DESCRIPTION
ANTICORROSIVE COATING COMPOSITION, ANTICORROSIVE COATING FILM,
AND METHOD FOR PREVENTING CORROSION OF SUBSTRATE
Technical Field
[ 0001] The present invention relates to an anticorrosive
coating composition, an anticorrosive coating film, and a method
for preventing corrosion of a substrate. More particularly, the
10 invention relates to an anticorrosive coating composition capable
of forming an anticorrosive coating film excellent in adhesion
to metal substrates, anticorrosive properties, and the like, an
anticorrosive coating film formed from the composition, and a
method for preventing corrosion,of metal substrates using the
15 composition.
Background Art
[ 0002] Usually, for prevention of corrosion, large-sized
steel structures such as ships, land structures, and bridges are
subjected to anticorrosive coating using an anticorrosive coating
20 composition. In the anticorrosive coating, an anticorrosive
coating composition is applied on a surface of a steel plate or
the like to form an anticorrosive coating film having a thickness
of several hundred to several thousand micrometers. This allows
the surface of the steel plate or the like to be covered with the
SF-2761 2
anticorrosive coating film to prevent the steel plate or the like
from contacting with oxygen, salt, vapor, and the like, thereby
preventing the corrosion of the steel plate or the like.
[0003] In addition, when it is necessary to form a thick film
5 having a thickness of several hundred to several thousand
micrometers, an anticorrosive coating composition including an
amide wax-based thixotropic agent as an anti-sagging and
anti-settling agent (a thixotropic agent) iscused. Such an
anticorrosive coating composition is excellent in adhesion to
10 substrate surfaces of steel structures and the like and
anticorrosive properties under usual coating conditions.
[0004] As the coating composition, the present inventor has
disclosed an anticorrosive coating composition including a
non-tar-based epoxy resin, a curing agent, an epoxy
15 group-containing alkoxysilane compound, a specific flaky pigment,
and an extender pigment (Patent Literature 1).
In addition, in Patent Literature 2, there has been
disclosed an epoxy resin coating composition that includes a
bisphenol epoxy resin, an ethylene-vinyl acetate copolymer, and
20 an amine-based curing agent.
Citation List
Patent Literature
[0005] Patent Literature 1: JP-A-2000-129168.
Patent Literature 2: JP-A-2009-197106.
SF-2761 3
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0006] A structure of a ship, such as a ballast tank, is also
required to have anticorrosive properties and thus subjected to
5 anticorrosive coating. For such a structure, an epoxy-based
anticorrosive coating composition is usually used. In order to
form an anticorrosive coating film having a sufficient film
thickness, the coating composition including ~n amide wax-based
thixotropic agent is applied and dried, and then furthermore, the
10 coating composition is applied thereon and dried, thereby forming
an anticorrosive coating film (double coating). In this case,
for obtaining anticorrosive properties, it is important to ensure
not only adhesion between a substrate and the coating film (or
anticorrosive coating film) formed by the first coating, but also
15 adhesion between the coating film (or the anticorrosive coating
film) formed by the first coating and the coating film (or
anticorrosive coating film) formed by the second coating.
[0007] Spray coating is often used to apply an anticorrosive
coating composition on such a ship structure. In this case, for
20 example, during the spray coating of a wall surface or a ceiling
surface, spray dust tends to attach onto a surface different from
a surface currently being coated, such as a floor surface.
[0008] In addition, particularly when the anticorrosive
coating composition is coated by the double coating, there are
SF-2761 4
cases in which a first coating film is formed on a part (A), and
then, without or while drying the coating film, a first coating
film is formed on another part (B) . During the formation of the
coating film on the part (B), spray dust (or the composition which
5 gives a spray dust through drying) can attach to the coating film
formed on the part (A) . In such a case, the spray dust is partially
taken into the coating film in a process up to drying the coating
film formed on the part (A) . It is thus diffi,cul t to remove the
spray dust attached to the coating film surface when performing
10 .a second coating.
[0009] The pres·ent inventors performed spray coatings using
conventionally known anticorrosive coating compositions such as
the coating compositions described in Patent Literature mentioned
above and found that spray dust as above tends to occur and reduce
15 the adhesion of a film formed thereon.
[ 0010 l In addition, even in the spray coating of an inside
of a ship, such as a ballast tank, where ventilation after coating
is difficult, a composition, which will become spray dust, can
attach, particularly, onto a floor surface and the like of the
20 ballast tank. Herein, due to the structure of the ballast tank,
the vapor of a solvent contained in the coating composition tends
to stay near the floor surface. Accordingly, the composition
attached onto the floor surface and the like tends to be dried
in the solvent atmosphere. In this case, the occurring spray dust
SF-2761 5
has been found to tend to significantly reduce the adhesion of
a film formed thereon.
[0011] The present invention has been accomplished in view
of such circumstances. It is an object of the present invention
5 to provide an anticorrosive coating composition that is excellent
in adhesion to a substrate and anticorrosive properties and whose
spray dust hardly reduces the adhesion of a film formed thereon
to an object to be coated (a target to be coated) even when the
spray dust has attached to the object to be coated.
10 TECHNICAL SOLUTION
[0012] As a result of diligent research to solve the problems
described above, the present inventors discovered that the
problems could be solved by mixing a specific liquid acrylic
polymer in an anticorrosive coating composition comprising an
15 epoxy resin, a curing agent, and an amide wax, thereby completing
the present invention. The structure of the present invention
is as follows:
[0013] [ 1] An anticorrosive coating composition, comprising
an epoxy resin (a), a curing agent (b), an amide wax (c), and a
20 liquid acrylic polymer (d) including a structural unit derived
from an acrylate having an alkyl group of 4 to 18 carbon atoms.
[0014] [2] The anticorrosive coating composition according
to the [1], wherein the liquid acrylic polymer (d) includes a
structural unit derived from an acrylate having an alkyl group
SF-2761 6
of 4 to 18 carbon atoms containing a branched structure.
[0015] [3] The anticorrosive coating composition according
to the [1] or [2], wherein the liquid acrylic polymer (d) includes
a structural unit derived from isobutyl acrylate or 2-ethylhexyl
5 acrylate.
[ 4] The anticorrosive coating composition according to the
[3], wherein the liquid acrylic polymer (d) includes the
structural unit derived from isobutyl acrylate or 2-ethylhexyl
acrylate in an amount of from 30 to 100% by weight with respect
10 to the whole of the liquid acrylic polymer (d) .
[0016] [5] The anticorrosive coating composition according
to the [3] or [4], wherein the liquid acrylic polymer (d) further
includes a structural unit derived from n-butyl acrylate.
[0017] [6] The anticorrosive coating composition according
15 to any one of the [1] to [5], wherein the liquid acrylic polymer
(d) has a glass transition temperature of 0°C or less.
[ 0018] [7] The anticorrosive coating composition according
to any one of the [1] to [6], wherein the composition comprises
the liquid acrylic polymer (d) in an amount of from 0. 01 to 5 parts
20 by weight (a nonvolatile content) with respect to 100 parts by
weight of a nonvolatile content in the anticorrosive coating
composition.
[0019] [8] The anticorrosive coating composition according
to any one of the [1] to [7], wherein the composition comprises
SF-2761 7
the amide wax (c) in an amount of from 0. 05 to 15 parts by weight
(a nonvolatile content) with respect to 100 parts by weight of
a nonvolatile content in the anticorrosive coating composition.
[0020] [9] The anticorrosive coating composition according
5 to any one of the [ 1] to [ 8] , further comprising a silane coupling
agent (e).
10
[0021] [ 10] The anticorrosive coating composition according
to any one of the [ 1] to [ 9], further comprising an extender pigment
(f) •
[11] The anticorrosive coating composition according to the
[10], wherein the extender pigment (f) includes at least a flaky
pigment (g) .
[0022] [12] An anticorrosive coating film formed from the
anticorrosive coating composition according to any one of the [1]
15 to [11].
20
[13] A method for preventing corrosion of a substrate,
comprising a step of coating the substrate with the anticorrosive
coating composition according to any one of the [1] to [11].
Advantageous Effects of Invention
[0023] The present invention can provide an anticorrosive
coating composition that is excellent in adhesion to a substrate
and anticorrosive properties and 'whose spray dust hardly reduces
the adhesion of a film formed thereon to an object to be coated
even when the spray dust has attached to the object to be coated.
1.
5
SF-2761 8
BRIEF DESCRIPTION OF DRAWINGS
[0024] FIG. 1 is a schematic view for explaining an adhesion
test in Examples.
DESCRIPTION OF EMBODIMENTS
[0025] <>
An anticorrosive coating composition of the present
invention (hereinafter also referred to simply as "composition
of the present invention") comprises an epoxy resin (a), a curing
agent (b), amide wax (c), and a liquid acrylic polymer (d)
10 including a structural unit derived from an acrylate having. an
alkyl group of 4 to 18 carbon atoms.
Since the composition of the present invention comprises
these (a) to (d), it is an anticorrosive coating composition that
is excellent in adhesion to a substrate and anticorrosive
15 properties and whose spray dust hardly reduces the adhesion of
a film formed thereon to an object to be coated even when the spray
dust has attached to the object to be coated.
[0026] Therefore, the composition of the present invention
is suitably used for use in the formation of a thick film having
20 a thickness of about 100 }liD or more, used for ship structures such
as a ballast tank, used for spray coating and used as a coating
composition under conditions in which spray dust of the
composition of the invention attaches.
[0027] The conditions in which spray dust of the composition
SF-2761 9
of the invention attaches are not particularly limited as long
as the conditions are those as below where spray dust is formed
from the composition of the present invention.
Specific examples of such conditions include conditions in
5 which during spray coating of the coating composition, the coating
composition attaches to a part different from a part currently
being coated (a part desired to be coated), and more specifically,
conditions in which in the spray coating of a ,large-sized steel
structure such as a ship, a land structure, or a bridge, there
10 is a part to be coated on a floor surface or the like located ,at
a distance of 1m or more below from a position of the spray coating,
and environmental conditions of coating in which a solvent that
can be contained in the composition readily evaporates such as
a temperature ranging from 10 tq 40°C and a humidity of 85% or
15 less.
