U.S. patent application number 10/151825 was filed with the patent office on 2003-06-05 for flow-and-leveling agents for waterborne coatings.
This patent application is currently assigned to KUSUMOTO CHEMICALS, LTD.. Invention is credited to Horiguchi, Takashi, Kawahito, Shigehiro, Kawase, Masafumi.
Application Number | 20030105228 10/151825 |
Document ID | / |
Family ID | 19020484 |
Filed Date | 2003-06-05 |
United States Patent
Application |
20030105228 |
Kind Code |
A1 |
Kawase, Masafumi ; et
al. |
June 5, 2003 |
Flow-and-leveling agents for waterborne coatings
Abstract
Provided is a flow-and-leveling agent for waterborne coatings
which provides the coated surface with a flow-and-leveling property
by blending into waterborne coatings taking a serious view of
finishing and which improves coating defects such as ruptures and
craters to contribute to a rise in the appearance of the coating
film. The above flow-and-leveling agent is an acryl base copolymer
containing a trimethylsilyl group in a proportion of 2 to 64% by
weight and has a number average molecular weight of 500 to
30000.
Inventors: |
Kawase, Masafumi;
(Saitama-ken, JP) ; Horiguchi, Takashi;
(Saitama-ken, JP) ; Kawahito, Shigehiro;
(Saitama-ken, JP) |
Correspondence
Address: |
Leonard W. Sherman
Sherman & Shalloway
413 N. Washington Street
Alexandria
VA
22314
US
|
Assignee: |
KUSUMOTO CHEMICALS, LTD.
|
Family ID: |
19020484 |
Appl. No.: |
10/151825 |
Filed: |
May 22, 2002 |
Current U.S.
Class: |
525/100 |
Current CPC
Class: |
C08F 230/08 20130101;
C09D 7/47 20180101; C08F 8/42 20130101; C08F 8/42 20130101; C08F
220/00 20130101 |
Class at
Publication: |
525/100 |
International
Class: |
C08F 008/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 14, 2001 |
JP |
2001-179999 |
Claims
1. A flow-and-leveling agent for a water base coating comprising a
trimethylsilyl group-containing copolymer obtained by
copolymerizing a reactive monomer (A) having a trimethylsilyl group
represented by a structural formula:--Si(CH.sub.3).sub.3in a
molecular structure and/or a reactive monomer (B) having a
trimethylsilyl group in the form of a tris(trimethylsiloxy)silyl
group represented by a structural
formula:--Si[OSi(CH.sub.3)).sub.3].sub.3in a molecular structure
with a (meth)acrylic acid ester (C) represented by a formula:
6[wherein R.sub.1 represents a hydrogen atom or methyl, and R.sub.2
represents an alkyl group having 1 to 12 carbon atoms] and/or a
(meth)acrylic acid ester (d) represented by a formula: 7[wherein
R.sub.3 represents a hydrogen atom or methyl; R.sub.4 represents an
alkyl group having 1 to 18 carbon atoms; and n represents an
integer of 2, 3 or 4] and acrylamide (E) represented by a formula:
8[wherein R.sub.5 and R.sub.6 each represent a hydrogen atom or an
alkyl group having 1 to 8 carbon atoms] and/or a (meth)acrylc acid
ester (F) represented by a formula: 9[wherein R.sub.7 represents a
hydrogen atom or methyl; R.sub.8 represents a hydrogen atom or an
alkyl group having 1 to 18 carbon atoms; m represents an integer of
2 to 100, and n represents an integer of 2, 3 or 4; and
--(C.sub.nH.sub.2nO).sub.m-- - means that 2 to 100 units of only
one kind of a glycol unit out of three kinds of the glycol units in
which n is 2, 3 and 4 are present and that total 2 to 100 units of
two or three kinds of the glycol units out of three kinds of the
above glycol units are present] and/or a (meth)acrylic acid (G)
represented by a formula: 10[wherein R.sub.9 represents a hydrogen
atom or methyl], wherein the above trimethylsilyl group-containing
copolymer contains a trimethylsilyl group originating in the
monomer (A) and/or the monomer (B) in a proportion of 2 to 64% by
weight; it contains a copolymerization unit originating in the
(meth)acrylic acid ester (C) and/or the (meth)acrylic acid ester
(D) in a proportion of 2% by weight or more; it contains a
copolymerization unit originating in the acrylamide (E) and/or the
(meth)acrylic acid ester (F) and/or the (meth)acrylic acid (G) in a
proportion of 5% by weight or more; and it has a number average
molecular weight of 500 to 30000.
