP |
2006-054860 |
Claims
1-23. (canceled)
24. A metal material treated by a metal surface treatment method
comprising: a treatment solution contact step of contacting with
said metal material, a metal surface treatment solution containing
at least one selected from the group consisting a zirconium
compound and titanium compound, and a polyamine compound having a
number average molecular weight from 150 to 500,000, wherein said
polyamine compound contains from 0.1 mmol to 17 mmol of at least
one selected from the group consisting primary and secondary amino
group per 1 g of solid content, a content of at least one selected
from the group consisting said zirconium compound and titanium
compound in said metal surface treatment composition is from 10 ppm
to 10,000 ppm with respect to the metal element, a mass ratio of at
least one selected from the group consisting zirconium element and
titanium element included in at least one selected from the group
consisting said zirconium compound and titanium compound is from
0.1 to 100, with respect to said polyamine compound, and said
polyamine compound is a compound having at least one siloxane unit;
and a water washing step of washing with water the metal material
after said treatment solution contact step.
25. The metal material according to claim 24, having a surface
treatment coating layer on an iron-based metal material surface,
wherein said surface treatment coating layer contains at least 10
mg/m.sup.2 of zirconium element or titanium element, and a mass
ratio of at least one selected from the group consisting zirconium
element and titanium element with respect to nitrogen element
according to XPS analysis of said surface treatment coating layer
is from 0.05 to 500.
26. The metal material according to claim 24 having a surface
treatment coating layer on a zinc-based metal material surface,
wherein said surface treatment coating layer contains at least 10
mg/m.sup.2 of at least one selected from the group consisting
zirconium element and titanium element, and a mass ratio of at
least one selected from the group consisting zirconium element and
titanium element with respect to nitrogen element according to XPS
analysis of said surface treatment coating layer is from 0.05 to
500.
27. The metal material according to claim 24 having a surface
treatment coating layer on an aluminum-based metal material
surface, wherein said surface treatment coating layer contains at
least 5 mg/m.sup.2 of at least one selected from the group
consisting zirconium element and titanium element, and a mass ratio
of at least one selected from the group consisting the zirconium
element and titanium element with respect to nitrogen according to
XPS analysis of said surface treatment coating layer is from 0.05
to 500.
28. The metal material according to claim 24 having a surface
treatment coating layer on a magnesium metal material surface,
wherein said surface treatment coating layer contains at least 5
mg/m.sup.2 of at least one selected from the group consisting
zirconium element and titanium element, and a mass ratio of at
least selected from the group consisting the zirconium element and
titanium, element with respect to nitrogen according to XPS
analysis of said surface treatment coating layer is from 0.05 to
500.
29. A metal surface treatment method for treating the surface of a
metal material, comprising: a treatment solution contact step of
contacting with said metal material, a metal surface treatment
solution containing at least one selected from the group consisting
a zirconium compound and titanium compound, and a polyamine
compound having a number average molecular weight from 150 to
500,000, wherein said polyamine compound is a product produced by
interaction of at least one selected from the group consisting a
primary and secondary amino group-containing compound, and an amine
activity reducing compound B containing at least one functional
group B which interacts with at least one selected from the group
consisting said primary and secondary amino group and reduces amine
activity, a content of at least one selected from the group
consisting said zirconium compound and titanium compound in said
metal surface treatment composition is from 10 ppm to 10,000 ppm
with respect to the metal element, a mass ratio of at least one
selected from the group consisting zirconium element and titanium
element included in at least one selected from the group consisting
said zirconium compound and titanium compound is from 0.1 to 100,
with respect to said polyamine compound, and said polyamine
compound is a compound having at least one siloxane unit; and a
water washing step of washing with water the metal material after
said treatment solution contact step.
30. The metal surface treatment method according to claim 29,
wherein the metal material is simultaneously subjected to
degreasing treatment in the treatment solution contact step.
31. The metal surface treatment method according to claim 29,
wherein the metal material is electrolyzed as a cathode in the
treatment solution contact step.
32. The metal surface treatment method according to claim 29,
comprising an acid contact step of contacting the metal material
after the water washing step with an acidic aqueous solution
containing at least one selected from the group consisting of
cobalt, nickel, tin, copper, titanium, and zirconium.
33. The metal surface treatment method according to claim 29,
comprising a polymer-containing solution contact step of contacting
the metal material after the water washing step with a
polymer-containing solution containing at least one of a
water-soluble polymer compound and a water-dispersible polymer
compound.
34. A metal material treated by a metal surface treatment method
according to claim 29.
35. The metal material according to claim 34, having a surface
treatment coating layer on an iron-based metal material surface,
wherein said surface treatment coating layer contains at least 10
mg/m.sup.2 of zirconium element or titanium element, and a mass
ratio of at least one selected from the group consisting zirconium
element and titanium element with respect to nitrogen element
according to XPS analysis of said surface treatment coating layer
is from 0.05 to 500.
36. The metal material according to claim 34 having a surface
treatment coating layer on a zinc-based metal material surface,
wherein said surface treatment coating layer contains at least 10
mg/m.sup.2 of at least one selected from the group consisting
zirconium element and titanium element, and a mass ratio of at
least one selected from the group consisting zirconium element and
titanium element with respect to nitrogen element according to XPS
analysis of said surface treatment coating layer is from 0.05 to
500.
37. The metal material according to claim 34 having a surface
treatment coating layer on an aluminum-based metal material
surface, wherein said surface treatment coating layer contains at
least 5 mg/m.sup.2 of at least one selected from the group
consisting zirconium element and titanium element, and a mass ratio
of at least one selected from the group consisting the zirconium
element and titanium element with respect to nitrogen according to
XPS analysis of said surface treatment coating layer is from 0.05
to 500.
38. The metal material according to claim 34 having a surface
treatment coating layer on a magnesium metal material surface,
wherein said surface treatment coating layer contains at least 5
mg/m.sup.2 of at least one selected from the group consisting
zirconium element and titanium element, and a mass ratio of at
least selected from the group consisting the zirconium element and
titanium element with respect to nitrogen according to XPS analysis
of said surface treatment coating layer is from 0.05 to 500.
39. The metal surface treatment method according to claim 29,
wherein the polyamine compound having a number average molecular
eight from 5,000 to 500,000.
40. The metal surface treatment method according to claim 29,
wherein the polyamine compound is a polyaminosiloxane.
41. The metal surface treatment method according to claim 40,
wherein the polyaminosiloxane is selected from at least one of
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane and hydrochlorides of
N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.
42. The metal surface treatment method according to claim 29,
wherein said polyamine compound contains from 0.1 mmol to 17 mmol
of at least one selected from the group consisting primary and
secondary amino group per 1 g of solid content.
Description
TECHNICAL FIELD
[0001] The present invention relates to a metal surface treatment
composition for use in metal surface treatment, a metal surface
treatment method for treating the surface of a metal material using
the surface treatment composition, and a metal material treated
with the metal surface treatment method.
BACKGROUND ART
[0002] When an article to be processed is to be coated, it is
commonly subjected to surface treatment from the viewpoint of
ensuring the corrosion resistance and adhesiveness of a coating
film. In particular, when a metal (metal material, metal structure)
is to be coated, the metal surface is subjected to chemical
conversion treatment (surface treatment) for chemically forming a
chemical conversion coating film.
[0003] An example of the chemical conversion treatment is chromate
conversion treatment with a chromate containing composition;
however, adverse effects of chromium have been noted. In recent
years, treatment with zinc phosphate treatment agents (zinc
phosphate treatment), which are chromium-free treatment agents
(surface treatment agents, chemical conversion treatment agents)
has become widespread (see, for example, Patent Document 1).
[0004] However, the zinc phosphate treatment agent is highly
reactive due to the high content of metal ions and acids that it
contains, hence this treatment agent offers an unfavorable impact
on both the cost and the workability during drainage treatment. In
addition, metal surface treatment with the zinc phosphate treatment
agent involves the generation and sedimentation of water-insoluble
salts. Such precipitates are generally referred to as sludge, and
the removal and disposal of sludge generates an additional
undesirable cost. Furthermore, the use of phosphate ions is not
preferable because they may affect the environment through
eutrophication, and the treatment of phosphate ion effluent
requires considerable labor. Moreover, metal surface treatment with
the zinc phosphate treatment agent requires surface adjustment,
which can prolong the total treatment process.
[0005] In addition to the zinc phosphate treatment agent and
chromate conversion treatment agent, a chemical conversion
treatment agent containing a zirconium compound is known (see, for
example, Patent Document 2). The chemical conversion treatment
agent including a zirconium compound is a treatment agent with
concentrations of metal ions and acids which are not as high, and
hence its reactivity is also not as high. This offers a favorable
cost advantage and improved workability during drainage treatment.
Such a chemical conversion treatment agent is also superior to the
above-described zinc phosphate treatment agent in regard to the
inhibition of sludge generation.
[0006] However, a chemical conversion coating film formed with a
treatment agent including a zirconium compound cannot be said to
have good adhesiveness to a coating film obtained by cationic
electro-deposition or the like. Therefore, the treatment agent,
including a zirconium compound, has been combined with phosphate
ions or other components in order to improve its adhesive
properties and corrosion resistance. However, the combination of
phosphate ions can cause the above-described eutrophication.