[0028] The term "spray dust" in the present invention means
a coating composition dried after having attached to a part
different from a part currently being coated (a part desired to
be coated) during spray coating with a coating composition, for
20 example, onto a floor surface or the like during the coating of
a wall surface and a ceiling surface. Such spray dust usually
attaches to a part distant to some extent from a part currently
being coated (a part desired to be coated) in spray coating with
a coating composition.
SF-2761 10
In addition, spray dust causing reduction in the adhesion
of a film to an object to be coated tends to occur in the use of
an anticorrosive coating composition that is required to form a
thick film. This seems to be due to the fact that it is necessary
5 for an anticorrosive coating composition required to form a thick
film not to sag by itself in the formation of the thick film, namely,
to have excellent adhesion to a substrate, and in order to meet
the need, the composition includes amide wax as ,an anti-sagging
and anti-settling agent (a thixotropic agent) .
10 [0029] In addition, in the present invention, the term
"coating film" means a film that is undried or not completely dried
after applying the anticorrosive coating composition; the term
"anticorrosive coating film" means a film that has been dried and
cured after applying the anticorrosive coating composition; and
15 the term "film" means a film (whether dried or undried) formed
from a coating compo.sition (including an anticorrosive coating
composition) .
Additionally, in the present invention, the term "double
coating" means that after applying the composition of the present
20 invention to form a coating film, the film is dried and cured as
needed, and additionally, the same composition is applied thereon;
and the term "top coating" means that applying a composition
different from the composition of the formed the anticorrosive
coating film of the invention on the film.
5
SF-2761 11
[0030] From viewpoints such as preservation stability, the
composition of the present invention is preferably a two-component
type composition prepared by mixing a main agent component and
a curing agent component.
[0031]
The epoxy resin (a) is not particularly limited, and
examples of the epoxy resin (a) include non-tar-based .epoxy resins
described in JP-A-Hll-343454 and JP-A-Hl0-259~51.
[0032] Examples of the epoxy resin (a) include polymers or
10 oligomers containing two or more epoxy groups in molecules thereof
and polymers or oligomers produced by ring-opening reactions of
the epoxy groups. Examples of such epoxy resins include bisphenol
epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy
resins, phenol novolac epoxy resins, cresol epoxy resins, dimer
15 acid-modified epoxy resins, aliphatic epoxy resins, alicyclic
epoxy resins, and epoxidized oil-based epoxy resins.
Among them, from viewpoints such as that.there can be
obtained an anticorrosive coating film having excellent adhesion
to a substrate, preferred are bisphenol epoxy resins, more
20 preferred are bisphenol A-type and bisphenol F-type epoxy resins,
and particularly preferred are bisphenol A-type epoxy resins.
[0033] Examples of such epoxy resins (a) include
epichlorohydrin-bisphenol A epoxy resins (bisphenol A diglycidyl
ether type); epichlorohydrin-bisphenol AD epoxy resins;
SF-2761 12
bisphenol F-type epoxy resins obtained from epichlorohydrin and
bisphenol F(4,4'-methylene bisphenol); epoxy novolac resins;
alicyclic epoxy resins obtained from
3, 4-epoxyphenoxy-3' , 4' -epoxyphenyl carboxy methane and the like;
5 brominated epoxy resins in which at least one of hydrogen atoms
bonded to a benzene ring in an epichlorohydrin-bisphenol A epoxy
resin is substituted with a bromine atom; aliphatic epoxy resins
obtained from epichlorohydrin and aliphatic dihyr~ric alcohol; and
multifunctional epoxy resins obtained from epichlorohydrin and
10 tri(hydroxyphenyl)methane.
[0034] Examples of bisphenol A-type epoxy resins that are
particularly preferably used include polycondensates of
bisphenol A-type diglycidyl ethers, such as bisphenol A diglycidyl
ether, bisphenol A polypropylene,oxide diglycidyl ether,
15 bisphenol A ethylene oxide diglycidyl ether, hydrogenated
bisphenol A diglycidyl ether, and hydrogenated bisphenol A
propylene oxide diglycidyl ether.
[0035] The epoxy resin (a) may be obtained by synthesizing
using a conventionally known method or may be a commercially
20 available product.
Examples of commercially available products that are liquid
under room temperature include ''E028" (a bisphenol A diglycidyl
ether resin manufactured by Ohtake-Meishin Chemical Co., Ltd.,
epoxy equivalent: from 180 to 190, viscosity: from 12,000 to 15,000
SF-2761 13
mPa·s/25"C), ftjER-807" (a bisphenol F diglycidyl ether resin
manufactured by Mitsubishi Chemical Corporation, epoxy
equivalent: from 160 to 175, viscosity: from 3,000 to 4,500 mPa
· s/25"C), ftFLEP 60" (manufactured by Toray Fine Chemicals Co. Ltd.,
5 epoxy equivalent: about 280, viscosity: about 17,000 mPa·s/25"C),
ftE-028-90X" (a xylene solution of a bisphenol A diglycidyl ether
resin (a 828 type epoxy resin solution) manufactured by
Ohtake-Meishin Chemical Co., Ltd., epoxy equiv;alent: about 210).
Examples thereof that are semi-solid under room temperature
10 include ftjER-834" (a bisphenol A-type epoxy resin manufactured
by Mitsubishi Chemical Corporation, epoxy equivalent: from 230
to 270), and ftE-834-85X" (a xylene solution of a bisphenol A-type
epoxy resin (a 834 type epoxy resin solution) manufactured by
Ohtake-Meishin Chemical Co., Ltd., epoxy equivalent: about 300).
15 Examples thereof that are solid under room temperature
include ftjER 1001" (a bisphenol A-type epoxy resin manufactured
by Mitsubishi Chemical Corporation, epoxy equivalent: from 450
to 500) and ftE-001-75" (a xylene solution of a bisphenol A-type
epoxy resin (a 1001 type epoxy resin solution) manufactured by
20 Ohtake-Meishin Chemical Co., Ltd., epoxy equivalent: about 630) .
[0036] The epoxy resin (a) may be used as one kind alone or
in combination of two or more kinds.
[0037] The epoxy resin (a) is preferably liquid or semi-solid
under room temperature (a temperature of from 15 to 25"C;
SF-2761 14
hereinafter the same shall apply) , from viewpoints such as that
there can be obtained a composition having excellent adhesion to
a substrate.
[ 0038] The epoxy resin (a) has an epoxy equivalent of
5 preferably from 150 to 1000, more preferably from 150 to 600, and
particularly preferably from 180 to 500, from viewpoints such as
anticorrosive properties.
[0039] A weight-average molecular weight nf the epoxy resin
(a) measured by GPC (gel permeation chromatograph) is preferably
10 from 350 to 20,000, although the weight-average molecular weight
thereof varies depending on coating and curing conditions for the
composition to be obtained (examples: ordinary temperature drying
coating or baked coating) and the like and thus it is not determined
unconditionally.
15 [0040] The composition of the present invention includes the
epoxy resin (a) in an amount of preferably from 5 to 40% by weight
and more preferably from 10 to 30% by weight.
In addition, when the composition of the present invention
is a two-component type composition comprising a main agent
20 component and a curing agent component, the epoxy resin (a) is
included in the main agent component and is desirably included
therein in an amount of preferably from 5 to 80% by weight, and
more preferably from 5 to 50% by weight.
[0041]
SF-2761 15
The curing agent (b) is not particularly limited and
examples of the curing agent (b) include amine-based curing agents
and acid anhydride-based curing agents. Preferred are amine
curing agents, such as aliphatic, alicyclic, aromatic, and
5 heterocyclic amine curing agents.
[0042] Examples of the aliphatic amine curing agents include
alkylene polyamine and polyalkylene polyamine.
[ 0043] Examples of the alkylene polyamine ]nclude compounds
represented by a formula: H2N-R1-NH2 (R1 represents a divalent
10 hydrocarbon group of 1 to 12 carbon atoms, and an arbitrary.
hydrogen atom of the hydrocarbon group may be substituted with
a hydrocarbon group of 1 to 10 carbon atoms) . Specific examples
of such compounds include methylene diamine, ethylene diamine,
1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane
15 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane,
1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and
trimethyl hexamethylene diamine.
[0044] Examples of the polyalkylene polyamine include
compounds represented by a formula: H2N- (CmH2mNH) nH (m represents
20 an integer of from 1 to 10, and n represents an integer of from
2 to 10, and preferably from 2 to 6). Specific examples of such
compounds include diethylene triamine, dipropylene triamine,
triethylene tetramine, tripropylene tetramine, tetraethylene
pentamine, tetrapropylene pentamine, pentaethylene hexamine, and
SF-2761 16
nonaethylene decamine.
[0045] Examples of aliphatic amine curing agents other than
these include tetra(aminomethyl)methane,
tetrakis(2-aminoethylaminomethyl)methane,
5 1, 3-bis (2' -aminoethylamino) propane,
triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine,
bis(hexamethylene)triamine, and bis(cyanoethyl)diethylene
triamine.
[0046] Specific examples of the alicyclic amine curing
10 agents include 1, 4-cyclohexanediamine,
4,4'-methylenebiscyciohexylamine,
4,4'-isopropylidenebiscyclohexylamine, norbornanediamine,
bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane,
isophoronediamine, and menthenediamine (MDA) .
15 [0047] Examples of the aromatic amine curing agents include
bis(aminoalkyl)benzene, bis(aminoalkyl)naphthalene, and
aromatic polyamine compounds containing two or more primary amino
groups bound to benzene ring.
[0048] More specific examples of the aromatic amine curing
20 agents include o-xylylenediamine, m-xylylenediamine (MXDA),
p-xylylenediamine, phenylenediamine, napthylenediamine,
diaminodiphenylmethane, diaminodiethylphenylmethane,
2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylether,
4,4'-diaminobenzophenone, 4,4'-diaminodiphenylether,
SF-2761 17
4,4'-diaminodiphenylsulfone,
2,2'-dimethyl-4,4'-diaminodiphenylmethane,
2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-dimethoxy-4,4'-diaminobiphenyl,
5 bis(aminomethyl)naphthalene, and bis(aminoethyl)naphthalene.