2. A flow-and-leveling agent for a water base coating comprising a
trimethylsilyl group-containing copolymer obtained by reacting a
copolymer of a multifunctional monomer into which a trimethylsilyl
group or a tris(trimethylsiloxy)silyl group can be introduced, the
(meth)acryhc acid ester (C) and/or the (meth)acrylic acid ester (D)
described in the above item (1) and the acrylamide (E) and/or the
(meth)acrylic acid ester (F) and/or the (meth)acrylic acid (G)
described in the above item (1) with a trimethylsilyl
group-containing compound and/or a tris(trimethylsiloxy)silyl
group-containing compound, wherein the above trimethylsilyl
group-containing copolymer contains a trimethylsilyl group in a
proportion of 2 to 64% by weight; it contains a copolymerization
unit originating in the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) in a proportion of 2% by weight or
more; it contains a copolymerization unit originating in the
acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or the
(meth)acrylic acid (G) in a proportion of 5% by weight or more; and
it has a number average molecular weight of 500 to 30000.
3. A flow-and-leveling agent for a water base coating comprising a
trimethylsilyl group-containing copolymer obtained by
copolymerizing the monomer (A) and/or the monomer (B) described in
the above item (1), the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) described in the above item (1) and
the acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or
the (meth)acrylic acid (G) described in the above item (1) with a
reactive monomer (H) capable of being copolymerized with them,
wherein the above copolymer contains a trimethylsilyl group
originating in the monomer (A) and/or the monomer (B) in a
proportion of 2 to 64% by weight; it contains a copolymerization
unit originating in the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) in a proportion of 2% by weight or
more; it contains a copolymerization unit originating in the
acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or the
(meth)acrylic acid (G) in a proportion of 5% by weight or more; it
contains a copolymerization unit originating in the monomer (H) in
a proportion of not exceeding 50% by weight; and it has a number
average molecular weight of 500 to 30000.
4. A flow-and-leveling agent for a water base coating comprising a
trimethylsilyl group-containing copolymer obtained by reacting a
copolymer of the multifunctional monomer described in the above
item (2), the (meth)acrylic acid ester (C) and/or the (meth)acrylic
acid ester (D) described in the above item (1), the acrylamide (E)
and/or the (meth)acrylic acid ester (F) and/or the (meth)acrylic
acid (G) described in the above item (1) and a reactive monomer (H)
capable of being copolymerized with them with a trimethylsilyl
group-containing compound and/or a tris(trimethylsiloxy)silyl
group-containing compound, wherein the above trimethylsilyl
group-containing copolymer contains a trimethylsilyl group in a
proportion of 2 to 64% by weight; it contains a copolymerization
unit originating in the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) in a proportion of 2% by weight or
more; it contains a copolymerization unit originating in the
acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or the
(meth)acrylic acid (G) in a proportion of 5% by weight or more; it
contains a copolymerization unit originating in the monomer (H) in
a proportion of not exceeding 50% by weight; and it has a number
average molecular weight of 500 to 30000.
5. The flow-and-leveling agent for a water base coating as
described in any of claims 1 to 4, wherein the monomer (A) and/or
the monomer (B) are selected from the group consisting of
3-methacryloxypropyltrimethylsilane- ,
3-methacryloxypropyltris(trimethylsiloxy)silane, and
vinyltris(trimethylsiloxy)silane,
6. The flow-and-leveling agent for a water base coating as
described in any of claims 1 to 4, wherein the trimethylsilyl
group-containing compound and/or the tris(trimethylsiloxy)silyl
group-containing compound are selected from the group consisting of
trimethylchlorosilane, hexamethyldisilazane,
tris(trimethylsiloxy)hydrosilane,
3-aminopropyltris(trimethylsiloxy)silane and
3-mercaptopropyltris(trimeth- ylsiloxy)silane.