[0007] Further, an increase in the coating film adhesiveness by
addition of a water soluble resin component has been attempted (for
example, refer to Patent Document 3). In patent Document 3, a
chemical conversion treatment agent which is a metal surface
treatment composition including the following constitution is
disclosed. Namely, this chemical conversion treatment agent is a
chemical conversion treatment agent including a water soluble
resin, the water soluble resin having at least the constituent
units shown by the following Formulas (1), (2).
##STR00001##
[0008] Based on this chemical conversion treatment agent, with
zirconium as a film forming component of the chemical conversion
film, and fluorine as an etching agent for the metal material,
their respective actions can respectively improve the corrosion
resistance and adhesiveness of the metal material. Further, a water
soluble resin having an amino group, specifically a polyvinylamine
resin and a polyallylamine resin, by acting on not only the surface
of the metal material, but also on the coating film formed after
the chemical conversion treatment, can improve the adhesion between
the surface of the metal material and the coating film. [0009]
Patent Document 1: Japanese Unexamined Patent Application
Publication No. H10-204649 [0010] Patent Document 2: Japanese
Unexamined Patent Application Publication No. H7-310189 [0011]
Patent Document 3: Japanese Unexamined Patent Application
Publication No. 2004-218074
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0012] However, in the chemical conversion treatment agent
disclosed in Patent Document 3, if the amino group of the water
soluble resin is present in excess in the chemical conversion
treatment agent, water molecules will be attracted by the excess
amino groups. These attracted water molecules will generate
blisters where the coating film is lifted, deteriorating the base
metal concealing properties along with the coating film
adhesiveness and the corrosion resistance.
[0013] The present invention has been made in view of the
above-described problems, and an objective thereof is to provide: a
metal surface treatment composition capable of forming a chemical
conversion coating film which can offer sufficient base metal
concealing properties, coating film adhesiveness, and corrosion
resistance; a metal surface treatment method for carrying out
surface treatment of a metal material using this metal surface
treatment composition; and a metal material treated with this metal
surface treatment method.
Means for Solving the Problems
[0014] The present inventors have carried out diligent research in
order to solve the above problem. As a result, they have discovered
that the above problem can be solved by specifying the content of
primary and/or secondary amino groups of a polyamine compound in a
metal surface treatment composition containing a zirconium compound
and/or titanium compound, and a polyamine compound, and thus
arrived at and completed the present invention. More specifically,
the invention provides the following.
[0015] The first aspect of the present invention is a metal surface
treatment composition used for surface treatment of a metal,
containing a zirconium compound and/or titanium compound, and a
polyamine compound having a number average molecular weight from
150 to 500,000; wherein said polyamine compound has from 0.1 mmol
to 17 mmol of primary and/or secondary amino group per 1 g of solid
content, and the content of said zirconium compound and/or titanium
compound in said metal surface treatment composition is from 10 ppm
to 10,000 ppm with respect to the metal element, and a mass ratio
of zirconium element and/or titanium element included in said
zirconium compound or titanium compound, with respect to said
polyamine compound, is from 0.1 to 100.
[0016] The second aspect of the present invention is a metal
surface treatment composition according to the first aspect,
wherein said polyamine compound is a product produced by a reaction
between a primary and/or secondary amino group-containing compound,
and an amine activity reducing compound having a functional group A
which has reactivity with said primary or secondary amino
group.
[0017] The third aspect of the present invention is a metal surface
treatment composition according to the second aspect, wherein said
product is produced by reacting from 1 mmol to 60 mmol of said
functional group A with respect to 100 mmol or said primary and/or
secondary amino group.
[0018] The fourth aspect of the present invention is a metal
surface treatment composition according to the second or third
aspect, wherein said functional group A is at least one kind
selected from the group consisting of a glycidyl group, isocyanate
group, aldehyde group, and an acid anhydride group.
[0019] The fifth aspect of the present invention is a metal surface
treatment composition used for surface treatment of a metal,
containing a zirconium compound and/or titanium compound, and a
polyamine compound having a number average molecular weight from
150 to 500,000, wherein said polyamine compound is a product
produced by interaction between a primary and/or secondary amino
group-containing compound, and an amine activity reducing compound
B containing at least one functional group B which interacts with
said primary and/or secondary amino group and reduces the amine
activity, and a content of said zirconium compound and/or titanium
compound in said metal surface treatment composition is from 10 ppm
to 10,000 ppm with respect to the metal element, and the mass ratio
of zirconium element and/or titanium element included in said
zirconium compound and/or titanium compound, with respect to said
polyamine compound, is 0.1 to 100.
[0020] The sixth aspect of the present invention is a metal surface
treatment composition according to the fifth aspect, wherein said
product is produced by interaction of from 1 mmol to 60 mmol of
said functional group B with respect to 100 mmol of said primary
and/or secondary amino group.
[0021] The seventh aspect of the present invention is a metal
surface treatment composition according to the fifth or sixth
aspect, wherein said functional group B is at least one kind
selected from the group consisting of a carboxyl group, sulphonic
group, phosphate group, silanol group, and a phosphorous group.
[0022] The eighth aspect of the present invention is a metal
surface treatment composition according to any one of the first to
seventh aspects, wherein said polyamine compound is a compound
having at least one kind of constituent unit shown by the following
Formula (1), Formula (2), and Formula (3).
##STR00002##
(in Formula (3), R.sub.1 is an alkylene group having a carbon
number of 1 to 6, R.sub.2 is a substituent group shown by the
Formula (4) to Formula (6) below, and R.sub.3 is --OH, --OR.sub.4,
or --R.sub.5 (R.sub.4 and R.sub.5 represent alkyl groups having a
carbon number of 1 to 6.))
##STR00003##
(In Formula (6), R.sub.6 is a hydrogen atom, aminoalkyl group
having a carbon number of 1 to 6, or alkyl group having a carbon
number of 1 to 6, and R.sub.7 is a hydrogen atom or an aminoalkyl
group having a carbon number of 1 to 6.)
[0023] The ninth aspect of the invention is a metal surface
treatment composition according to any one of the first to eighth
aspects, wherein the metal surface treatment composition has a pH
from 1.5 to 6.5.
[0024] The tenth aspect of the present invention is a metal surface
treatment composition according to any one of the first to ninth
aspects, further including a fluorine compound, wherein the content
of a free fluorine element in the metal surface treatment
composition is from 0.01 ppm to 100 ppm.
[0025] The eleventh aspect of the present invention is a metal
surface treatment composition according to any one of the first to
tenth aspects, further including at least one oxidizing agent
selected from the group consisting of nitric acid, nitrous acid,
sulfuric acid, sulfurous acid, persulfuric acid, phosphoric acid,
carboxylic acid group-containing compound, sulfonic acid
group-containing compound, hydrochloric acid, bromic acid, chloric
acid, hydrogen peroxide, HMnO.sub.4, HVO.sub.3, H.sub.2WO.sub.4,
H.sub.2MoO.sub.4, and salts thereof.
[0026] The twelfth aspect of the present invention is a metal
surface treatment composition according to any one of the first to
eleventh aspects, further including at least one metal element
selected from the group consisting of magnesium, zinc, calcium,
aluminum, gallium, indium, copper, iron, manganese, nickel, cobalt,
cerium, strontium, rare earth elements, and silver.
[0027] The thirteenth aspect of the present invention is a metal
surface treatment composition according to any one of the first to
twelfth aspects, further including at least one kind selected from
the group consisting of nonionic surfactants, anionic surfactants,
cationic surfactants, and ampholytic surfactants.
[0028] The fourteenth aspect of the present invention is a metal
surface treatment method for treating the surface of a metal
material, comprising: a treatment solution contact step of
contacting a metal surface treatment solution containing the metal
surface treatment composition according to any one of the first to
thirteenth aspects of the present invention with said metal
material; and a water washing step of washing the metal material
which has been subjected to the treatment solution contact step,
with water.
[0029] The fifteenth aspect of the present invention is a metal
surface treatment method according to the fourteenth aspect,
wherein said metal material is simultaneously subjected to a
degreasing treatment during said treatment solution contact
step.
[0030] The sixteenth aspect of the present invention is a metal
surface treatment method according to the fourteenth or fifteenth
aspect, wherein said metal material is electrolyzed as a cathode in
said treatment solution contact step.
[0031] The seventeenth aspect of the present invention is a metal
surface treatment method according to any one of the fourteenth to
sixteenth aspects, further comprising an acid contact step of
contacting the metal material which has been subjected to said
water washing step, with an acidic aqueous solution containing at
least one selected from the group consisting of cobalt, nickel,
tin, copper, titanium, and zirconium.
[0032] The eighteenth aspect of the present invention is a metal
surface treatment method according to any one of the fourteenth to
seventeenth aspects, including a polymer-containing solution
contact step of contacting the metal material which has been
subjected to said water washing step, with a polymer-containing
solution containing at least one of a water-soluble polymer
compound and a water-dispersible polymer compound.
[0033] The nineteenth aspect, of the present invention is a metal
material treated with the metal surface treatment method according
to any one of the fourteenth to eighteenth aspects.
[0034] The twentieth aspect of the present invention is a metal
material according to the nineteenth aspect having a surface
treatment coating layer on an iron-based metal material surface,
wherein said surface treatment coating layer contains at least 10
mg/m.sup.2 of zirconium element and/or titanium element, and a mass
ratio of zirconium element and/or titanium element with respect to
nitrogen element by XPS analysis of said surface treatment coating
layer is from 0.05 to 500.