[0049] Specific examples of the heterocyclic amine curing
agents include N-methylpiperazine, morpholine,
1,4-bis-(3-aminopropyl)-piperazine,
piperazine-1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine),
10 1-[2'-(2''-aminoethylamino)ethyl]piperazine,
1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.
[0050] Other examples of the amine curing agents that can
be used include amines (amine compounds) mentioned in
cTP-B-S49-48480.
15 [0051] Still other examples of the amine curing agents
include diethylaminopropylamine and polyether diamine.
Furthermore, additional examples of the amine curing agents
include modified products of the above-mentioned amine curing
agents, such as polyamide, polyamideamine (polyamide resin),
20 amine adducts with epoxy compound, Mannich compounds (example:
Mannich-modified polyamideamine), Michael adducts, ketimine,
aldimine, and phenalkamine.
[ 0 0 52] The curing agent (b) may be obtained by synthesizing
using a conventionally known method or may be a commercially
SF-2761 18
available product.
Examples of the commercially available product include an
aliphatic polyamine: "ACI HARDNER K-39" (manufactured by PTI JAPAN
Corporation), polyamideamines: "PA-66", "PA-23", and "PA-290 (A)"
5 (all of which are manufactured by Ohtake-Meishin Chemical Co.,
Ltd.),a modified polyamine: "MAD-204(A)" (manufactured by
Ohtake-Meishin Chemical Co., Ltd.), a Mannich-modified
polyamideamine: "ADEKA HARDNER EH-342W3" (manpfactured by ADEKA
Co., Ltd.), a Mannich-modified aliphatic polyamine: "SUNMIDE
10 CX-1154" (manufactured by Sanwa Chemical Industry Co., Ltd.), and
a phenalkamine adduct: "CARDOLITE NC556X80" (manufactured by
Cardolite Corporation).
[0053] Examples of the acid anhydride-based curing agents
include phthalic anhydride, tetrahydrophthalic anhydride,
15 methyltetrahydrophthalic anhydride, 3,6-endomethylene
tetrahydrophthalic anhydride, hexachloroendomethylene
tetrahydrophthalic anhydride, and methyl-3,6-endomethylene
tetrahydrophthalic anhydride.
[0054] The curing agent (b) may be used as one kind alone
20 or in combination of two or more kinds.
[ 0055] The amine curing agent has an active hydrogen
equivalent of preferably from 50 to 1000 and more preferably from
80 to 400, from viewpoints such as anticorrosive properties.
[0056] In the composition of the present invention, the
SF-2761 19
curing agent (b) and the epoxy resin (a) are preferably used in
such amounts that an equivalent ratio therebetween (an amount of
the curing agent used/an active hydrogen equivalent)/(an amount
of the epoxy resin used/ epoxy equivalent) is preferably from 0. 3
5 to 1.5 and more preferably from 0.5 to 1.0.
[0057] When the composition of the present invention is a
two-component type composition comprising a main agent component
and a curing agent component, the curing ageq.t (b) is included
in the curing agent component. The curing agent component is
10 preferably prepared so as to have a nonvolatile content (a solid
content) of from so·to 100%. In this case, a viscosity of the
curing agent component measured by an E-type viscometer is
preferably 100000 mPa·s/25°C or less and more preferably from 50
to 10000 mPa·s/25°C, from viewpoints such as that excellent
15 handleability and coatability.
[ 0058]
The amide wax (c) is not particularly limited and examples
of the amide wax (c) include amide waxes synthesized from vegetable
oil fatty acids and amines.
20 Such an amide wax (c) may be obtained by synthesizing using
a conventionally known method or may be a commercially available
product.
[, Examples of the commercially available product include
"DISPARLON A630-20X" and "DISPARLON 6650 ... manufactured by
SF-2761 20
Kusumoto Chemicals, Ltd., and "ASA T-250F" manufactured by Itoh
Oil Chemicals Co., Ltd.
[0059] The amide wax (c) may be used as one kind alone or
in combination of two or more kinds.
5 [0060] As the results of diligent research, the present
inventors found that spray dust formed from the conventional
anticorrosive coating compositions including fatty acid amide wax
causes reduction in the adhesion of a film formect thereon to an
object to be coated.
10 Accordingly, when considering only the inhibition of
reduction in the adhesion of the film formed on the spray
dust-attached surface to the object to be coated, the composition
of the present invention preferably does not include the amide
wax (c). However, when the composition of the present invention
15 is used for purposes requiring anticorrosive properties,
particularly, for steel structures forming ships, an
anticorrosive coating film to be formed is required to have a
thickness of about 100 J..lffi or more. When forming an anticorrosive
coating film having such a thickness, for example, on wall surface
20 ,and ceiling surface substrates, it is necessary that the
composition does not sag during coating, in other words, the
composition should be excellent in adhesion to the substrates.
Herein, it is preferable to use amide wax from viewpoints
such as its excellent anti-sagging effect, although various
I
I
SF-2761 21
compounds have been conventionally known to be used as an
anti-sagging and anti-settling agent (a thixotropic agent) in
order to improve adhesion of such a coating composition to a
substrate.
5 Taking all described above into consideration, the amide
wax (c) in the composition of the present invention has a content
(a nonvolatile content) of preferably from 0.05 to 15 parts by
weight, more preferably from 0.3 to 5 parts by,weight, and still
more preferably from 0.5 to 3 parts by weight, with respect to
10 100 parts by weight of the nonvolatile content in the composition
of the present invention.
[0061]
The liquid acrylic polymer (d) includes a structural unit
derived from an acrylate having ~n alkyl group of 4 to 18 carbon
15 atoms.
Since the composition of the present invention includes such
a liquid acrylic polymer (d), spray dust occurring from the
composition of the invention hardly reduces the adhesion of a film
formed thereon to an object to be coated, even when the composition
20 includes amide wax.
Therefore, the composition of the present invention has
well-balanced excellence in anticorrosive properties, adhesion
to a substrate (particularly, anti-sagging properties), and the
properties in which spray dust of the composition hardly reduces
SF-2761 22
the adhesion of a film formed thereon to an object to be coated
even when the spray dust has attached to the object to be coated.
[0062] The composition of the present invention exhibiting
the above advantageous effects can be obtained by using the liquid
5 acrylic polymer (d) that is neither solid nor semi-solid, but
liquid under room temperature; that is a polymer whose main raw
material is not methacrylate but acrylate; and that is not a
pol,ymer including no structural unit derived ,from an acrylate
having an alkyl group of 4 to 18 carbon atoms but a polymer
10 including a structural unit derived from an acrylate having ,an
alkyl group of 4 to 18 carbon atoms.
[0063] Examples of the liquid acrylic polymer (d) include
homopolymers or copolymers of acrylates having an alkyl group of
4 to 18 carbon atoms, such as n-butyl acrylate, iso-butyl acrylate,
15 tert-butyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate,
heptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl
acrylate, isononyl acrylate, decyl acrylate, lauryl acrylate,
tridecyl acrylate, and stearyl acrylate.
[0064] The liquid acrylic polymer (d) may be a copolymer of
2\) the acrylate having an alkyl group of 4 to 18 carbon atoms and
other(s) monomer capable of polymerization with the acrylate.
Examples of the other monomer capable of polymerization with
the acrylate having an alkyl group of 4 to 18 carbon atoms include
(meth) acrylic acid ester monomers such as methyl (meth) acrylate,
SF-2761 23
ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,
2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate,
2-(2-ethylhexaoxy)ethyl (meth)acrylate,
1-methyl-2-methoxyethyl (meth)acrylate, 3-methoxybutyl
5 (meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate,
m-methoxyphenyl (meth)acrylate, p-methoxyphenyl (meth)acrylate,
o-methoxyphenyl ethyl (meth)acrylate, m-methoxyphenyl ethyl
(meth) acrylate, p-methoxyphenyl ethyl (meth) a,r::rylate, n-propyl
(meth)acrylate, iso-propyl (meth)acrylate, n-butylmethacrylate,
10 iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl
methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl
(meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate,
cyclohexyl (meth)acrylate, glycidyl (meth)acrylate,
dicyclopentenyl (meth) acrylate, ... and 2-dicyclopentenoxy ethyl
15 (meth)acrylate; hydroxyl group-containing monomers such as
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate
and 4-hydroxybutyl (meth)acrylate; adducts of 2-hydroxyethyl
(meth)acrylate and ethylene oxide, propylene oxide,
20 y-butyrolactone, E-caprolactone, or the like; dimers or trimmers
of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth) acrylate, or the like; ntonomers having a plurality of
hydroxyl groups such as glycerol (meth)acrylates; primary or
secondary amino group-containing vinyl monomers such as
i
SF-2761 24
buthylaminoethyl (meth)acrylate and (meth)acrylamide; tertiary
amino group-containing vinyl monomers such as dimethylaminoethyl
(meth)acrylate, diethylaminoethyl (meth)acrylate,
dimethylaminopropyl (meth)acrylate, dimethylaminobutyl
5 (meth)acrylate, dibutylaminoethyl (meth)acrylate,
dimethylaminoethyl (meth)acrylamide, and dimethylaminopropyl
(meth)acrylamide; heterocyclic-based basic monomers such as
vinylpyrrolidone, vinylpyridine, and vinylcar,bazole; and
vinyl-based monomers such as stylene, vinyl toluene, a-methyl
10 stylene, (meth) acrylonitrile, vinyl acetate, and vinyl
propionate.
[0065] An acrylate having an alkyl group of 4 to 18 carbon
atoms and other(s) monomer used in a copolymer of the acrylate
and other (s) monomer capable of P()lymerization. with the acrylate,
15 respectively, can be used by selecting only one kind or a
combination of two or more kinds as needed.