7. The flow-and-leveling agent for a water base coating as
described in any of claims 1 to 4, wherein the (meth)acrylic acid
ester (C) is selected from the group consisting of methyl
(meth)acrylate, ethyl (meth)acrylate, normal propyl (meth)acrylate,
isopropyl (meth)acrylate, normal butyl (meth)acrylate, isobutyl
(meth)acrylate, tertiary butyl (meth)acrylate, normal octyl
(meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl
(meth)acrylate and lauryl (meth)acrylate.
8. The flow-and-leveling agent for a water base coating as
described in any of claims 1 to 4, wherein the (meth)acrylic acid
ester (D) is selected from the group consisting of 2-methoxyethyl
(meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl
(meth)acrylate, 2-octoxyethyl (meth)acrylate, 2-lauroxyethyl
(meth)acrylate, 2-stearoxyethyl (meth)acrylate, 3-methoxybutyl
(meth)acrylate and 4-methoxybutyl (meth)acrylate.
9. The flow-and-leveling agent for a water base coating as
described in any of claims 1 to 4, wherein the acrylamide (E) is
selected from the group consisting of acrylamide,
N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide,
N-normal butylacrylamide, N-tertiary butylacrylamide,
N-2-ethylhexylacrylamide, N,N-dimethylacrylamide,
N,N-diethylacrylamide and diacetoneacrylamide.
10. The flow-and-leveling agent for a water base coating as
described in any of claims 1 to 4, wherein the (meth)acrylic acid
ester (F) is selected from the group consisting of ethylcarbitol
(meth)acrylate, methoxypolyethylene glycol (meth)acrylate,
methoxypolypropylene glycol (meth)acrylate,
methoxypoly(ethylene-propylene) glycol (meth)acrylate,
methoxypoly(ethylene-tetramethylene) glycol (meth)acrylate,
butoxypoly(ethylene-propylene) glycol (meth)acrylate,
octoxypoly(ethylene-propylene) glycol (meth)acrylate,
lauroxypolyethylene glycol (meth)acrylate and
lauroxypoly(ethylene-propylene) glycol (meth)acrylate.
11. The flow-and-leveling agent for a water base coating as
described in claim 2 or 4, wherein the multifunctional monomer is
selected from the group consisting of (meth)acrylic acid,
2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate,
2-isocyanatoethyl (meth)acrylate, those in which R.sub.8 is a
hydrogen atom in the formula representing the (meth)acrylic acid
ester (F), allyl glycidyl ether, 2-hydroxyethyl vinyl ether and
4-hydroxybutyl vinyl ether.
12. The flow-and-leveling agent for a water base coating as
described in claim 3 or 4, wherein the monomer (H) is selected from
the group consisting of (meth)acrylates other than (C), (D) and (F)
described above such as tridecyl (meth)acrylate, myristyl
(meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate,
behenyl (meth)acrylate, cyclohexyl (meth)acrylate, isobonyl
(meth)acrylate and nonylphenoxypolyethylene glycol (meth)acrylate;
aromatic hydrocarbon base vinyl compounds such as styrene,
.alpha.-methylstyrene, chlorostyrene and vinyltoluene; vinyl esters
or allyl compounds such as vinyl acetate, vinyl propionate and
diallyl phthalate; vinyl ethers such as ethyl vinyl ether, normal
propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl
ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal
octyl vinyl ether, 2-ethylhexyl vinyl ether, methyl vinyl ether and
cyclohexyl vinyl ether; vinyl chloride; vinylidene chloride;
chloroprene; propylene; butadiene; isoprene; and
fluoroolefinmaleimide.
Description
TECHNICAL FIELD TO WHICH THE INVENTION BELONGS
[0001] The present invention relates to novel acryl silicone base
flow-and-leveling agents for waterborne coatings which can provide
the coating surfaces with a flow-and-leveling property by adding
them to waterborne coatings in small amounts.