[0035] The twenty-first aspect of the present invention is a metal
material according to the nineteenth aspect having a surface
treatment coating layer on a zinc-based metal material surface,
wherein said surface treatment coating layer contains at least 10
mg/m.sup.2 of zirconium element and/or titanium element, and a mass
ratio of zirconium element and/or titanium element with respect to
nitrogen element by XPS analysis of said surface treatment coating
layer is 0.05 to 500.
[0036] The twenty-second aspect of the present invention is a metal
material according to the nineteenth aspect having a surface
treatment coating layer on an aluminum-based metal material
surface, wherein said surface treatment coating layer contains at
least 5 mg/m.sup.2 of zirconium element and/or titanium element,
and the mass ratio of zirconium element and/or titanium element
with respect to nitrogen element by XPS analysis of said surface
treatment coating layer is 0.05 to 500.
[0037] The twenty-third aspect of the present invention is a metal
material according to the nineteenth aspect having a surface
treatment coating layer on a magnesium-based metal material
surface, wherein said surface treatment coating layer, on its
outermost surface, contains at least 5 mg/m.sup.2 of zirconium
element and/or titanium element, and the mass ratio of zirconium
element and/or titanium element with respect to nitrogen element by
XPS analysis of said surface treatment coating layer is 0.05 to
500.
Effects of the Invention
[0038] According to the present invention, it is possible to
provide a metal surface treatment composition which can form a
chemical conversion coating film having sufficient base metal
concealing properties, coating film adhesiveness, and corrosion
resistance, with a metal surface treatment composition containing a
zirconium compound and/or titanium compound, and a polyamine
compound having an amino group, wherein said polyamine compound has
a number average molecular weight from 150 to 500,000, and further
has from 0.1 mmol to 17 mmol of primary and/or secondary amino
group per 1 g of solid content, and the content of said zirconium
compound and/or titanium compound in said metal surface treatment
composition is from 10 ppm to 10,000 ppm, with respect to the metal
element, and the mass ratio of zirconium element and/or titanium
element included in said zirconium compound or titanium compound,
with respect to said polyamine compound, is 0.1 to 100. Further, it
is possible to provide a metal surface treatment method whereby a
surface treatment of a metal material is carried out using this
metal surface treatment composition, and a metal material which has
been treated according to this metal surface treatment method.
PREFERRED MODE FOR CARRYING OUT THE INVENTION
[0039] An embodiment of the invention is described in detail
below.
Metal Surface Treatment Composition
[0040] A metal surface treatment composition according to the
present embodiment is used for metal surface treatment, and
includes a zirconium compound and/or titanium compound, and a
polyamine compound.
[0041] Further, the metal surface treatment composition according
to the present embodiment is diluted with water, and adjusted to
make a metal surface treatment solution, which is used for metal
surface treatment.
Zirconium Compound and/or Titanium Compound Component
[0042] Zirconium and/or titanium derived from the zirconium
compound and/or titanium compound component contained in the metal
surface treatment composition is a component for forming a chemical
conversion coating film. The formation of a chemical conversion
coating film including zirconium and/or titanium on a metal
material allows the improvement of corrosion resistance and
abrasion resistance of the metal material.
[0043] When a metal material is subjected to surface treatment with
the metal surface treatment composition including zirconium and/or
titanium according to the present embodiment, a dissolution
reaction of the metal constituting the metal material occurs. Upon
the occurrence of the metal dissolution reaction, in the presence
of zirconium fluoride and/or titanium fluoride, hydroxides or
oxides of zirconium and titanium are generated by the extraction of
fluorine from ZrF.sub.6.sup.2- and TiF.sub.6.sup.2-, respectively,
by metal ions eluted into the metal surface treatment composition,
and the increase of pH at the interface. Subsequently, hydroxides
or oxides of zirconium and/or titanium are thought to deposit on
the surface of the metal material. The metal surface treatment
composition according to the present embodiment is a reactive
chemical conversion treatment agent, and hence, it can be used for
immersion treatment of a metal material of complicated shape.
Further, chemical reaction produces a chemical conversion coating
film firmly attached to a metal material, which may be subjected to
water washing after the chemical conversion treatment.
[0044] The zirconium compound is not particularly limited, and
examples thereof include alkali metal fluorozirconates such as
K.sub.2ZrF.sub.6, fluorozirconates such as
(NH.sub.4).sub.2ZrF.sub.6, soluble fluorozirconates such as
H.sub.2ZrF.sub.6, zirconium fluoride, zirconium oxide, zirconyl
nitrate, and zirconium carbonate and the like.
[0045] The titanium compound is not particularly limited, and
examples thereof include alkali metal fluorotitanates,
fluorotitanates such as (NH.sub.4).sub.2TiF.sub.6, soluble
fluorotitanates like fluorotitanic acids such as H.sub.2TiF.sub.6,
titanium fluoride, titanium oxide and the like.
Content of Zirconium and/or Titanium
[0046] The content of zirconium and/or titanium in the metal
surface treatment composition according to the present embodiment
is preferably within the range from 10 ppm to 10000 ppm with
respect to the metal element. If the content is less than 10 ppm, a
sufficient amount of coating cannot be provided on a metal
material, and if it is more than 10000 ppm, no further improvement
is expected and cost efficiency decreases. The content is more
preferably from 50 ppm to 1000 ppm with respect to the metal
element.
Free Fluorine Component
[0047] In the metal surface treatment composition according to the
present embodiment, it is possible to further include a fluorine
compound.
[0048] The fluorine element included in the metal surface treatment
composition according to the present embodiment plays the role of
an etching agent of the metal material, and a complexing agent of
the zirconium and/or titanium. The source of the fluorine element
is not particularly limited, and for example, fluoride compounds
such as hydrofluoric acid, ammonium fluoride, fluoroboric acid,
ammonium hydrogen fluoride, sodium fluoride, and sodium hydrogen
fluoride can be mentioned. Further, is it also possible to use
complex fluorides as the source, for example, hexafluorosilicate,
and specifically, (hydro)silicofluoric acid, zinc
(hydro)silicofluoric acid, manganese (hydro)silicofluoric acid,
magnesium (hydro)silicofluoric acid, nickel (hydro)silicofluoric
acid, iron (hydro)silicofluoric acid, and calcium
(hydro)silicofluoric acid can be mentioned.
Content of Free Fluorine Component
[0049] The content of the free fluorine element in the metal
surface treatment composition according to the present embodiment
is from 0.01 ppm to 100 ppm. Herein, "content of free fluorine
element" means the concentration of the fluorine ion in a free
state in the treatment solution, as obtained by measurement of the
treatment solution with a meter having a fluorine ion electrode. If
the content of free fluorine element in the metal surface treatment
composition is less than 0.01 ppm, the solution becomes unstable
and precipitation may occur, and further the etching strength is
reduced, and coating film formation does not sufficiently occur. On
the other hand, if it exceeds 100 ppm, the etching is excessive,
and zirconium coating film formation does not occur. This content
of free flourine element in the metal surface treatment composition
is more preferably from 0.1 ppm to 20 ppm.
Polyamine Compound
[0050] The polyamine compound included in the metal surface
treatment composition according to the present embodiment is a
polymer compound having a plurality of amino groups per molecule.
This polyamine compound having amino groups acts upon both the
chemical conversion coating film and the subsequently formed
coating film, and can increase the adhesiveness of both.
Molecular Weight of Polyamine Compound
[0051] The polyamine compound has a number average molecular weight
within the range from 150 to 500,000. If less than 150, it is not
possible to obtain a chemical conversion coating film having
sufficient coating film adhesiveness, which is not preferable. If
over 500,000, there is concern that coating film formation will be
inhibited. The above lower limit is more preferably 5,000, and the
above upper limit is more preferably 70,000.
Structural Formula of the Amino Group-Containing Compound
[0052] As one example of the polyamine compound, the polyamine
compound having the structure below can be mentioned. Namely, this
polyamine compound is a compound having one kind of the constituent
units shown by the following formulas (1), (2) and (3) below in at
least one portion thereof.
##STR00004##
(In Formula (3), R.sub.1 is an alkylene group having a carbon
number of 1 to 6, R.sub.2 is a substituent group shown by the
formulas (4) to (6) below, and R.sub.3 is --OH, --OR.sub.4, or
--R.sub.5 (R.sub.4 and R.sub.5 are alkyl groups having a carbon
number of 1 to 6).)
##STR00005##
(In formula (6), R.sub.6 is a hydrogen atom, aminoalkyl group
having a carbon number of 1 to 6, or an alkyl group having a carbon
number of 1 to 6, R.sub.7 is a hydrogen atom, or an aminoalkyl
group having a carbon number of 1 to 6.)
[0053] It is particularly preferable if the polyamine compound is a
polyvinylamine resin consisting only of the constituent units shown
by the above Formula (1), a polyallylamine resin consisting only of
the constituent units shown by the above Formula (2), and a
polysiloxane consisting only of the constituent units shown by the
above Formula (3). As one example of the polysiloxane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltriethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,
N-phenyl-3-aminopropyltrimethoxysilane, hydrochlorides of
N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, and the
like can be mentioned. The above polyvinylamine resin,
polyallylamine resin, and polysiloxane are particularly preferable
in the point of having an excellent effect of improving the
adhesiveness.