[0066] When the liquid acrylic polymer (d) is a copolymer
of the acrylate having an alkyl group of 4 to 18 carbon atoms and
other ( s) monomer capable of polymerization with the acrylate, the
20 term "acrylic polymer·" means a polymer obtained by using an
acrylate , as a synthetic raw material monomer of the copolymer,
in an amount of 55% by weight or more, preferably 70% by weight
or more, and still more preferably 80% by weight or more with
respect to 100% by weight of the synthetic raw material monomer.
SF-2761 25
[0067] The alkyl group of 4 to 18 carbon atoms is preferably
an alkyl group of 4 to 12 carbon atoms and more preferably an alkyl
group of 4 to 8 carbon atoms, from viewpoints such as that there
can be obtained a composition having well-balanced excellence in
5 adhesion to a substrate (particularly, anti-sagging properties)
and the properties in which spray dust of the composition hardly
reduces the adhesion of a film formed thereon to an object to be
coated even when the spray dust has attached to the object to be
coated.
10 [0068] The liquid acrylic polymer (d) includes preferably
a structural unit derived from an acrylate having an alkyl group
of 4 to 18 carbon atoms having a branched structure, preferably
a structural unit derived from an acrylate having an alkyl group
of 4 to 12 carbon atoms having a branched structure, more
15 preferably a structural unit derived from isobutyl acrylate or
2-ethylhexyl acrylate, particularly preferably a structural unit
derived from isobutyl acrylate or 2-ethylhexyl acrylate and a
structural unit derived from n-butyl acrylate, and particularly
preferably a structural unit derived from isobutyl acrylate and
20 n-butyl acrylate or a structural unit derived from 2-ethylhexyl
acrylate, from viewpoints such as that there can be obtained a
compostion having well-balanced excellence in adhesion to a
substrate and the properties in which spray dust of the composition
hardly reduces the adhesion of a film formed. thereon to an object
SF-2761 26
to be coated even when the spray dust has attached to the object
to be coated.
[0069] When the liquid acrylic polymer (d) includes a
structural unit derived from an acrylate having an alkyl group
5 of 4 to 18 carbon atoms having a branched structure, the liquid
acrylic polymer (d) includes a structural unit derived from an
acrylate having an alkyl group of 4 to 18 carbon atoms having a
branched structure in an amount of preferably from 30 to 100% by
weight, more preferably from 40 to 100% by weight, and particularly
10 preferably from 50 to 100% by weight with respect to a total 100%
by weight of the liquid acrylic polymer (d), from viewpoints such
as that there can be obtained a composition that is excellent in
adhesion to a substrate and anticorrosive properties and whose
spray dust hardly reduces the adhesion of a film formed thereon
15 to the object to be coated even when the spray dust has attached
to the object to be coated. In addition, due to the same reasons,
the liquid acrylic polymer (d) includes a structural unit derived
from isobutyl acrylate or 2-ethylhexyl acrylate in an amount of
preferably from 30 to 100% by weight, more preferably from 40 to
20 100% by weight, and particularly preferably from 45 to 100% by
weight.
[0070] In addition, when the liquid acrylic polymer (d)
includes a structural unit (i) derived from isobutyl acrylate or
2-ethylhexyl acrylate and a structural unit (ii) derived from
SF-2761 27
n-butyl acrylate, the liquid acrylic polymer (d) preferably
includes the structural units (i) and (ii) such that a total of
the structural units (i) and (ii) is preferably from 30 to 100%
by weight, more preferably from 50 to 100% by weight, and
5 particularly preferably from 75 to 100% by weight with respect
to the total 100% by weight of the liquid acrylic polymer (d) and
such that a ratio of the structural unit (i) to the structural
~nit (ii) (the structural unit (i): the struc~ural unit (ii)) is
preferably from 10:90 to 99:1 and more preferably from 10:90 to
10 90:10 (provided that the total of the structural units (i) and
(ii) is 100), from viewpoints such as that there can be obtained
a composition that is excellent in adhesion to a substrate and
anticorrosive properties and whose spray dust hardly reduces the
adhesion of a film formed thereon to an object to be coated even
15 when the spray dust has attached to the object to be coated.
[0071] The liquid acrylic polymer (d) has. a glass transition
temperature of preferably 0°C or less and more preferably -30°C
or less, from viewpoints such as that there can be obtained a
composition whose spray dust hardly reduces the adhesion of a film
20 formed thereon to an object to be coated even when the spray dust
has attached to the object to be coated.
Such a glass transition temperature can be measured by DSC
(a differential scanning calorimeter) .
[0072] A weight-average molecular weight of the liquid
SF-2761 28
acrylic polymer (d) measured by GPC is preferably from 1000 to
100000 and more preferably from 1000 to 30000, from viewpoints
such as that there can be obtained a composition that is excellent
in adhesion to a substrate and whose spray dust hardly reduces
5 the adhesion of a film formed thereon to an object to be coated
even when the spray dust has attached to the object to be coated.
[0073] A viscosity of an acrylic polymer solution prepared
by diluting the liquid acrylic polymer (d) w5_th an equivalent
weight of butyl acetate, measured by an E-type viscometer, varies
10 depending on an average molecular weight of the polymer. The
viscosity thereof is preferably from 5 to 3000 mPa · s/25°C and more
preferably from 5 to 300 mPa·s/25°C, from viewpoints such as that
there can be obtained a composition that is excellent in adhesion
to a substrate and whose spray dust hardly reduces the adhesion
15 of a film formed thereon to the object to be coated even when the
spray dust has attached to the object to be coated.
[0074] The liquid acrylic polymer (d) may be obtained by
synthesizing using a conventionally known method or may be a
commercially available product.
20 The liquid acrylic polymer (d) can be synthesized by
reacting the acrylate having an alkyl group of 4 to 18 carbon atoms
with other(s) monomer used as needed, and if needed adding an
additive such as a polymerization initiator, in the presence of
an organic solvent under heating at from 30 to 180°C for from 2
- ·~--
SF-2761 29
to 18 hours.
In this reaction, the monomer to be used in the reaction
is preferably used in such an amount that the obtained liquid
acrylic polymer (d) includes a structural unit derived from the
5 monomer in an amount within the above range.
[0075] The organic solvent is not particularly limited.
Examples of the organic solvent include aromatic
hydrocarbon-based solvents such as toluene and xylene,
ketone-based solvents such as methyl ethyl ketone and methyl
10 isobutyl ketone, ester-based solvents such as butyl acetate,
alcohol-based solvents such as isopropanol, and aliphatic
hydrocarbon-based solvents such as mineral spirit, n-hexane,
n-octane, 2,2,2-trimethylpentane, isooctane, n-nonane,
cyclohexane, and methylcyclohexane.
15 These may be used as one kind alone or in combination of
two or more kinds.
[0076] In the composition of the present invention, a varnish
including the liquid acrylic polymer (d) obtained in the above
reaction may be used as it is, or a resultant obtained by removing
20 the polymerization initiator from the varnish may be used.
Accordingly, as the organic sol vent, it is preferable to use the
same compound as any of solvents below that can be used in the
composition of the present invention.
[0077] The polymerization initiator is not particularly
SF-2761 30
limited. Examples of the polymerization initiator that can be
used include azo-based initiators such as azobisisobutyronitrile,
2,2-azobis(2-methylbutyronitrile),
2,2-azobis(2-methylpropionitrile),
5 2,2-azobis(2,4-dimethylvaleronitrile) and peroxide-based
initiators such as benzoyl peroxide, t-butyl peroxyoctanoate,
diisobutylperoxide, di-(2-ethylhexyl) peroxypivalate, decanoyl
peroxide, t-butylperoxy-2-ethylhexanoate, and t-butylperoxy
benzoate.
10 These may be used as one kind alone or in combination.of
two or more kinds.
[0078] The liquid acrylic polymer (d) in the composition of
the present invention has a content (a nonvolatile content) of
preferably from 0.01 to 5 parts .by weight, more preferably from
15 0.03 to 5 parts by weight, and still more preferably from 0.05
to 2 parts by weight with respect to 100 parts by weight of the
nonvolatile content in the composition of the invention.
When the composition of the present invention includes the
liquid acrylic polymer (d) in such an amount, spray dust formed
20 from the composition hardly reduces the adhesion of a film formed
thereon to an object to be coated, although amide wax is included
in the composition.
[0079]
The composition of the present invention may include, in
SF-2761 31
addition to the (a) to (d), a silane coupling agent (e), an extender
pigment (f), a coloring pigment, an anti-sagging and anti-settling
agent, a solvent, a plasticizer, a curing accelerator, an
inorganic dehydrating agent (a stabilizer) , a defoaming agent,
5 an antifouling agent, and/or the like, as needed, as long as the
object of the invention is not impaired.
The other components mentioned above are not limited as long
as they are conventionally known ones that are used in
anticorrosive coating compositions.
10 [0080]
The use of the silane coupling agent (e) can further improve
not only the adhesion of an obtained anticorrosive coating film
to a substrate, but also can improve anticorrosive properties of
the obtained anticorrosive coating film, such as salt water
15 resistance. Thus, the composition of the present invention
preferably comprises. the silane coupling agent (e).
Such a silane coupling agent may be used as one kind alone
or in combination of two or more kinds.
[0081] The silane coupling agent (e) is not particularly
20 limited and can be a conventionally known one. The silane
coupling agent (e) is preferably a compound that contains at least
two functional groups in one molecule and can contribute to
improvement in adhesion to a substrate, reduction in the viscosity
of the composition, and the like, and more preferably a compound
SF-2761 32
represented by a formula: X-Si (OR) 3 [X represents a functional
group capable of reacting with an organic substance (such as an
amino group, a vinyl group, an epoxy group, a mercapto group, a
halo group, or a hydrocarbon group containing any of these groups,
5 in which the hydrocarbon group may have an ether bond and/or the
like) or represents an alkyl group; and OR represents a
hydrolyzable group (such as a methoxy group or an ethoxy group)] .
[0082] Specific examples of the preferablE> silane coupling
agents include "KBM 403" (y-glycidoxypropyltrimethoxysilane
10 manufactured by Shin-Etsu Chemical Co. , Ltd. ) and" SILA-ACE S-51 0"
(manufactured by JNC Corporation) .