PRIOR ART
[0002] In recent years, it has been tried to use waterborne
coatings in place of solventborne coatings from the viewpoints of
resource savings and measures for environmental pollution. For
example, it is investigated to use waterborne coatings for primer
coatings, base coatings and top coatings for automobiles. This
allows flow-and-leveling agents for waterborne coatings having
higher functions to be required. In order to meet this requirement,
acryl base polymers, modified silicone oils and the like have so
far been used as flow-and-leveling agents.
[0003] The Problems to be Solved by the Invention
[0004] However, a satisfactory flow-and-leveling property and an
improvement in coating defects are not necessarily achieved with
these conventional techniques in the fields requiring a high
appearance such as uses for automobiles which have been researched
in recent years, and if large amounts of flow-and-leveling agents
are added in order to obtain a good appearance, adverse effects are
exerted on a layer-to-layer adhesive property in recoating or
adverse effects such as roughening the surfaces of the recoated
films and separating of the flow-and-leveling agents in coatings
are often observed.
[0005] Accordingly, an object of the present invention is to
provide flow-and-leveling agents capable of being utilized for uses
requiring a high appearance which has not been obtained with
conventional flow-and-leveling agents for waterborne coatings.
[0006] Means for Solving the Problems
[0007] Various investigations repeated by the present inventors
have resulted in finding that flow-and-leveling agents of (1), (2),
(3) and (4) described below make it possible to provide the coating
films of the waterborne coatings with such a good flow-and-leveling
property as has so far never been obtained and that adverse effects
are not exerted on the recoating property.
[0008] (1) A flow-and-leveling agent for a water base coating
comprising a trimethylsilyl group-containing copolymer obtained by
copolymerizing a reactive monomer (A) having a trimethylsilyl group
represented by a structural formula:
--Si(CH.sub.3).sub.3
[0009] in a molecular structure and/or a reactive monomer (B)
having a trimethylsilyl group in the form of a
tris(trimethylsiloxy)silyl group represented by a structural
formula:
--Si[OSi(CH.sub.3).sub.3].sub.3
[0010] in a molecular structure with a (meth)acrylic acid ester (C)
represented by a formula: 1
[0011] [wherein R.sub.1 represents a hydrogen atom or methyl, and
R.sub.2 represents an alkyl group having 1 to 12 carbon atoms]
and/or a (meth)acrylic acid ester (D) represented by a formula:
2
[0012] [wherein R.sub.3 represents a hydrogen atom or methyl;
R.sub.4 represents an alkyl group having 1 to 18 carbon atoms; and
n represents an integer of 2, 3 or 4] and acrylamide (E)
represented by a formula; 3
[0013] [wherein R.sub.5 and R.sub.6 each represent a hydrogen atom
or an alkyl group having 1 to 8 carbon atoms] and/or a
(meth)acrylic acid ester (F) represented by a formula: 4
[0014] [wherein R.sub.7 represents a hydrogen atom or methyl;
R.sub.8 represents a hydrogen atom or an alkyl group having 1 to 18
carbon atoms; m represents an integer of 2 to 100, and n represents
an integer of 2, 3 or 4; and --(C.sub.nH.sub.2nO).sub.m-- means
that 2 to 100 units of only one kind of a glycol unit out of three
kinds of the glycol units in which n is 2, 3 and 4 are present and
that total 2 to 100 units of two or three kinds of the glycol units
out of three kinds of the above glycol units are present] and/or a
(meth)acrylic acid (G) represented by a formula: 5
[0015] [wherein R.sub.9 represents a hydrogen atom or methyl],
wherein the above trimethylsilyl group-containing copolymer
contains a trimethylsilyl group originating in the monomer (A)
and/or the monomer (B) in a proportion of 2 to 64% by weight,
preferably 5 to 40% by weight; it contains a copolymerization unit
originating in the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) in a proportion of 2% by weight or
more, preferably 5% by weight or more; it contains a
copolymerization unit originating in the acrylamide (E) and/or the
(meth)acrylic acid ester (F) and/or the (meth)acrylic acid (G) in a
proportion of 5% by weight or more, preferably 10% by weight or
more; and it has a number average molecular weight of 500 to 30000,
preferably 1000 to 10000.