[0054] The above polyvinylamine resin is not particularly limited,
and for example it is possible to use commercially available
polyvinylamine resins such as PVAM-0595B (manufactured by
Mitsubishi Chemical Corporation) and the like. The above
polyallylamine resin is not particularly limited, and for example
it is possible to use commercially available polyallylamine resins
such as PAA-01, PAA-10C, PAA-H-10C, PAA-D041HCI (all manufactured
by NittoBoseki Co., Ltd.) and the like. The above polyaminosiloxane
is not particularly limited, and it is possible to use commercially
available polysiloxanes. Further, is it possible to use in
combination two or more of the polyvinylamine resin, polyallylamine
resin, and polysiloxane.
[0055] The above polyamine compound has a primary and/or secondary
amino group. In the metal surface treatment composition of the
present embodiment, it is necessary to appropriately control the
active hydrogen of the primary and/or secondary amino group
included in the above polyamine compound, specifically, the primary
or secondary amino group (below referred to as the amine activity).
If the primary and/or secondary amino groups of the polyamine
compound are few, it is not possible to obtain adhesiveness, and
conversely, if there are more than necessary, the excess primary
and/or secondary amino groups will exert adverse effects, and as a
result of the generation of blisters, the base metal concealing
properties, along with the adhesiveness and the corrosion
resistance will be degraded.
First Means for Appropriately Controlling the Amine Activity
[0056] The first means for appropriately controlling the amine
activity of the polyamine compound is to control the primary and/or
secondary amino groups of the polyamine compound to from 0.1 mmol
to 17 mmol per 1 g of the solid content. More preferably, it is
controlled to from 3 mmol to 15 mmol per 1 g of the solid
content.
[0057] However, if the mole number of the primary and/or secondary
amino group per 1 g of the resin solid content is less than 0.1
mmol, adhesiveness to the subsequently formed coating film is not
obtained, and if the mole number of the primary and/or secondary
amino group per 1 g of the resin solid content exceeds 17 mmol, the
excess amino groups will exert adverse effects, and as a result of
the generation of blisters, the base metal concealing properties,
along with the adhesiveness and the corrosion resistance will be
degraded.
[0058] Among the polyamine compounds, for example, the amine value
(as the number of mmol of the primary and/or secondary amino groups
per 1 g of the resin solid content) of a polyvinylamine resin which
is a compound consisting only of the constituent units shown by the
above Formula (1) is 23.3, and the amine value of a polyallylamine
resin which is a compound consisting only of constituent units
shown by the above Formula (2) is 17.5, and because all of the
above resins contain primary and/or secondary amino groups
exceeding 17 mmol per 1 g of the resin solid content, it is
necessary to control the primary and/or secondary amino groups so
that they do not exceed 17 mmol per 1 g of solid content. Further,
is it possible to measure the above amine value according to the
American Society for Testing and Materials (ASTM D 2073 and ASTM D
2074).
[0059] In contrast, if the polyamine composition is a polysiloxane
consisting only of the constituent units shown by the above Formula
(3), 17 mmol per 1 g of the solid content is not exceeded.
[0060] From the above, in order to control the primary and/or
secondary amino groups to "from 0.1 mmol to 17 mmol per 1 g of the
solid content", the polyamine compound is preferably a compound (a
product) produced by a reaction of a compound containing primary
and/or secondary amino groups (below referred to as a primary
and/or secondary amino group-containing compound), and an amine
activity reducing compound having a functional group A which is
reactive with said primary and/or secondary amino group. Namely, it
is desirable to control the primary and/or secondary amino group to
not exceed 17 mmol per 1 g of the solid content by making the
primary and/or secondary amino groups react with other functional
groups, or by copolymerizing vinylamine and allylamine with another
vinyl group-containing compound or allyl group-containing
compound.
Reaction Ratio
[0061] Further, the above product is preferably produced by
reacting from 1 mmol to 60 mmol of functional group A with respect
to 100 mmol of the primary and/or secondary amino groups. If less
than 1 mmol, the excess amino groups will exert an adverse effect,
and as a result of the generation of blisters, the base metal
concealing properties, along with the adhesiveness and the
corrosion resistance will be degraded. If exceeding 60 mmol, the
adhesiveness to the subsequently formed coating film cannot be
obtained. The above product is more preferably produced by reacting
from 1 mmol to 30 mmol of functional group A with respect to 100
mmol of primary and/or secondary amino groups.
Functional Group A
[0062] The functional group A which has reactivity with the primary
and/or secondary amino group is not particularly limited, and for
example, glycidyl groups, isocyanate groups, aldehyde groups, acid
anhydride groups, and the like can be mentioned.
[0063] Here, for example, if the primary and/or secondary amino
group-containing compound is polyallylamine, and the functional
group A is isocyanate, then the polyamine compound produced by
reaction of the polyallylamine and the amine activity reducing
compound A having isocyanate groups has 17 mmol or less of primary
and/or secondary amino groups per 1 g of solid content.
Accordingly, the result of qualitative measurements of the metal
surface treatment composition according to the present embodiment,
for the case that the above polyamine compound is detected, the
polyamine compound is presumed to have 17 mmol or less of the
primary and/or secondary amino group per 1 g of solid content.
Second Means for Appropriately Controlling the Amine Activity
[0064] Further, the second means for appropriately controlling the
amine activity of the polyamine compound is to make the polyamine
compound a product produced by the interaction of a primary and/or
secondary amino group-containing compound, and an amine activity
reducing compound B containing as least one functional group B
which interacts with a primary and/or secondary amino group and
reduces the amine activity. Namely, the amine activity of the
polyamine compound is appropriately controlled by interaction of
the primary and/or secondary amino groups and another functional
group B. In the present invention, "interaction of the primary
and/or secondary amino groups and another functional group B"
refers to an interaction deriving from ionic bonding forces,
hydrogen bonding forces, dipole-dipole interaction forces, and van
der Waals forces between the primary and/or secondary amino group
and the other functional group B, and is an interaction which can
form a chemical conversion coating film having sufficient base
metal concealing properties, coating film adhesiveness, and
corrosion resistance.
Interaction Ratio
[0065] Further, the product produced by the interaction of the
primary and/or secondary amino group-containing compound and the
amine activity reducing compound B having a functional group B is
preferably produced by interacting from 1 mmol to 60 mmol of
functional group B with respect to 100 mmol of the primary and/or
secondary amino group. If less than 1 mmol, the excess amino groups
will exert an adverse effect, and as a result of the generation of
blisters, the base metal concealing properties, along with the
adhesiveness and the corrosion resistance will be degraded. If more
than 60 mmol, it is not possible to obtain adhesiveness to the
subsequently formed coating film. The above product is more
preferably produced by the interaction of from 1 mmol to 30 mmol of
the functional group B with respect to 100 mmol of the primary
and/or secondary amino group.
Functional Group B
[0066] The functional group B interacting with the primary and/or
secondary amino group is not particularly limited, and for example,
carboxyl group, sulphonic group, phosphate group, silanol group,
and phosphorous group can be mentioned.
[0067] As examples of a compound having at least one of the above
functional group A and the above functional group B,
3-isocyanatepropyl-triethoxysilane, colloidal silica, epoxy resin,
acetic anhydride, polyphosphoric acid and the like can be
mentioned, but it is not limited to these examples. Further, it is
possible to use as-is the commercially available KBE9007
(manufactured by Shin-Etsu Chemical Co., Ltd.), and XS1003
(manufactured by Chisso Corporation) and the like.
Mass Ratio of Zirconium Element and/or Titanium Element with
Respect to the Polyamine Compound
[0068] The mass ratio of the zirconium element and/or titanium
element in the zirconium compound and/or titanium compound with
respect to the polyamine compound is from 0.1 to 100. If less than
0.1, it is not possible to obtain corrosion resistance and
adhesiveness. If more than 100, cracks will readily occur in the
surface treatment coating layer, and it is difficult to obtain a
uniform coating layer. Preferably, the above mass ratio is from 0.5
to 20.
pH of Metal Surface Treatment Composition
[0069] The metal surface treatment composition used in the present
embodiment preferably has a pH from 1.5 to 6.5. When the pH is less
than 1.5, excessive etching may make sufficient film formation
impossible, and an uneven film may be formed that adversely affects
the appearance of the coating film. On the other hand, if the pH is
higher than 6.5, etching is insufficient to form a favorable
coating film. The pH is preferably from 2.0 to 5.0, and more
preferably in the range from 2.5 to 4.5.
[0070] The pH of the metal surface treatment composition may be
appropriately adjusted with an acidic compound such as nitric acid
and sulfuric acid, and a basic compound such as sodium hydrate,
potassium hydroxide, and ammonia.
Surfactant
[0071] Further, the metal surface treatment composition according
to the present embodiment may include at least one kind of
surfactant selected from the group consisting of a nonionic
surfactant, anionic surfactant, cationic surfactant, and amphoteric
surfactant. The nonionic surfactants, anionic surfactants, cationic
surfactants, and amphoteric surfactants may be known ones. In the
case where the metal surface treatment composition used in the
present embodiment includes the above surfactants, a favorable film
is formed with no necessity for degreasing and cleansing of the
metal material in advance.
Metal Element
[0072] The metal surface treatment composition according to the
present embodiment may include a metal element which is capable of
imparting adhesiveness and corrosion resistance to the coating
film. Examples of the metal element which may be contained in the
metal surface treatment composition as a chemical conversion
treatment agent include magnesium, zinc, calcium, aluminum,
gallium, indium, copper, iron, manganese, nickel, cobalt, cerium,
strontium, rare earth elements, and silver.