[0083] When the silane coupling agent (e) is mixed in the
composition of the present invention, an amount of the silane
coupling agent (e) to be mixed is l?referably from 0.1 to 10 parts
15 by weight and more preferably from 0. 3 to 5 parts by weight with
respect to 100 parts by weight of the composition of the invention.
The use of the composition including the silane coupling agent
(e) in such an amount can improve the performances of an
anticorrosive coating film such as adhesion to a substrate, and
20 can reduce the viscosity of the composition of the invention, thus
improving coating workability.
[0084]
The use of the extender pigment (f) can not only be
cost-effective for a composition to be obtained, but also can lead
SF-2761 33
to the formation of an anticorrosive coating film excellent in
anticorrosive properties, salt water resistance, high
temperature and high humidity resistance, and the like.
Therefore, the composition of the present invention preferably
5 comprises the extender pigment (f) .
[0085] Specific examples of the extender pigment (f) include
barium sulphate, potassium feldspar, barite powder, silica,
calcium carbonate, talc, mica, and glass fla~e.
Such an extender pigment (f) may be used as one kind alone
10 or in combination of two or more kinds.
[0086] The composition of the present invention preferably
comprises at least a flaky pigment (g) as the extender pigment
(f), from viewpoints such as that there can be formed an
anticorrosive coating film excellent in anticorrosive properties,
15 salt water resistance, high temperature and high humidity
resistance, and the like.
Examples of such a flaky pigment (g) include mica and glass
flake. Mica is preferable from viewpoints such as that it is
easily available at low cost and there can be formed an
20 anticorrosive coating film more excellent in terms of the
above-mentioned effects.
The flaky pigment (g) may be used as one kind alone or in
combination of two or more kinds.
[0087] The mica is preferably mica having a high aspect ratio
SF-2761 34
of from 30 to 90, from viewpoints such as improvement in blistering
resistance, reduction in creeping properties, and relaxation of
internal stress in an anticorrosive coating film to be obtained.
Examples of such mica having a high aspect ratio include "SUZORITE
5 MICA 200HK" (manufactured by Kuraray Trading Co., Ltd., aspect
ratio: from 40 to 60).
[0088] When the extender pigment (f) is mixed in the
composition of the present invention, an amount of the extender
pigment (f) to be mixed is preferably from 5 to 8 0 parts by weight
10 and more preferably from 10 to 70 parts by weight with respect
to 100 parts by weight of the nonvolatile content of the
composition of the invention.
In addition, an amount of the flaky pigment (g) to be mixed
is preferably from 1 to 40 parts by weight and more preferably
15 from 3 to 20 parts by weight with respect to 100 parts by weight
of the nonvolatile content of the composition of the present
invention, from viewpoints such as improvement in the performances
of an anticorrosive coating film, such as water-resistant and
anticorrosive properties and bending resistance.
20 [0089]
Examples of the coloring pigment include titanium white,
red iron oxide, yellow iron oxide, and carbon black.
The coloring pigment may be used as one kind alone or in
combination of two or more kinds.
SF-2761 35
[0090] When the coloring agent is mixed in the composition
of the present invention, an amount of the coloring agent to be
mixed is preferably from 0.1 to 15 parts by weight and more
preferably from 0. 5 to 10 parts by weight with respect to 100 parts
5 by weight of the nonvolatile content of the composition of the
invention.
[0091] In addition, the extender pigment and the coloring
pigment are preferably included in the composi~ion of the present
invention in such amounts that an anticorrosive coating film
10 formed from the composition of the present invention has a pigm,ent
volume concentration (PVC: a volume concentration of the extender
pigment (E) and the coloring pigment in the anticorrosive coating
film) of preferably from 10 to 75% by weight and preferably from
25 to 50% by weight, from viewpoints such as anticorrosive
15 properties.
[0092]
The anti-sagging and anti-settling agent (a compound other
than the amide wax (c)) can provide thixotropy to the composition
of the present invention to improve the adhesion of the composition
20 to a substrate. Although the amide wax (c) is also an anti-sagging
and anti-settling agent, the composition of the present invention
may further comprise an anti-sagging and anti-settling agent as
needed.
The anti-sagging and anti-settling agent is not
5
10
SF-2761 36
particularly limited and examples thereof include organic
thixotropic agents and inorganic thixotropic agents.
The anti-sagging and anti-settling agent may be used as one
kind alone or in combination of two or more kinds.
[0093] Examples of the organic thixotropic agents include
hydrogenated castor oil-based, oxidized polyethylene-based,
vegetable oil polymerized oil-based, and surfactant-based
thixotropic agents and thixotropic agents as combinations of two
or more kinds thereof.
[0094] In addition, examples of the inorganic thixotropic
agents include fine powdered silica, bentonite, silica
surface-treated with a silane compound or the like, bentonite
surface-treated with quaternary ammonium salt or the like (organic
bentonite), ultrafine surface-treated calcium carbonate, and
15 mixtures thereof. Specific examples of the inorganic thixotropic
agents include silica fine powder obtained by micronization by
a drying method [for example, product name: AEROSIL 300
manufactured by Nippon Aerosil Co., Ltd.], fine powder obtained
by modifying silica fine powder with hexamethyldisilazane [for
20 example, product name: AEROSIL RX300 manufactured by Nippon
Aerosil Co., Ltd.] , fine powder obtained by modifying silica fine
powder with polydimethylsiloxane [for example, product name:
AEROSIL RY300 manufactured by Nippon Aerosil Co., Ltd.],
hydrophobic fine powdered silica obtained by modifying silica fine
SF-2761 37
powder with dimethyldichlorosilane [for example, product name:
AEROSIL R972 manufactured by Nippon Aerosil Co., Ltd.], and
organic bentonite (product name: BENTONE SD-2 manufactured by
Elementis Specialties, Inc).
5 [0095] Among them, a combination of a silica surface-treated
with a silane compound or the like and a bentonite surface-treated
with quaternary ammonium salt or the like is preferably used as
the anti-sagging and anti-settling agent, from,viewpoints such
as that there can be obtained a composition excellent in adhesion
10 to a substrate.
[0096] When the anti-sagging and anti-settling agent is
mixed in the composition of the present invention, an amount of
the anti-sagging and anti-settling agent to be mixed is preferably
from 0.1 to 5 parts by weight and more preferably from 0.3 to 2
15 parts by weight with respect to 100 parts by weight of the
nonvolatile content of the composition of the invention, from
viewpoints such as that there can be obtained a composition
excellent in coating material viscosity, coating workability, and
storage stability. I ! .
20 [0097] In addition, in the composition of the present
invention, a total content of the amide wax (c) and the
anti-sagging and anti-settling agent is preferably from 0.3 to
6 parts by weight and more preferably from 0. 5 to 3 parts by weight
with respect to 100 parts by weight of the nonvolatile content
SF-2761 38
of the composition of the invention, from viewpoints such as that
there can be obtained a composition having well-balanced
excellence, for example, in anti-sagging properties and the
properties in which spray dust of the composition hardly reduces
5 the adhesion of a film formed thereon to an object to be coated
even when the spray dust has attached to the object to be coated.
Additionally, in this case, the amide wax (c) and the
anti-sagging and anti-settling agent are desirp.bly included such
that a mass ratio between the contents of the amide wax (c) and
10 the anti-sagging and anti-settling agent (the content of the amide
wax (c): the content of the anti-sagging and ant.i-settling agent)
in the composition of the present invention is preferably from
10: 90 to 90: 10 and more preferably from 15: 8 5 to 85: 15 (provided
that the total content of the amide wax (c) and the anti-sagging
15 and anti-settling agent is 100).
[0098]
The solvent is not particularly limited and can be used a
conventionally known one. Examples of known solvents that can
be used include xylene, toluene, methyl isobutyl ketone,
20 methoxypropanol, methyl ethyl ketone, butyl acetate, butanol,
isopropyl alcohol, and 1-methoxy-2-propanol.
These solvents may be used as one kind alone or in
combination of two or more kinds.
[0099] When the solvent is mixed in the composition of the
SF-2761 39
present invention, an amount of the solvent to be mixed is not
particularly limited and can be adjusted as needed depending on
a coating method used in the coating of the composition of the
invention. When considering coatability and the like of the
5 composition of the present invention, the solvent is desirably
included in such an amount that the nonvolatile content of the
composition of the invention has a concentration of preferably
from 55 to 98% by weight and more preferably,from 65 to 95% by
weight.
10 In addition, when the composition of the present invention
is spray coated, the solvent is desirably included in such an
amount that the nonvolatile content of the composition of the
invention has a concentration of preferably from 55 to 95% by
weight and more preferably from 65 to 90% by weight, from
15 viewpoints such as coatability.
[0100]
The composition of the present invention preferably
comprises a plasticizer, from viewpoints such as improvement in
flexibility and weather resistance of an anticorrosive coating
20 film to be obtained. ,
The plasticizer may be used as one kind alone or in
combination of two or more kinds.
[0101] The plasticizer can be selected from a wide range of
conventionally known ones, and examples thereof include liquid
-., _
SF-2761 40
hydrocarbon resins of low boiling point fractions or the like
obtained by thermal decomposition of naphtha, petroleum resins
that are solid under room temperature, xylene resins, ·and
coumarone-indene resins. Specific examples thereof include a
5 liquid hydrocarbon resin and a flexibility-imparting resin
described in JP-A-2006-342360.
[0102] Among them, preferred are liquid hydrocarbon resins,
and petroleum resins that are solid under roomtemperature, xylene
resins and coumarone-indene resins, which contain a hydroxyl group,
10 from viewpoints such as good compatibility with the epoxy resi.n
(a) •
[ 0103] Examples of commercially available products of the
liquid hydrocarbon resins include "NECIRES EPX-L" and "NECIRES
EPX-L2" (both of which are phenol-modified hydrocarbon resins
15 manufactured by NEVCIN Polymers Co.), "HILENOL PL-10008" (a liquid
hydrocarbon resin manufactured by Kolon Chemical Co). Examples
of commercially available products of the petroleum-based resins
that are solid under room temperature include "NEO POLYMER E-100",
"NEO POLYMER K-2", and "NEO POLYMER K-3" (all of which are C9-based
20 hydrocarbon resins manufactured by Nippon Petrochemicals Co.