[0016] (2) A flow-and-leveling agent for a water base coating
comprising a trimethylsilyl group-containing copolymer obtained by
reacting a copolymer of a multifunctional monomer into which a
trimethylsilyl group or a tris(trimethylsiloxy)silyl group can be
introduced, the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) described in the above item (1) and
the acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or
the (meth)acrylic acid (G) described in the above item (1) with a
trimethylsilyl group-containing compound and/or a
tris(trimethylsiloxy)silyl group-containing compound, wherein the
above trimethylsilyl group-containing copolymer contains a
trimethylsilyl group in a proportion of 2 to 64% by weight,
preferably 5 to 40% by weight; it contains a copolymerization unit
originating in the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) in a proportion of 2% by weight or
more, preferably 5% by weight or more; it contains a
copolymerization unit originating in the acrylamide (E) and/or the
(meth)acrylic acid ester (F) and/or the (meth)acrylic acid (G) in a
proportion of 5% by weight or more, preferably 10% by weight or
more; and it has a number average molecular weight of 500 to 30000,
preferably 1000 to 10000.
[0017] (3) A flow-and-leveling agent for a water base coating
comprising a trimethylsilyl group-containing copolymer obtained by
copolymerizing the monomer (A) and/or the monomer (B) described in
the above item (1), the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) described in the above item (1), the
acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or the
(meth)acryhc acid (G) described in the above item (1) with a
reactive monomer (H) capable of being copolymerized with them,
wherein the above copolymer contains a trimethylsilyl group
originating in the monomer (A) and/or the monomer (B) in a
proportion of 2 to 64% by weight, preferably 5 to 40% by weight; it
contains a copolymerization unit originating in the (meth)acrylic
acid ester (C) and/or the (meth)acrylic acid ester (D) in a
proportion of 2% by weight or more, preferably 5% by weight or
more; it contains a copolymerization unit originating in the
acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or the
(meth)acrylic acid (G) in a proportion of 5% by weight or more,
preferably 10% by weight or more; it contains a copolymerization
unit originating in the monomer (H) in a proportion of not
exceeding 50% by weight; and it has a number average molecular
weight of 500 to 30000, preferably 1000 to 10000.
[0018] (4) A flow-and-leveling agent for a water base coating
comprising a trimethylsilyl group-containing copolymer obtained by
reacting a copolymer of the multifunctional monomer described in
the above item (2), the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) described in the above item (1), the
acrylamide (E) and/or the (meth)acrylic acid ester (F) and/or the
(meth)acrylic acid (G) described in the above item (1) and a
reactive monomer (H) capable of being copolymerized with them with
a trimethylsilyl group-containing compound and/or a
tris(trimethylsiloxy)silyl group-containing compound, wherein the
above trimethylsilyl group-containing copolymer contains a
trimethylsilyl group in a proportion of 2 to 64% by weight,
preferably 5 to 40% by weight; it contains a copolymerization unit
originating in the (meth)acrylic acid ester (C) and/or the
(meth)acrylic acid ester (D) in a proportion of 2% by weight or
more, preferably 5% by weight or more; it contains a
copolymerization unit originating in the acrylamide (E) and/or the
(meth)acrylic acid ester (F) and/or the (meth)acrylic acid (G) in a
proportion of 5% by weight or more, preferably 10% by weight or
more; it contains a copolymerization unit originating in the
monomer (H) in a proportion of not exceeding 50% by weight; and it
has a number average molecular weight of 500 to 30000, preferably
1000 to 10000.
[0019] In the copolymer in which a trimethylsilyl group originating
in the monomer (A) and/or the monomer (B) has a content of smaller
than 2% by weight, a satisfactory effect as the flow-and-leveling
agent for a water base coating is not observed. On the other hand,
if it is more than 64% by weight, a phenomenon close to rough
surface which is observed in silicone base flow-and-leveling agents
is more likely to appear.
[0020] The (meth)acrylic acid ester (C) and/or the (meth)acrylic
acid ester (D) are copolymerized in order to provide an effect of
obtaining a good flow-and-leveling property, and the satisfactory
flow-and-leveling property can not be obtained with monomers other
than them. When both of (C) and (D) are used, a proportion of the
amounts thereof is optional, and they are preferably used so that a
trimethylsilyl group is contained in the trimethylsilyl
group-containing copolymer in a proportion of 2 to 64% by weight,
preferably 5 to 40% by weight; the copolymerization unit
originating in (E) and/or (F) and/or (G) accounts for 5% by weight
or more, preferably 10% by weight or more altogether; and the
copolymerization unit originating in both of (C) and (D) accounts
for 2% by weight or more, preferably 5% by weight or more
altogether.