Oxidizing Agent
[0073] The metal surface treatment composition according to the
present embodiment may further include an oxidizing agent for
promoting the film formation reaction. Examples of the oxidizing
agent which may be contained in the metal surface treatment
composition include nitric acid, nitrous acid, sulfuric acid,
sulfurous acid, persulfuric acid, phosphoric acid, carboxylic acid
group-containing compounds, sulfonate group-containing compounds,
hydrochloric acid, bromic acid, chloric acid, hydrogen peroxide,
HMnO.sub.4, HVO.sub.3, H.sub.2WO.sub.4, and H.sub.2MoO.sub.4, and
salts of these oxygen acids.
Metal Surface Treatment Method
[0074] The metal surface treatment method for carrying out surface
treatment of a metal according to the present embodiment is not
particularly limited, and can be carried out by contacting a metal
surface treatment solution including the metal surface treatment
composition according to the present embodiment with a metal
material. More specifically, the metal surface treatment method
according to the present embodiment includes a treatment solution
contact step of contacting a metal surface treatment solution
containing the metal surface treatment composition with a metal
material. Examples of the above metal surface treatment method
include an immersion method, spray method, roll coat method, and
flow coating.
Surface Treatment Conditions
[0075] The treatment temperature in the surface treatment is
preferably within the range of 20.degree. C. to 70.degree. C. If
less than 20.degree. C., there is a possibility that sufficient
coating film formation does not occur, and further there are
disadvantages, such that, in the summertime, temperature adjustment
is necessary, and if above 70.degree. C., there is no particular
effect, and it is economically disadvantageous. This treatment
temperature is more preferably within the range from 30.degree. C.
to 50.degree. C.
[0076] The treatment time for the surface treatment is preferably
within the range from 5 seconds to 1100 seconds. If less than 5
seconds, there is the disadvantage that a sufficient coating film
amount cannot be obtained, and there is no meaning for a time over
1100 seconds, because there is no effect from further increasing
the coating film amount. The treatment time is more preferably
within the range from 30 seconds to 120 seconds.
[0077] The metal surface treatment method according to the present
embodiment, in contrast with the conventional chemical conversion
treatment method with a zinc phosphate chemical conversion
treatment agent, does not require surface adjustment treatment in
advance. This allows chemical conversion treatment of a metal
material with fewer processes.
[0078] Further, in the metal surface treatment method according to
the present embodiment, a metal material may be electrolyzed as a
cathode. In this case, hydrogen is reduced at the interface of the
metal material, which is the cathode, to increase the pH. With the
increase of pH, stability of the compound containing the zirconium
and/or titanium element decreases at the interface of the cathode,
by which a surface treatment film deposits as an oxide or hydroxide
containing water.
Metal Material
[0079] The metal material for use in the metal surface treatment
method according to the present embodiment is not particularly
limited, and examples thereof include a steel sheet and aluminum
sheet. Steel sheet is not particularly limited and includes
cold-rolled steel, hot-rolled steel, mild steel, or high tensile
steel, and also include iron-based base materials (iron-based metal
materials), aluminum-based base materials (aluminum-based metal
materials), zinc-based base materials (zinc-based metal materials),
and magnesium-based base materials (magnesium-based metal
materials). Iron-based base materials refer to base materials
(metal materials) including iron and/or iron alloy, aluminum-based
base materials refer to base materials (metal materials) including
aluminum and/or aluminum alloy, and zinc-based base materials refer
to base materials (metal materials) including zinc and/or zinc
alloy. Magnesium-based base materials refer to base materials
(metal materials) including magnesium and/or magnesium alloy.
[0080] Furthermore, the metal surface treatment method according to
the present embodiment may be simultaneously applied to a metal
material including a plurality of metal base materials, such as
iron-based base materials, aluminum-based base materials, and
zinc-based base materials. Automobile bodies and automobile parts
are constituted of various metal materials such as iron, zinc,
aluminum and the like, but according to the metal surface treatment
method according to the present embodiment, a satisfactory surface
treatment can be carried out with a single treatment even for such
automobile bodies and automobile body parts.
[0081] Iron-based base materials used as a metal material according
to the present embodiment are not particularly limited, and
examples thereof include cold-rolled steel and hot-rolled steel.
The aluminum-based base materials are also not particularly
limited, and examples thereof include 5000 series aluminum alloy,
6000 series aluminum alloy, and aluminum-coated steel plates
treated by aluminum-based electroplating, hot dipping, or vapor
deposition plating. Zinc-based base materials are also not
particularly limited, and examples thereof include zinc or
zinc-based alloy coated steel plates treated by zinc-based
electroplating, hot dipping, or vapor deposition plating, such as
zinc coated steel plate, zinc-nickel coated steel plate, zinc-iron
coated steel plate, zinc-chromium coated steel plate, zinc-aluminum
coated steel plate, zinc-titanium coated steel plate,
zinc-magnesium coated steel plate, and zinc-manganese coated steel
plate. High tensile steel plates are available in various grades
depending on strength and manufacturing process, and examples
thereof include JSC440J, 440P, 440W, 590R, 590T, 590Y, 780T, 780Y,
980Y, and 1180Y.
Amount of Surface Treatment Film
[0082] In order to increase the corrosion resistance of iron-based
metal materials such as cold-rolled steel sheets, hot-rolled steel
sheets, cast iron, sintered materials, and the like, and to form a
uniform surface treatment coating film, and to obtain satisfactory
adhesiveness, if the surface treatment coating layer formed on an
iron-based metal material surface contains at least 10 mg/m.sup.2
or more of zirconium element or titanium element, it is preferable
that the mass ratio of the zirconium element and/or titanium
element with respect to the nitrogen element as analyzed by XPS of
the surface treatment coating layer is 0.05 to 500.
[0083] Further, in order to increase the corrosion resistance of
zinc-based metal materials such as zinc or galvanized steel sheets,
alloy hot dip galvanized steel sheets and the like, and to form a
uniform chemical conversion coating film, and to obtain a
satisfactory adhesiveness, if the surface treatment coating layer
formed on a zinc-based metal material surface contains at least 10
mg/m.sup.2 or more of zirconium element or titanium element, it is
preferable that the zirconium element and/or titanium element mass
ratio with respect to the nitrogen element as analyzed by XPS of
the surface treatment coating layer is 0.05 to 500.
[0084] Further, in order to increase the corrosion resistance of
aluminum-based metal materials such as cast aluminum, aluminum
alloy sheets and the like, to form a uniform chemical conversion
coating film, and to obtain a satisfactory adhesiveness, if the
surface treatment coating layer formed on an aluminum-based metal
material surface contains at least 5 mg/m.sup.2 or more of
zirconium element or titanium element, it is preferable that the
zirconium element and/or titanium element mass ratio with respect
to the nitrogen element as analyzed by XPS of the surface treatment
coating layer is 0.05 to 500.
[0085] Further, in order to increase the corrosion resistance of
magnesium-based metal materials such as magnesium alloy sheets,
cast magnesium and the like, and to form a uniform chemical
conversion coating film, and to obtain a satisfactory adhesiveness,
if the surface treatment coating layer formed on a magnesium-based
metal material surface contains at least 5 mg/m.sup.2 or more of
zirconium element or titanium element, it is preferable that the
zirconium element and/or titanium element mass ratio with respect
to the nitrogen element as analyzed by XPS of the surface treatment
coating layer is 0.05 to 500.
[0086] For any of the metal materials, there is no particular upper
limit for the amount of the surface treatment coating layer, but if
the amount is excessive, the surface treatment coating layer tends
to cause cracking, which makes difficult the operation of forming a
uniform coating film. Accordingly, the amount of the surface
treatment film formed by the metal surface treatment method of the
present embodiment preferably is 1 g/m.sup.2 or less, more
preferably 800 mg/m.sup.2 or less of zirconium and/or titanium with
respect to the metal element.
Pretreatment of Metal Material
[0087] The metal material according to the present embodiment is
preferably a metal material which has been cleansed by degreasing
treatment. After the degreasing treatment, the metal material of
the present embodiment is preferably subjected to water washing
treatment. The degreasing treatment and water washing treatment are
conducted for removing oil and stains from the surface of the metal
material. In usual cases, immersion treatment is conducted for
several minutes at a temperature from 30.degree. C. to 55.degree.
C. using a degreasing agent such as a phosphate-free and
nitrogen-free degreasing detergent. If desired, preliminary
degreasing treatment may be conducted before the degreasing
treatment. Furthermore, for removing the degreasing agent, water
washing treatment is conducted after the degreasing treatment at
least once by spray treatment with a large amount of washing
water.
[0088] As described above, in the case where the metal surface
treatment composition includes the surfactant, a favorable film is
formed with no necessity of degreasing and cleansing of the metal
material in advance. More specifically, in such a case, degreasing
treatment of the metal material is simultaneously achieved in the
treatment solution contact step.
Aftertreatment of Metal Material
[0089] A metal material having formed thereon a chemical conversion
coating film by the metal surface treatment method according to the
present embodiment is preferably subjected to water washing
treatment before the subsequent formation of a coating film. More
specifically, the metal surface treatment method according to the
present embodiment includes a treatment solution contact step of
contacting a metal surface treatment solution containing the metal
surface treatment composition with the metal material, and a water
washing step of washing the metal material with water after the
treatment solution contact step. Impurities on the surface of the
chemical conversion coating film are removed by the water washing
treatment before the formation of a coating film, which further
improves the adhesiveness to a coating film to offer favorable
corrosion resistance.