Ltd.); examples of commercially available products of the
coumarone-indene resins include"NOVARES CA 100" (manufactured
by Rutgers Chemicals AG); and examples of commercially available
products of the xylene resins include "NIKANOL Y-51" (manufactured
SF-2761 41
by Mitsubishi Gas Chemical Company, Inc).
[0104] In the mixing of the plasticizer in the composition
of the present invention, an amount of the plasticizer to be mixed
is preferably from 1 to 50 parts by weight and more preferably
5 from 3 to 30 parts by weight with respect to 100 parts by weight
of the composition of the invention, from viewpoints such as that
there can be obtained an anticorrosive coating film excellent in
weather resistance, anti-cracking properties, and the like.
[0105]
10 The composition of the present invention preferably
comprises a curing accelerator that can contribute to the
adjustment of curing rate, particularly acceleration thereof.
Examples of the curing accelerator include tertiary amines.
These curing accelerators may be used as one kind alone or
15 in combination of two or more kinds.
[0106] Specific examples of the curing accelerators include
triethanol amine, dialkylaminoethanol, triethylenediamine
[1,4-diazacyclo(2,2,2)octane],
2,4,6-tri(dimethylaminomethyl)phenol (examples: product name
20 "VERSAMINE EH30" (manufactured by Henkel Hakusui Corporation) and
product name: "ANCAMINE K-54" (manufactured by Air Products Japan,
Inc.)) . These curing accelerators are preferably included in an
amount of from 0.05 to 2.0% by weight in the composition of the
present invention.
SF-2761 42
[0107] <>
The anticorrosive coating film of the present invention is
not particularly limited as long as it is a film formed from the
composition of the invention. The anticorrosive coating film of
5 the present invention is preferably a film obtained by forming
a coating film from the composition of the invention applied on
a substrate and then drying and curing the coating film.
Thus anticorrosive coating film has excell,ent anticorrosive
properties such as salt water resistance and high temperature and
10 high humidity resistance, excellent adhesion to a substrate, and
excellent properties in which spray dust of the composition hardly
reduces the adhesion of a film formed thereon to an object to be
coated even when the spray dust has attached to the object to be
coated.
15 [0108] The substrate is not particularly limited but
preferably a substrate for which anticorrosive properties are
required, from viewpoints such as that the effects of the present
invention can be further exhibited.
As such a substrate, preferred are substrates comprising
20 steel, non-ferrous metals (such as zinc, aluminium, and stainless
steel), or the like. Among structures such as ships, land
structures, and bridges comprising these materials, more
preferred ones are ship structures, among which a ballast tank
is more preferred. The ballast tank may be one subjected to
SF-2761 43
electric anticorrosion treatment by installation of an anode made
of zinc, zinc-aluminium, or the like. The electric anticorrosion
treatment is performed at a current density of preferably from
1 to 10 rnA/m2
•
5 [0109] The substrate may be one whose surface has been
treated (for example, blast treatment (ISO 8501-1 Sa2 1/2), a
friction method, an oil and dust removal treatment by degreasing,
and/or the like) as needed in order to remove .,rust, oil and fat,
water, dust, slime, salt, and the like and in order to improve
10 the adhesion of an anticorrosive coating film to be obtained. In
addition, from viewpoints such as anticorrosive properties,
weldability, and shearability of the substrate, the substrate may
be one whose surface when needed has been coated with a coating
material for thin-film formation, such as a conventionally known
15 primary anti-rust coating material (a shop primer), another primer,
or the like and then dried.
[0110] A method for applying the composition of the present
invention on the substrate is not particularly limited, and a
conventionally known method can be unlimitedly used. Preferred
20 is spray coating, from viewpoints such as that it is excellent
in workability, productivity, and the like; coating can be easily
performed even on a substrate with a large area; and the effects
of the present invention can be further exhibited.
When the composition of the present.invention is a
l-:
SF-2761 44
two-component type composition, a main agent component and a
curing agent component may be mixed together immediately before
coating and then spray coating or the like may be performed.
[0111] Conditions for the spray coating can be adjusted as
5 needed, in accordance with the thickness of an anticorrosive
coating film desired to be formed. For airless spraying, coating
conditions may be set to, for example, a primary (air) pressure
ranging from 0.4 to 0.8 Mpa, a secondary (coating material)
pressure ranging from 10 to 26 MPa, and a gun moving speed ranging
10 from 50 to 120 em/second.
[0112] A method for drying and curing the coating film is
not particularly limited. In order to shorten a time for drying
and curing, the coating film may be dried and cured by heating
at a temperature ranging from s,to 60°C. · How.ever, usually, the
15 coating film is dried and cured by allowing the film to stand at
room temperature in the air for from 1 to 14 days.
[0113] A film thickness of the anticorrosive coating film
is not particularly limited as long as the thickness can prevent
the corrosion of a substrate. The film thickness thereof is
20 preferably from 100 to 450 fill\ and more preferably from 250 to 400
J.lm.
In the formation of an anticorrosive coating film having
such a film thickness, single coating may be performed to form
an anticorrosive coating film having a desired thickness, or
SF-2761 45
depending on the anticorrosive properties, double coating (or more
than that, if needed) may be performed to form an anticorrosive
coating film having a desired thickness. Preferably, double
coating is performed to form an anticorrosive coating film having
5 a thickness in the above range, from viewpoints such as that there
can be formed an anticorrosive coating film having excellent
anticorrosive properties.
[0114] In the case of forming the anticorrosive coating film
on a ship structure such as a ballast tank as the substrate, the
10 film is required to have a thickness of 300 ~ or so. The
composition of the present invention has excellent adhesion to
a substrate, specifically, has excellent anti-sagging properties,
thereby facilitating the formation of an anticorrosive coating
film having such a thickness.
15 [0115] <>
A method for preventing corrosion of a substrate according
to the present invention is not particularly limited as long as
the method includes a step of applying the composition of the
invention on a substrate. Preferred is a method for preventing
20 corrosion of a substrate in which the composition of the invention
is applied on a substrate to form a coating film and then the
coating film is dried and cured.
In this method, the substrate, the coating method, and the
like may be the same as those described in the section of the
SF-2761 46
anticorrosive coating film.
[0116] In addition, in the method for preventing corrosion
of a substrate, a conventionally known top coating material such
as an antifouling paint may be applied, dried, and cured on an
5 obtained coating film or anticorrosive coating film depending on
the desired purpose.
[ 011 7] For example, a method for preventing corrosion of a
ballast tank will be performed as follows:
First, the composition of the present invention is spray
10 coated on a floor surface of the ballast tank (a first coating) .
Without or while drying the obtained coating film, the composition
of the invention is spray coated on a wall surface and a ceiling
surface. In this case, the composition which gives a spray dust
through drying, attaches onto the floor surface, and then drying
15 proceeds in a sol vent atmosphere. After the coating film on the
floor surface has been dried, the composition previously used is
spray coated again on the floor surface (a second coating). In
addition, the previously used composition is also similarly spray
coated again on the wall surface and the ceiling surface, resulting
20 in the formation of an anticorrosive coating film having a
thickness of 320 ~-tm or so on the floor surface, the wall surface,
and the ceiling surface.
The above method for preventing corrosion of a ballast tank
is the condition in which the spray dust tends to reduce the
SF-2761 47
adhesion of a film (which is a coating film and a dried coating
film obtained by the second coating) formed thereon to an object
to be coated (which is a spray dust-attached dried coating film
obtained by the first coating), as described above. However, the
5 use of the composition of the present invention hardly causes such
adhesion reduction.
10
On the other hand, the uses of the conventional
anticorrosive coating compositions result in, significant
adhesion reduction.
Examples
[0118] Hereinafter, the present invention will be further
described with reference to Examples. However, the invention is
not limited thereto.
[0119] Regarding anticorrosive coating films formed from
15 compositions obtained in Examples and Comparative Examples below,
tests (1) to (6) as below were conducted. Table 2 shows the
results.
(1) Salt Water Resistance Test
Salt water resistances of the anticorrosive coating films
20 were measured based on JIS K-5600 6-1. Specifically, the
measurements were conducted as follows:
Each of the compositions obtained in the Examples and
Comparative Examples below was spray coated to give a dry film
thickness of about 250 ~ on a steel plate having a size of 150
SF-2761 48
mm x 70 mm x 1.6 mm (thickness) subjected to blasting treatment
(hereinafter referred to also as "test plate") . The obtained test
plates with the coating film were dried in an atmosphere of 23°C
and 50% RH for 7 days to produce test plates with an anticorrosive
5 coating film. Using the test plates with the anticorrosive
coating film, the appearances of the anticorrosive coating films
after having been immersed in 3% salt water at 40°C for 90 days
were visually evaluated according to the fo~lowing criteria:
(Evaluation Criteria)
10 A: There are no changes on blistering, cracking, rust,
peeling, and hue.
B: There are slight defects (changes) on any of blistering,
cracking, rust, peeling, and hue.
C: There are obvious changes on any of blistering, cracking,
15 rust, peeling, and hue.
[ 012 0 l (2) Electric Anticorrosion Test
A zinc anode was connected to each of test plates with an
anticorrosive coating film produced in the same manner as in the
salt water resistance test to give an electric current density
20 of 5 mA/m2 or less, and then the test plates were immersed in 3%
salt water at 40°C for 90 days. After that, the appearances of
the anticorrosive coating films,,were visually evaluated according
to the following criteria:
(Evaluation Criteria)
!<
5
SF-2761 49
A: There are no changes on blistering, cracking, rust,
peeling, and hue.
B: There are slight defects (changes) on any of blistering,
cracking, rust, peeling, and hue.
C: There are obvious changes on any of blistering, cracking,
rust, peeling, and hue.