[0021] The acrylamide (E) and/or the (meth)acrylic acid ester (F)
(specifically, polyalkylene glycol ester) and/or the (meth)acrylic
acid (G) are copolymerized in order to provide the acryl silicone
polymer with hydrophilicity to make it possible to disperse the
polymer homogeneously in the water base coating. When each of (E),
(F) and (G) is used, a proportion of the amounts thereof is
optional, and they are preferably used so that a trimethylsilyl
group is contained in the trimethylsilyl group-containing copolymer
in a proportion of 2 to 64% by weight, preferably 5 to 40% by
weight; the copolymerization unit originating in (C) and/or (D)
accounts for 2% by weight or more, preferably 5% by weight or more
altogether; and the copolymerization unit originating in each (E),
(F) and (G) accounts for 5% by weight or more, preferably 10% by
weight or more altogether.
[0022] The multifunctional monomer into which a trimethylsilyl
group or a tris(trimethylsiloxy)silyl group can be introduced is
copolymerized in advance with (C) and/or (D) and (E) and/or (F)
and/or (G), a trimethylsilyl group-containing compound and/or a
tris(trimethylsiloxy)si- lyl group-containing compound can be
introduced into the resulting copolymer by addition reaction or
condensation reaction. Also in this case, an effect of providing
the coated surface with a good flow-and-leveling property is
observed if a trimethylsilyl group is contained in the
trimethylsilyl group-containing copolymer in a proportion of 2 to
64% by weight, preferably 5 to 40% by weight; the copolymerization
unit originating in (C) and/or (D) is contained in a proportion of
2% by weight or more, preferably 5% by weight or more; and the
copolymerization unit originating in each (E), (F) and (G) is
contained in a proportion of 5% by weight or more, preferably 10%
by weight or more.
[0023] An effect of providing the coated surface with a good
flow-and-leveling property is observed as well in the acryl
silicone copolymer containing a copolymerization unit originating
in the other reactive monomer (H) in a proportion falling in a
range of not exceeding 50% by weight based on the copolymer if a
trimethylsilyl group is contained in the synthesized copolymer in a
proportion of 2 to 64% by weight, preferably 5 to 40% by weight;
the copolymerization unit originating in (C) and/or (D) is
contained in a proportion of 2% by weight or more, preferably 5% by
weight or more; and the copolymerization unit originating in (E)
and/or (F) and/or (C) is contained in a proportion of 5% by weight
or more, preferably 10% by weight or more.
[0024] Even if the copolymerization unit originating in the other
reactive monomer (H) is contained in a proportion falling in a
range of not exceeding 50% by weight based on the copolymer, an
effect of providing the coated surface with a good
flow-and-leveling property is observed as well in the acryl
silicone copolymer obtained by introducing a trimethylsilyl
group-containing compound and/or a tris(trimethylsiloxy)si- lyl
group-containing compound into the copolymer of the multifunctional
monomer into which a trimethylsilyl group or a
tris(trimethylsiloxy)silyl group can be introduced, (C) and/or (D),
(E) and/or (F) and/or (G) and the reactive monomer (H)
copolymerizable with them by addition reaction or condensation
reaction, if a trimethylsilyl group is contained in a proportion of
2 to 64% by weight, preferably 5 to 40% by weight; the
copolymerization unit originating in (C) and/or (D) is contained in
a proportion of 2% by weight or more, preferably 5% by weight or
more; and the copolymerization unit originating in (E) and/or (F)
and/or (G) is contained in a proportion of 5% by weight or more,
preferably 10% by weight or more.
[0025] If the copolymer has a number average molecular weight of
smaller than 500, the above copolymer blended into the coating does
not provide a sufficiently high ability to spread on a coated
surface in coating, so that the satisfactory flow-and-leveling
property can not be obtained. On the other hand, if the copolymer
has a number average molecular weight of larger than 30000, the
copolymer can not evenly be dispersed in the water base coating and
is more likely to cause coating defects such as cissing.