[0090] The chemical conversion coating film formed by the metal
surface treatment method according to the present embodiment can be
subjected to a water washing treatment before the coating film
formation because a polyamine compound which is a polymer is
incorporated. Namely, in the case of monomer amine compounds, there
is concern that they will be removed by the water washing
treatment, whereas for a polyamine compound which is a polymer,
there is a strong interaction with hydroxides or oxides of
zirconium and/or titanium which form the chemical conversion
coating film, thus there is no such concern. Accordingly, the
chemical conversion coating film formed by the metal surface
treatment method according to the present embodiment will not lose
its adhesiveness by water washing treatment.
[0091] In the water washing treatment after the surface treatment,
the final water washing is preferably conducted with pure water.
The water washing treatment after the surface treatment may be
spray water washing, immersion water washing, or a combination
thereof.
[0092] Following the water washing treatment after the surface
treatment, drying may be conducted as necessary in accordance with
a known method, but in the case where a chemical conversion coating
film is formed by the metal surface treatment method according to
the present embodiment, the film may be coated after water washing
treatment with no necessity for drying treatment. More
specifically, the formation of a chemical conversion coating film
by the metal surface treatment method according to the present
embodiment could be followed by coating by a wet and wet coating
method. Accordingly, the metal surface treatment method according
to the present embodiment allows for the reduction of the surface
treatment process for metal materials before electro-deposition
coating, such as an automobile body, body shell of a two-wheel
vehicle or the like, various parts, and the like before
electro-deposition coating.
Subsequently Formed Coating Film
[0093] Following the formation of a chemical conversion coating
film by the metal surface treatment method according to the present
embodiment, a coating film is formed on the chemical conversion
coating film, and examples thereof include coating films formed by
conventionally known paints such as an electro-deposition paint,
solvent paint, aqueous paint, and powder paint.
[0094] Among these paints, electro-deposition paint, particularly
cationic electro-deposition paint, is preferable for forming a
coating film. The reason is that the cationic electro-deposition
paint usually includes a resin having a functional group which
exhibits reactivity or compatibility with amino groups, and hence,
it acts on the polyamine compound having amino groups contained in
the metal surface treatment composition as a chemical conversion
treatment agent to further improve the adhesiveness between the
electro-deposition coating film and the chemical conversion coating
film. The cationic electro-deposition paint is not particularly
limited, and examples thereof include known cationic
electro-deposition paints such as an aminated epoxy resin, aminated
acrylic resin, and sulfonated epoxy resin.
[0095] Following the water washing step of washing the metal
material with water after the treatment solution contact step of
contacting the metal surface treatment solution containing the
metal surface treatment composition according to the present
embodiment, or following electrolytic treatment by contact, the
metal material may be contacted with an acidic aqueous solution
containing at least one selected from the group consisting of
cobalt, nickel, tin, copper, titanium, and zirconium. More
specifically, the metal surface treatment method according to the
present embodiment may include, following the water washing step of
washing with water the metal material after the treatment solution
contact step, an acid contact step of contacting the metal material
with an acidic aqueous solution containing at least one selected
from the group consisting of cobalt, nickel, tin, copper, titanium,
and zirconium. This further improves the corrosion resistance.
[0096] The supply source of at least one metal element selected
from the group consisting of cobalt, nickel, tin, copper, titanium
and zirconium is not particularly limited. Preferable examples
thereof include oxides, hydroxides, chlorides, nitrates,
oxynitrates, sulfates, oxysulfates, carbonates, oxycarbonates,
phosphates, oxyphosphates, oxalates, oxyoxalates, and organic metal
compounds of the metal elements which are readily available.
[0097] The acidic aqueous solution containing the metal elements
preferably has a pH of 2 to 6. The pH of the acidic aqueous
solution may be adjusted with an acid such as phosphoric acid,
nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid,
and organic acid, and alkali such as sodium hydroxide, potassium
hydroxide, lithium hydroxide, alkali metal salt, ammonia, ammonium
salt, and amine.
[0098] Following the water washing step of washing the metal
material with water after the treatment solution contact step of
contacting the metal surface treatment solution containing the
metal surface treatment composition according to the present
embodiment with the metal material, or following electrolytic
treatment by contact, the metal material may be contacted with a
polymer-containing solution which contains at least one of a
water-soluble polymer compound and water-dispersible polymer
compound. More specifically, the metal surface treatment method
according to the present embodiment may include, following the
water washing step of washing with water the metal material after
the treatment solution contact step, a polymer-containing solution
contact step of contacting the metal material with a
polymer-containing solution which contains at least one of a
water-soluble polymer compound and water-dispersible polymer
compound. This further improves corrosion resistance.
[0099] The water-soluble polymer compound and water-dispersible
polymer compound are not particularly limited, and examples thereof
include polyvinyl alcohol, poly(meth)acrylic acid, copolymer of
acrylic acid and methacrylic acid, copolymers of ethylene and
acrylic monomer such as (meth)acrylic acid and (meth)acrylate,
copolymer of ethylene and vinyl acetate, polyurethane,
aminomodified phenolic resin, polyester resin, epoxy resin, tannin,
tannic acid and its salts, and phytic acid.
EXAMPLES
[0100] The invention is further illustrated by the following
Examples and Comparative Examples, but the invention should not be
limited to them. The blending quantity represents parts by mass
unless otherwise noted.
Example 1
[0101] A commercial cold-rolled steel sheet (SPC, Manufactured by
Nippon Testpanel Co., Ltd., 70 mm.times.150 mm.times.0.8 mm) was
prepared as a metal material.
Pretreatment of Metal Material Before Chemical Conversion
Treatment
(Degreasing Treatment)
[0102] Specifically, the metal material was subjected to degreasing
treatment at 40.degree. C. for two minutes using "SURFCLEANER EC92"
(product name, manufactured by Nippon Paint Co., Ltd.) as an alkali
degreasing treatment agent.
(Water Washing Treatment after Degreasing Treatment)
[0103] Following the degreasing treatment, the metal material was
subjected to immersion washing in a water-washing bath, followed by
spray washing with tap water for about 30 seconds.
Chemical Conversion Treatment
[0104] Before the surface treatment (chemical conversion treatment)
of the metal material, a metal surface treatment composition was
prepared. Specifically, as a polyamine compound having a primary
and/or secondary amino group, "PAA10C" (polyallylamine, effective
concentration 10%, manufactured by NittoBoseki Co., Ltd.) at 1 mass
%, and as a compound having a functional group A and/or functional
group B, "KBM403" (3-glycidoxypropyl-trimethoxysilane, effective
concentration 100%, manufactured by Shin-Etsu Chemical Co., Ltd.)
were reacted at a mass ratio of 1:0.5, at a reaction temperature of
25.degree. C., and reaction time of 60 min to obtain a PAA-epoxy
reactant (1:0.5). Next, using the above PAA-epoxy reactant (1:0.5),
and as a zirconium, a zircon hydrofluoric acid (reagent), a metal
surface treatment composition was prepared so that the zirconium
concentration was 200 ppm, and the PAA-epoxy reactant (1:0.5)
concentration was 200 ppm. This metal surface treatment composition
was adjusted to pH 3.5 with a sodium hydroxide aqueous solution, to
prepare a metal surface treatment solution. The temperature of the
metal surface treatment solution was adjusted to 30.degree. C., and
then a metal material which had been subjected to a water washing
treatment was immersion treated for 60 sec.
[0105] Further, the amount of primary and/or secondary amino groups
(the mol number of the primary and/or secondary amino groups per 1
g of solid content of the polyamine compound) of the above
PAA-epoxide reactant (1:0.5) was determined according to the
following Equation (1). The results are shown in Table 1. Further,
in the following Examples and Comparative Examples, when the
calculation of the amount of primary and/or secondary amino groups
according to c was possible, the results are shown in Table 1 and
Table 2. In the following Examples and Comparative Examples, as a
substitute for amine values determined by measurement, the amine
group amount determined by calculation is used.
amine group amount=(mX-nY)/(m+n) Equation (1)
[0106] (In the above equation, m:n is the solid content mass ratio
of the polyamine compound and the compound having the functional
group A and/or the functional group B; Y is the mmol number of the
functional group A and/or the functional group B per 1 g of the
compound having the functional group A and/or functional group B;
and X is the mmol number of the primary and/or secondary amino
groups included per 1 g of the polyamine compound in the case that
the above compound having functional group A and/or functional
group B is not included in the metal surface treatment
composition.)
[0107] For example, in the case of the PAA-epoxy reactant (1:0.5)
of Example 1, the amine equivalent of the PAA10C is 57, and the
primary and/or secondary amino group amount per 1 g of the PAA10C
is (1/57).times.1000=17.5 (mmol/g). Further, the epoxy equivalent
amount of KBM403 is 236, and the epoxy group amount per 1 g of
KBM403 is (1/236).times.1000=4.2 (mmol/g). The PAA-epoxy reactant
(1:0.5) is a condensate where PAA10C and KBM403 were reacted in a
mass ratio of 1:0.5, and thus, the amine group amount of the
PAA-epoxy reactant (1:0.5), according to the above Equation (1),
where m=1, n=0.5, X=17.5, Y=4.2, is calculated as
(1.times.17.5-0.5.times.4.2)/(1+0.5)=10.3.