[ 0 121] (3) Salt Water Spray Test
Based on JIS K-5600 7-1, a solution with a salt water
concentration of 5% was sprayed onto each of test plates with an
10 anticorrosive coating film produced in the same manner as in the
salt water resistance test, continuously for 90 days under a
condition of 35°C. Then, the appearances of the anticorrosive
coating films were visually evaluated according to the following
criteria:
15 (Evaluation Criteria)
20
A: There are no changes on blistering, cracking, rust,
peeling, and hue.
B: There are slight defects (changes) on any of blistering,
cracking, rust, peeling, and hue.
C: There are obvious changes on any of blistering, cracking,
rust, peeling, and hue.
[0122] (4) High Temperature and High Humidity Resistance
Test
High temperature and high humidity r.esistances of
SF-2761 50
anticorrosive coating films were measured based on JIS K-5600 7-2.
Specifically, the measurement was conducted as follows.
Using test plates with an anticorrosive coating film
produced in the same manner as in the salt water resistance test,
5 each of the test plates was kept in a tester with a temperature
of 50°C and a humidity of 95% for 90 days. Then, the appearances
of the anticorrosive coating films were evaluated according to
the following criteria:
(Evaluation Criteria)
10 A: There are no changes on blistering, cracking, rust,
peeling, and hue.
B: There are slight defects (changes) on any of blistering,
cracking, rust, peeling, and hue.
C: There are obvious changes on any of blistering, cracking,
15 rust, peeling, and hue.
[0123] (5) Second Coating Adhesion
Second coating adhesions of anticorrosive coating films
were measured based on JIS K-5400 8.5.3. Specifically, the
following steps were taken.
20 Each of the compositions obtained in the Examples and
Comparative Examples below was spray coated on each test plate
to give a dry film thickness of'about 160 f.Ull, whereby test plates
with a coating film were obtained. The obtained test plates with
the coating film were dried in an atmosphere of 23°C and 50% RH
SF-2761 51
for 1 day. Then, the same composition as that used to form the
coating film was spray coated on each of the obtained test plates
with the dried coating film to give a dry film thickness of about
160 ~m. The resulting test plates were dried in an atmosphere
5 of 23°C and 50% RH for 7 days to obtain test plates with an
anticorrosive coating film having a film thickness of 320 ~m.
[0124] Using the obtained test plates with the anticorrosive
coating film, a peeling state between. the ant~corrosive coating
films (a peeling rate) was evaluated according to the following
10 criteria. The evaluation will be described with reference to F.IG.
1.
An X-shaped incision 2 was formed on a surface of the
anticorrosive coating film 1 of each of the obtained test plates
with the anticorrosive coating film. In this case, an area within
15 a quadrangle formed by connecting four end portions of the two
cuts of the incision 2 was designated as an incision-formed area
3.
After that, an adhesive cellophane tape was stuck onto the
X-shaped incision and one end of the tape was peeled off at an
20 angle close to 90 degrees with respect to the surface of the
anticorrosive coating film to evaluate the peeling state between
the anticorrosive coating films (a peeling rate). Visual
estimation was made on a rate of the anticorrosive coating film
peeled off from the test plate with respect t.o the incision-formed
SF-2761 52
area 3 after peeling off the tape.
(Evaluation Criteria)
A: No peeling is observed.
B: Peeling rate is from 1 to 15% of the entire film.
5 C: Peeling rate is more than 15% of the entire film.
[0125] (6) Adhesion to Spray Dust-Attached Surface
Adhesion of anticorrosive coating films to a spray dust
(dust spray)-attached surface was measured b~sed on JIS K-5400
8. 5. 3. Specifically, the measurements were conducted as follows.
10 Test plates having a size of 150 x 70 x 1. 6 (thickness), mm
were placed in such a manner that surfaces thereof were
substantially vertical with respect to gravity, and then coated
with each of the anticorrosive coating compositions obtained in
the Examples and Comparative Examples below such that an obtained
15 anticorrosive coating film had a film thickness of 160 fUll, thereby
obtaining test plates with the coating film.
A coating film surface of each of the obtained test plates
with the coating film was coated with the same composition as that
used to form the coating film, by spray coating from a height of
20 3 m above the test plate, whereby the composition which gives a
spray dust through drying, was attached to about 95% or more of
a surface, area of the coating film. Immediately after the
attachment of the composition, the obtained test plate with the
composition that gives a spray dust was placed in a plastic box
SF-2761 53
at a height position of 8 em from the bottom of the box, the plastic
box having an opened top part with a size of 60 x 40 x 30 (height)
em, and having 200 g of xylene sprayed on a bottom thereof. Then,
the test plate was dried for 1 day.
5 The condition for attachment of the composition that gives
a spray dust and the condition for drying after the attachment
are those for recreating conditions similar to one example of
conditions for attachment of spray dust that can occur when the
composition of the present invention is used in a place where
10 coating is performed.
[0126] After drying in the above atmosphere for 1 day, the
same composition as that used to form the coating film was again
spray coated on obtained test plates with a dried coating film
to give a dry film thickness of about 160 J.U!l. Then, the test plates
15 were dried in an atmosphere of 23°C and 50% RH for 7 days to obtain
test plates with an anticorrosive coating film having a film
thickness of about 320 ~m.
[0127] After that, an X-shaped incision was formed on
surfaces of the anticorrosive coating films of the obtained test
20 plates with the anticorrosive coating film. Next, an adhesive
cellophane tape was stuck onto the X-shaped incision, and one end
of the tape was peeled off at an angle close to 90 degrees with
respect to the surface of the anticorrosive coating film to
evaluate a peeling state between the anticorrosive coating films
5
10
SF-2761 54
(a peeling rate) according to the following criteria. Numerical
values of the following evaluation criteria were estimated in the
same manner as the above description (5).
(Evaluation Criteria)
[ 012 8]
A: No peeling is observed.
B: Peeling rate is from 1 to 15% of the entire film.
C: Peeling rate is more than 15% of the entire film.
Table 1 below shows materials used in Examples of the
present invention.
[ 012 9] Table 1
-.,:·~o_::·· ·-;·z·
SF-2761 55
(Note 1) "E-028-90X" (product name) : Bisphenol A-type liquid epo~y resin, nonvolatile content
90% (manufactured by Ohtake-Meishin Chemical Co., Ltd.)
(Note 2) "E-834-85X" (product name) : Bisphenol A-type semi-solid epoxy resin, nonvolatile
cotent 85% (manufactured by Ohtake-Meishin Chemical Co., Ltd.)
(Note 3) "NEOPOLYMER E-100": hydroxyl group-containing petroleum resin, softening point 100°C
(manufactured by Nippon Petrochemicals Co. Ltd.)
(Note 4) "NOVARES CA 100": hydroxyl group-containing coumarone resin, softening point 100°C
(manufactured by Rutgers Chemicals AG)
(Note 5) "HILENOL PL-1000S" (product name) : liquid hydrocarbon resin, nonvolatile content 97%
(manufactured by Kolon Chemical Co., Ltd.)
(Note 6) "KBM 403" (product name) : silane coupling agent (manufactured by Shin-Etsu Chemical
Co., Ltd.)
(Note 7) "TALC F-2" (product name) : talc (manufactured by Fuji Talc Industrial Co., Ltd.)
(Note 8) "SUZORITE MICA 200-HK" (product name) : mica (manufactured by Kuraray Trading Co.,
Ltd.)
(Note 9) "POTASSIUM FELDSPAR KM325" '(product name) : potassium feldspar(manufactured by
Commercial Minerals Ltd.)
(Note 10) "TITANIUM WHITE R-5N": titanium white (titanium dioxide, manufactured by Sakai
Chemical Industry Co., Ltd.)
(Note 11) "TAROX LL-XLO": yellow iron oxide (manufactued by Titan Kogyo, Ltd.)
. (Note 12) "ASA T-250F" (product name) : amide wax (manufactuerd by Itoh Oil Chemicals Co., Ltd.) ·
(Note 13) "DISPARLON 6650" (product name): amide wax (manufactured by Kusumoto Chemicals, Ltd.)
(Note 14) "BENTONE SD-2" (product name) : organic bentonite(manufactured by Elementis
Specialties, Inc.)
(Note 15) "AEROSIL R972" (product name) : silicon dioxide (surface-treated product)
(manufactured by Nippon Aerosil Co., Ltd.)
(Note 16) Butyl acetate solution of n-butyl acrylate and iso-butyl acrylate copolymer,
nonvolatile content 50%
(Note 17) Butyl acetate solution of n-butyl acrylate polymer, nonvolatile content 50%
. ~-:r~,., ..... ,. :: ~.-. .:.::.:.:c·::-.
SF-2761 56
(Note 18) Butyl acetate solution of 2-ethylhexyl acrylate polymer, nonvolatile content 50%
(Note 19) "DIANAL BR-106" (product name) : acryl copolymer (manufactured by Mitsubishi Rayon
Co., Ltd.)
(Note 20) "PA-290(A)" (product name) : polyamide amine, active hydrogen equivalent 277,
nonvolatile content 59% (manufactured by Ohtake-Meishin Chemical Co., Ltd.)
(Note 21) "MAD-204(A)" (product name): modified polyamine, active hydrogen equivalent 202,
nonvolatile content 65% (manufactured by Ohtake-Meishin Chemical Co., Ltd.)
(Note 22) "ANCAMINE K-54" (product name): tertiary amine (manufactured by Air Products Japan,
Inc.)
SF-2761 57
[0130] A liquid acrylic resin of (Note 16) was prepared as
follows.
Under a nitrogen gas flow, 200 g of butyl acetate was placed
in a 500 ml four-neck flask and heated to 125°C while stirring.
5 Then, 100 g of n-butyl acrylate, 100 g of iso-butyl acrylate, and
1.6 g of a polymerization initiator:
t-butylperoxy-2-ethylhexanoate (product name: KAYA ESTER 0
manufactured by Kayaku Akzo Co., Ltd.) were placed in a dropping
funnel, and the mixture was dropped in the heated flask over 3
10 hours. During the dropping, temperature inside the flask was
controlled to be a temperature of from 120 to 130°C.
After that, as a post reaction, the resultant was stirred
at 125°C for 4 hours, and then cooled down to 60°C or less to prepare
a butyl acetate solution of an acryl-based copolymer. The
15 obtained solution had a heating residue of 50%. A part of the
obtained solution was taken out and the solvent was evaporated
to obtain the acryl-based copolymer. A weight-average molecular
weight (Mw) of the acryl-based copolymer measured by GPC was about
15,000, and a glass transition temperature thereof measured by
20 DSC was about -36°C.
[0131] A liquid acrylic resin of (Note 17) was prepared as
follows:
The liquid acrylic resin of (Note 17) was prepared in the
same manner as the resin of (Note 16) except that, in the
SF-2761 58
preparation of the resin of (Note 16), 100 g of n-butyl acrylate,
100 g of iso-butyl acrylate, and KAYA ESTER 0 ( 1. 6 g) were replaced
by 200 g of n-butyl acrylate and KAYA ESTER 0 (0. 9 g). The obtained
resin had a weight-average molecular weight (Mw) of about 15000
5 and a glass transition temperature of about -52°C.
[0132] Additionally, the liquid acrylic resin of (Note 18)
was prepared in the same manner as the resin of (Note 16) except
that, in the preparation of the resin of (Note 16), 100 g of n-butyl
acrylate, 100 g of iso-butyl acrylate, and KAYA ESTER 0 (1. 6 g)
10 were replaced by 200 g of 2-ethylhexyl acrylate and, as a
polymerization initiator, 0.1 g of t-butylperoxy benzoate
(product name: KAYA BUTYL B manufactured by Kayaku Akzo Co., Ltd) .
The obtained resin had a weight-average molecular weight (Mw) of
about 11000 and a glass transition temperature of about -72°C.
15 [0133] [Example 1]
As shown in Table 2 below, 19 parts by weight of an epoxy
resin (Note 1) , 10 parts by weight of a petroleum resin (Note 3) ,
4 parts by weight of a liquid petroleum resin (Note 5) , 9. 7 parts
by weight of xylene, 2 parts by weight of butanol, 1 part by weight
20 of 1-methoxy-2-propanol, 1 part by weight of a silane coupling
agent (Note 6), 23 parts by weight of talc (Note 7), 6 parts by
weight of mica (Note 8), 15 parts by weight of potassium feldspar
(Note 9) , 6 parts by weight of titanium white (Note 10), 1. 5 parts
by weight of yellow iron oxide (Note 11), 1. 5 parts by weight of
SF-2761 59
an anti-sagging agent (Note 12), and 0.3 parts by weight of the
liquid acrylic resin (Note 16) were placed in a container. Then,
glass beads were added thereto and these mixing components were
mixed together using a paint shaker. Next, the glass beads were
5 removed and dispersion was conducted at from 56 to 60°C using a
high speed disper, followed by cooling down to 30°C or less to
prepare a main agent component.
[ 0134] In addition, as shown in Table 2 below, 9. 4 parts by
weight of polyamideamine (Note 20) , 4. 7 parts by weight of modified
10 polyamine (Note 21) , 0. 1 parts by weight of tertiary amine (Note
22), and 0. 8 parts by weight of 1-methoxy-2-propanol were mixed
together by a high speed disper to prepare a curing agent
component.
The obtained main agent component and curing agent component
15 were mixed together before coating to prepare a composition.
[0135] [Examples 2 to 8 and Comparative Examples 1 to 4]
Compositions were prepared in the same manner as Example
1 except that components and mixing amounts thereof to be used
in the main agent component and the curing agent component were
20 changed as those shown in Table 2 below.
[0136] Table 2
i
;
SF-2761 60
Example Example Example Example Example Example Example Example
comp. Comp. Camp. Cornp.
Example Example Example Example
1 2 3 4 5 6 7 8 1 2 3 4
Epoxy resin
(Note 1)
19 19 19 19 15.5 0 19 19 19 19 0 19
Epoxy resin
(Note 2)
0 0 0 0 3 20.5 0 0 0 0 22 0
Petroleum resin (Note 3) 10 14 0 0 10 4 10 10 10 10 4 10
Coumarone-indene resin
(Note 4)
0 0 10 10 0 0 0 0 0 0 0 0
Liquid petroleum resin
(Note 5)
4 0 4 4 4 10 4 4 4 4 10 4
Xylene 9.7 9 9.8 9.7 10 8.1 9.7 9.7 10 10 9 9.8
Butanol 2 2 2 2 2 2 2 2 2 2 2 2
1-methoxy-2-propanol 1 1 1 1 1 1 1 1 1 1 1 1
Silane coupling agent
1 1 1 1 1
(Note 6)
1 1 1 1 1 1 1
Talc (Note 7) 23 23 23 23 23 23 23 23 23 23 22 23
Mica (Note 8) 6 6 6 6 6 6 6 6 6 6 6 6
Potassium feldspar
(Note 9)
15 15 15 15 15 15 15 15 15 15 14 15
Titanium white (Note 10) 6 6 6 6 6 6 6 6 6 6 6 6
Yellow iron oxide
(Note 11)
1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Anti sagging agent
1.5 1 1 0 1.5 0 1.5 1.5 1.5 0 1.5 1.5
(Note 12)
Anti-sagging agent
0 0 0 1.5 0 1.5 0 0 0 1.5 0 0
(Note 13)
Organic bentonite
0 0.3 0.3 0 0 0 0 0 0 0 0 0
(Note 14)
Fumed silica (Note 15) 0 0.2 0.2 0 0 0 0 0 0 0 0 0
Liquid acrylic resin
0.3 1 0.2 0.3 0.5 0.4 0 0 0 0 0 0
(Note 16) .
Liquid acrylic resin
0 0 0 0 0 0 0.3 0 0 0 0 0
(Note 17)
Liquid acrylic resin
0 0 0 0 0 0 0 0.3 0 0 0 0
(Note 18)
Solid acrylic resin
0 0 0 0 0 0 0 0 0 0 0 0.2
(Note 19)
Subtotal
100 100 100 100 100 100 100
(parts by weight)
100 100 100 100 100
Polyamideamine 9.4 9.4 9. 4 9.4 9.4 8 9.4 9.4 9. 4 9.4 8 9.4
~-"'''': .. ~~:.:::;;:-:':• ~.x-.c:::: "'-:c--=...:.....:::.:.~:.._.-_:_·:c.
SF-2761 61
(Note 20)
Modified polyamine
4.7 4.7 4.7 4.7 4.7 4 4.7 4.7 4.7 4.7 4 4.7
(Note 21)
Tertiary amine (Note 22) 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.2 0.1
1 methoxy 2-propanol 0.8 0.8 0.8 0.8 0.8 0.3 0.8 0.8 0.8 0.8 0.3 0.8
Subtotal
15 15 15 15 15 {parts by.weight) 12.5 15 15 15 15 12.5 15
Total
115 115 115 115 115 {parts by weight) 112.5 115 115 115 115 112.5 115
Color of coating film Cream Cream cream Cream Cream Cream Cream cream Cream Cream Cream Cream
Salt water resistance A A A A A A A A A A A A
Electric anticorrosion
test
A A A A A A A A A A A A
Salt water spray test A A A A A A. A A A A A A
High temperature and
high humidity A A A A A A A A A A A A
resistance
Second coating adhesion A A A A A A A A A A A A
Adhesion onto dust spray A A A A A A B A c c c c
SF-2761 62
Reference Signs List
[0137] 1: Anticorrosive Coating Film
2: X-shaped incision
3: Incision-formed area
5
SF-2761 63
CLAIMS
1. An anticorrosive coating composition, comprising an
epoxy resin (a), a curing agent (b), an amide wax (c), and a liquid
acrylic polymer (d) including a structural unit derived from an
5 acrylate having an alkyl group of 4 to 18 carbon atoms.
10
2. The anticorrosive coating composition according to
Claim 1, wherein the liquid acrylic polymer (d) includes a
structural unit derived from an acrylate having an alkyl group
of 4 to 18 carbon atoms containing a branched'structure.
3. The anticorrosive coating composition according to
Claim 1 or 2, wherein the liquid acrylic polyme~ (d) includes 'a
structural unit derived from isobutyl acrylate or 2-ethylhexyl
acrylate.
4. The anticorrosive coating composition according to
15 Claim 3, wherein the liquid acryJic polymer (d) includes the
structural unit derived from isobutyl acrylate or 2-ethylhexyl
acrylate in an amount of from 30 to 100% by weight with respect
to the whole of the liquid acrylic polymer (d).
5. The anticorrosive coating composition according to
20 Claim 3 or 4, wherein the liquid acrylic polymer (d) further
includes a structural unit derived from n-butyl acrylate.
6. The anticorrosive coating composition according to any
one of Claims 1 to 5, wherein the liquid acrylic polymer (d) has
a glass transition temperature of 0°C or less.
); ---·-
SF-2761 64
7. The anticorrosive coating composition according to any
one of Claims 1 to 6, wherein the composition comprises the liquid
acrylic polymer (d) in an amount of from 0. 01 to 5 parts by weight
(a nonvolatile content} with respect to 100 parts by weight of
5 a nonvolatile content in the anticorrosive coating composition.
8. The anticorrosive coating composition according to any
one of Claims 1 to 7, wherein the composition comprises the amide
wax (c) in an amount of from 0.05 to 15 parts by weight (a
nonvolatile content} with respect to 100 parts•by weight of a
10 nonvolatile content in the anticorrosive coating composition.
,,,
9. The anticorrosive coating composition according to any
one of Claims 1 to 8, further comprising a silane coupling agent
( e} •
~
10. The anticorrosive coating composition according to any
15 one of Claims 1 to 9, further comprising an extender pigment (f) .
11. The anticorrosive coating composition according to
Claim 10, wherein the extender pigment (f) includes at least a'
flaky pigment (g).
12. An anticorrosive coating film formed from the
20 anticorrosive coating composition according to any one of Claims
1 to 11.
13. A method for preventing corrosion of a substrate,
comprising a step of coating the substrate with the anticorrosive
coating composition according to any_~n_e__(lf Cla_~IT\_8__}: to ~~ ·-~