Water Washing Treatment after Chemical Conversion Treatment
[0108] The metal material after the chemical conversion treatment
was subjected to spray treatment with tap water for 30 seconds.
Then, it was subjected to spray treatment with ion-exchanged water
for ten seconds
Drying Treatment
[0109] The metal material after the water washing treatment was
dried in an electric drying oven at 80.degree. C. for five minutes.
The amount of the chemical conversion coating film (mg/m.sup.2) was
determined by measuring the content of Zr, Si, and C contained in
the metal surface treatment composition using an "XRF1700" (X-ray
fluorescence spectrometer manufactured by Shimadzu Corporation).
Further, using an x-ray photoelectron spectrometer (XPS, product
name: ESCA3200, manufactured by Shimadzu Corporation), surface
analysis of the obtained test sheet was carried out, and the mass
ratio of the zirconium element with respect to the nitrogen element
of the coating film surface was determined. Specifically, the above
mass ratio was determined from the peak intensity ratio of the is
orbital of the nitrogen element and the 3d orbital of the zirconium
element. The result is shown in Table 1.
Electro-Deposition Coating
[0110] After the chemical conversion treatment and water washing
treatment, the metal materials in a wet condition were each coated
with "ELECTRODEPOSITION POWERNIX 110" (product name, manufactured
by Nippon Paint Co., Ltd.), a cationic electro-deposition paint, to
form an electro-deposition coating film. The dry film thickness
after the electro-deposition coating was 20 .mu.m. Subsequently,
each metal material was washed with water, and baked at 170.degree.
C. for 20 minutes to obtain test plates.
Example 2
[0111] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the concentration of the above PAA-epoxy reactant (1:0.5) was
not 200 ppm, but 50 ppm.
Example 3
[0112] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) was replaced with a
product (PAA-DENACOL EX322 reactant) where the above PAA10C at 1
mass %, and DENACOL EX211 (epoxy, manufactured by Nagase ChemteX
Corporation) were reacted in a mass ratio of 1:1.
Example 4
[0113] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) was replaced with a
product (PAA-KBE9007 reactant) where the above PAA10C at 1 mass %,
and KBE9007 (3-isocyanatepropyl-triethoxysilane, effective
concentration 100%, manufactured by Shin-Etsu Chemical Co., Ltd.)
were reacted in a mass ratio of 1:1, at a reaction temperature of
25.degree. C., and reaction time of 15 minutes.
Example 5
[0114] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) was replaced with a
product (PAA-acetic anhydride reactant) where the above PAA10C at 1
mass %, and acetic anhydride (reagent) were reacted in a mass ratio
of 1:0.5, at a reaction temperature of 25.degree. C., and reaction
time of 60 minutes.
Example 6
[0115] A test sheet was obtained by the same means as in Example 1,
except that instead of the above PAA-epoxy reactant, the above
PAA10C and further, SNOWTEX N (colloidal silica, manufactured by
Nissan Chemical Industries, Ltd.), were added to the metal surface
treatment composition and the metal surface treatment composition
was prepared so that the concentration of the PAA10C was 200 ppm,
and the concentration of the colloidal silica was 200 ppm.
Example 7
[0116] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) was replaced with a
product (low molecular PAA-epoxy reactant) where PAA-3 (low
molecular polyallylamine, effective concentration 15%, manufactured
by NittoBoseki Co., Ltd.) at 1 mass %, and the above KBM403 were
reacted in a mass ratio of 1:0.5.
Example 8
[0117] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) was replaced with
PAA-1112 (allylamine-dimethylallylamine copolymer, non-volatile
content 15 mass %, manufactured by NittoBoseki Co., Ltd.).
Example 9
[0118] Fifteen parts by mass of KBE903
(3-aminopropyl-triethoxysilane, effective concentration 100%,
manufactured by Shin-Etsu Chemical Co., Ltd.), and 15 parts by mass
of KBM603 (N-2(aminoethyl)-3-aminopropyl-trimethoxysilane,
effective concentration 100%, manufactured by Shin-Etsu Chemical
Co., Ltd.) were uniformly dropped over 60 minutes from a dropping
funnel into a solvent of 70 parts by mass of deionized water
(solvent temperature: 25.degree. C.), and a reaction was carried
out for 24 hours at 25.degree. C. under a nitrogen atmosphere, to
obtain a 30% active ingredient condensate of organosilane (below
referred to as KBE603-KBM903 cocondensate). A test sheet was
obtained by the same means as in Example 1, except that the metal
surface treatment composition was prepared so that the above
PAA-epoxy reactant (1:0.5) was replaced with this KBE603-KBM903
cocondensate.
Example 10
[0119] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that nitric acid (reagent) was further added to the metal surface
treatment composition, such that the nitric acid concentration was
200 ppm.
Example 11
[0120] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that aluminum nitrate (reagent) and hydrogen fluoride (reagent)
were further added to the metal surface treatment composition, and
the aluminum nitrate concentration was 500 ppm, and the hydrogen
fluoride concentration was 1000 ppm.
Example 12
[0121] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that RESITOP PL4012 (phenolic resin, manufactured by Gun Ei
Chemical Industry Co., Ltd.) was further added to the metal surface
treatment composition, and the phenolic resin concentration was 200
ppm.
Example 13
[0122] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) was replaced with a
product (PVA-epoxy reactant) where PVAM-0595B (polyvinylamine,
effective concentration 11%, manufactured by Dia-Nitrix Co., Ltd.)
at 1 mass %, and the above KBM403 were reacted in a mass ratio of
1:0.5.
Example 14
[0123] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) had a concentration of
not 200 ppm, but 50 ppm, and ADEKATOL LB-83 (surfactant,
manufactured by Asahi Denka Co., Ltd.) was further added to the
metal surface treatment composition, and the concentration of the
surfactant was 200 ppm.
Example 15
[0124] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) had a concentration of
not 200 ppm, but 50 ppm, and cerium nitrate (reagent) was further
added to the metal surface treatment composition, and the
concentration of the cerium nitrate was 10 ppm.
Example 16
[0125] A test sheet was obtained in the same manner as Example 1
except that a high tensile steel sheet (70 mm.times.150
mm.times.0.8 mm) was used as the metal material in place of the
SPC.
Comparative Example 1
[0126] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared
without adding the above PAA-epoxy reactant (1:0.5) to the metal
surface treatment composition.
Comparative Example 2
[0127] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) produced in Example 1 was
not added, and magnesium nitrate (reagent) was added such that the
concentration of the magnesium nitrate was 200 ppm.
Comparative Example 3
[0128] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) produced in Example 1 was
not added, and sodium nitrite (reagent) was added such that the
concentration of the sodium nitrite was 2000 ppm.
Comparative Example 4
[0129] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) produced in Example 1 was
not added, and KBM903 (3-aminopropyl-triethoxysilane, effective
concentration 100%, manufactured by Shin-Etsu Chemical Co., Ltd.),
was added such that the concentration of the KBE903 was 200
ppm.
Comparative Example 5
[0130] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that the above PAA-epoxy reactant (1:0.5) produced in Example 1 was
not added, and RESITOP PL4012 (aminomodified phenolic resin,
manufactured by Gun Ei Chemical Industry Co., Ltd.), was added such
that the concentration of the RESITOP PL4012 was 200 ppm.
Comparative Example 6
[0131] A test sheet was obtained by the same means as in Example 1,
except that the metal surface treatment composition was prepared so
that instead of the above PAA-epoxy reactant (1:0.5), the above
PAA10C was added to the metal surface treatment composition such
that the concentration of the PAA10C was 200 ppm.
Comparative Example 7
[0132] A test sheet was obtained by carrying out the same
operations as in Example 1, except that the chemical conversion
treatment was changed to zinc phosphate treatment as shown
below.
Zinc Phosphate Treatment
[0133] The above SPC was used as a metal material, and the metal
material after the degreasing treatment and water washing treatment
was subjected to surface adjustment by immersion in 0.3% SURFFINE
GL1 (surface adjusting agent manufactured by Nippon Paint Co.,
Ltd.) for 30 seconds at room temperature. Subsequently, the
material was immersed in SURFDINE SD-6350 (zinc phosphate chemical
conversion treatment agent manufactured by Nippon Paint Co., Ltd.)
at 42.degree. C. for two minutes.
Comparative Example 8
[0134] A test sheet was obtained by the same means as in
Comparative Example 7, except that as the metal material, the above
high-tensile steel sheet (70 mm.times.150 mm.times.0.8 mm) replaced
the above SPC.
Tests
Secondary Adhesiveness Test (SDT)
[0135] Two longitudinally parallel cuts reaching the base metal
were made in the steel plates obtained in the Examples and
Comparative Examples, and these were immersed in a 5 mass % NaCl
solution at 50.degree. C. for 480 hours. Next, after washing with
water and drying, adhesive tape ("L-Pack LP-24" (product name)
manufactured by Nichiban Co., Ltd.) was adhered to the cut
portions, and further the tape was abruptly detached. The maximum
width of the paint adhered to the detached adhesive tape was
measured. The results are shown in Table 1 and Table
TABLE-US-00001 TABLE 1 Metal Material Zr (ppm) pH Polyamine (ppm)
Polyamine/Zr Example 1 SPC 200 3.5 PAA-epoxy reactant (200) 1
Example 2 SPC 200 3.5 PAA-epoxy reactant (50) 0.25 Example 3 SPC
200 3.5 PAA-DENACOL EX211 reactant (200) 1 Example 4 SPC 200 3.5
PAA-KBE9007 reactant (200) 1 Example 5 SPC 200 3.5 PAA-acetic
anhydride reactant (200) 1 Example 6 SPC 200 3.5 PAA (200) 1
Example 7 SPC 200 3.5 low molecular PAA-epoxy reactant (200) 1
Example 8 SPC 200 3.5 allylamine, diallylamine cocondensate 1 (200)
Example 9 SPC 200 3.5 KBM603/KBE903 cocondensate (200) 1 Example 10
SPC 200 3.5 PAA-epoxy reactant (200) 1 Example 11 SPC 200 3.5
PAA-epoxy reactant (200) 1 Example 12 SPC 200 3.5 PAA-epoxy
reactant (200) 1 Example 13 SPC 200 3.5 PAA-epoxy reactant (200) 1
Example 14 SPC 200 3.5 PAA-epoxy reactant (50) 0.25 Example 15 SPC
200 3.5 PAA-epoxy reactant (50) 0.25 Example 16 high-tensile 200
3.5 PAA-epoxy reactant (200) 1 steel sheet Treatment Time Reaction
Conditions (additive mass ratio) Other Additives (ppm) (sec) Notes
Example 1 1% 25.degree. C. .times. 60 min -- 60 -- (1:0.5) Example
2 1% 25.degree. C. .times. 60 min -- 60 amine amount adjusted
(1:0.5) Example 3 1% 25.degree. C. .times. 60 min -- 60 amine value
adjusted (1:1) Example 4 1% 25.degree. C. .times. 60 min -- 60
reaction with isocyanate (1:1) Example 5 1% 25.degree. C. .times.
60 min -- 60 partially acylated PAA (1:0.5) Example 6 -- colloidal
silica (200) 60 ion bonding with silica low molecular PAA Example 7
1% 25.degree. C. .times. 60 min -- 60 (1:0.5) Example 8 -- -- 60
amine value reduced at time of synthesis Example 9 30% 25.degree.
C. .times. 24 h -- 60 polyamine from aminosilane (1:1) (solvent:
water) Example 10 1% 25.degree. C. .times. 60 min nitric acid
(3000) 60 oxidizing agent added (1:0.5) Example 11 1% 25.degree. C.
.times. 60 min Al nitrate (500) 60 metal ion added (1:0.5) HF
(1000) Example 12 1% 25.degree. C. .times. 60 min phenolic resin
(200) 60 adhesive resin added (1:0.5) Example 13 1% 25.degree. C.
.times. 60 min -- 60 polyvinylamine (1:0.5) Example 14 1%
25.degree. C. .times. 60 min surfactant (200) 60 amine amount
adjusted (1:0.5) Example 15 1% 25.degree. C. .times. 60 min cerium
nitrate (10) 60 amine amount adjusted (1:0.5) Example 16 1%
25.degree. C. .times. 60 min -- 60 high-tensile steel sheet (1:0.5)
Amine Amount of SPC Sludge Group Coating Film SDT Detached External
Amount (mg/m.sup.2) N/Zr Width (mm) CCT Appearance (mmol/g) Zr Si C
mass ratio Surface Edge (mm) Example 1 a 10.3 60 -- 8.5 5.2 none
none 6.7 Example 2 a 10.3 82 -- 9.6 not measured none none 7.2
Example 3 a 5.2 50 -- 7.4 not measured none none 7.3 Example 4 a
6.8 55 -- 8.2 not measured none none 6.9 Example 5 a 5.1 65 -- 7.2
not measured none none 6.9 Example 6 b 17.5 69 1.1 10.0 not
measured none 0.4 7.3 Example 7 a 10.3 55 0.3 19.0 not measured 0.6
1.2 7.5 Example 8 a 7.8 62 -- 8.8 not measured none none 6.9
Example 9 a 10.9 51 9.7 10.1 not measured none none 7.3 Example 10
a below 66 -- 9.1 not measured none none 7.5 10.3 Example 11 a
below 66 -- 9.1 not measured none none 6.9 10.3 Example 12 a below
52 -- 7.5 not measured none none 7.2 10.3 Example 13 a 14.1 58 --
10.2 not measured 0.8 2.4 7.2 Example 14 a below 77 -- 9.2 not
measured none none 7.5 10.3 Example 15 a below 72 -- 9.1 not
measured none none 6.6 10.3 Example 16 a 10.3 81 -- 9.9 not
measured 0.6 0.6 7.2
TABLE-US-00002 TABLE 2 Metal Material Zr (ppm) pH Polyamine (ppm)
Polyamine/Zr Comparative SPC 200 3.5 -- -- Example 1 Comparative
SPC 200 3.5 -- -- Example 2 Comparative SPC 200 3.5 -- Example 3
Comparative SPC 200 3.5 -- -- Example 4 Comparative SPC 200 3.5 --
-- Example 5 Comparative SPC 200 3.5 PAA10C (200) 1 Example 6
Comparative SPC 0.3% SURFFINE GL1/ Example 7 SURFDINE SD-6350 (zinc
phosphate) Comparative high-tensile 0.3% SURFFINE GL1/ Example 8
steel sheet SURFDINE SD-6350 (zinc phosphate) Reaction Conditions
(additive mass ratio) (sec) Other Additives (ppm) Treatment Time
Notes Comparative -- -- 60 Zr only Example 1 Comparative -- Mg
nitrate (200) 60 Zr + added metal Example 2 Comparative -- Na
nitrite (2000) 60 Zr + oxidizing agent Example 3 Comparative --
KBM903 (200) 60 Zr + aminosilane monomer Example 4 Comparative --
amine modified 60 Zr + adhesive resin Example 5 phenolic resin
(200) Comparative -- -- 60 Zr + PAA Example 6 Comparative 0.3%
SURFFINE GL1/SURFDINE 120 zinc phosphate Example 7 SD-6350 (zinc
phosphate) Comparative 0.3% SURFFINE GL1/SURFDINE 120 zinc
phosphate Example 8 SD-6350 (zinc phosphate) Amine Group Amount
Amount of SPC Coating Film (mg/m4) N/Zr SDT Detached Width (mm)
Sludge External Appearance (mmol/g) Zr Si C mass ratio Surface Edge
CCT (mm) Comparative b 10.3 38 -- -- not measured 7.6 7.8 9.4
Example 1 Comparative b -- 48 -- -- not measured 5.8 5.6 11.2
Example 2 Comparative b -- 42 -- -- not measured 5.9 5.9 10.6
Example 3 Comparative b 4.5 38 1.1 1.3 not measured 5.2 5.1 9.6
Example 4 Comparative c -- 35 -- 5.2 not measured 7.1 6.4 13.6
Example 5 Comparative b 17.5 52 -- 13.0 not measured 8.2 8.5 12.8
Example 6 Comparative d 10.3 1.6 g/m.sup.2 not measured 2.5 2.1
11.6 Example 7 Comparative d 10.3 1.7 g/m.sup.2 not measured 3.9
4.2 8.9 Example 8
Cyclic Corrosion Test (CCT)
[0136] The test plates obtained in the Examples and Comparative
Examples were sealed at their edges and back surface with a tape,
and scratched with a cross cut pattern (scratch extending to the
base metal) using a cutter, and subjected to a CCT test under the
following conditions. The results are shown in Tables 1 and 2.
CCT Test Conditions
[0137] The test plates were sprayed with a 5% NaCl aqueous solution
warmed to 35.degree. C. for 2 consecutive hours in a salt spray
tester kept at a temperature of 35.degree. C. and a humidity of
95%. Next, they were dried for 4 hours under conditions having a
temperature of 60.degree. C. and a humidity of 20 to 30%, followed
by standing for 2 hours under wet conditions having a temperature
of 50.degree. C. and a humidity of 95% or more. After repeating the
cycle 200 times, the swelling width of the coating film was
measured.
Sludge Observation
[0138] Chemical conversion treatment was conducted in the Examples
and Comparative Examples, and after standing for 30 days at room
temperature, turbidity in the chemical conversion treatment agent
(generation of sludge) was compared by visual observation, and the
workability was evaluated by the following criteria. The results
are shown in Tables 1 and 2.
[0139] a: Transparent liquid.
[0140] b: Slightly clouded.
[0141] c: Clouded.
[0142] d: Precipitate (sludge) generated.
[0143] As shown in Table 1 and Table 2, it was understood that for
the Examples where the specified polyamine compound was added, the
detachment of the coating was remarkably lower than for the
Comparative Examples where the polyamine compound was not added,
and the amount of coating film is greater. Accordingly, by adding a
polyamine compound with a specified content of included primary
and/or secondary amino groups, it is possible to obtain sufficient
base metal concealing properties and coating film adhesiveness, and
it is also possible to prevent corrosion.
INDUSTRIAL APPLICABILITY
[0144] The metal material treated by the metal surface treatment
method of the invention has sufficient base metal concealing
properties, coating film adhesiveness, and corrosion resistance.
Therefore, it is preferably used for applications followed by
coating treatment, such as an automobile body before coating, body
shell of a two-wheel vehicle or the like, various parts, the outer
surface of a container, and coil coating.
* * * * *