[0026] The examples of the reactive monomer (A) having a
trimethylsilyl group and the reactive monomer (B) having a
trimethylsilyl group in the form of a tris(trimethylsiloxy)silyl
group include 3-methacryloxypropyltrimethylsilane,
3-methacryloxypropyltris(trimethylsi- loxy)silane and
vinyltris(trimethylsiloxy)silane.
[0027] The examples of the trimethylsilyl group-containing compound
and the tris(trimethylsiloxy)silyl group-containing compound
include trimethylchlorosilane, hexamethyldisilazane,
tris(trimethylsiloxy)hydrosi- lane,
3-aminopropyltris(trimethylsiloxy)silane and
3-mercaptopropyltris(tr- imethylsiloxy) silane.
[0028] The (meth)acrylic acid ester (C) includes, for example,
methyl (meth)acrylate, ethyl (meth)acrylate, normal propyl
(meth)acrylate, isopropyl (meth)acrylate, normal butyl
(meth)acrylate, isobutyl (meth)acrylate, tertiary butyl
(meth)acrylate, normal octyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, isononyl (meth)acrylate and lauryl
(meth)acrylate.
[0029] The (meth)acrylic acid ester (D) includes, for example,
2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,
2-butoxyethyl (meth)acrylate, 2-octoxyethyl (meth)acrylate,
2-lauroxyethyl (meth)acrylate, 2-stearoxyethyl (meth)acrylate,
3-methoxybutyl (meth)acrylate and 4-methoxybutyl
(meth)acrylate.
[0030] The acrylamide (E) includes, for example, acrylamide,
N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide,
N-normal butylacrylamide, N-tertiary butylacrylamide,
N-2-ethylhexylacrylamide, N,N-dimethylacrylamide,
N,N-diethylacrylamide and diacetoneacrylamide.
[0031] The (meth)acrylic acid ester (F) includes, for example,
ethylcarbitol(meth)acrylate, methoxypolyethylene glycol
(meth)acrylate [the number (m) of the ethylene glycol units is 2 to
100], methoxypolypropylene glycol (meth)acrylate [the number (m) of
the propylene glycol units is 2 to 100],
methoxypoly(ethylene-propylene) glycol (meth)acrylate [the total
number (m) of the number of the ethylene glycol units and the
number of the propylene glycol units is 2 to 100],
methoxypoly(ethylene-tetramethylene) glycol (meth)acrylate [the
total number (m) of the number of the ethylene glycol units and the
number of the tetramethylene glycol units is 2 to 100],
butoxypoly(ethylene-propyle- ne) glycol(meth) acrylate [the total
number (m) of the number of the ethylene glycol units and the
number of the propylene glycol units is 2 to 100],
octoxypoly(ethylene-propylene) glycol (meth)acrylate [the total
number (m) of the number of the ethylene glycol units and the
number of the propylene glycol units is 2 to 100],
lauroxypolyethylene glycol (meth)acrylate [the number (m) of the
ethylene glycol units is 2 to 100] and
lauroxypoly(ethylene-propylene) glycol (meth)acrylate [the total
number (m) of the number of the ethylene glycol units and the
number of the propylene glycol units is 2 to 100].
[0032] The examples of the multifunctional monomer into which a
trimethylsilyl group or a tris(trimethylsiloxy)silyl group can be
introduced include, for example, (meth)acrylic acid, 2-hydroxyethyl
(meth)acrylate, glycidyl (meth)acrylate, 2-isocyanatoethyl
(meth)acrylate, those in which R.sub.8 is a hydrogen atom in the
formula (F), allyl glycidyl ether, 2-hydroxyethyl vinyl ether and
4-hydroxybutyl vinyl ether.
[0033] The monomer (H) includes, for example, (meth)acrylates other
than (C), (D) and (F) described above such as tridecyl
(meth)acrylate, myristyl (meth)acrylate, hexadecyl (meth)acrylate,
stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl
(meth)acrylate, isobonyl (meth)acrylate and
nonylphenoxypolyethylene glycol (meth)acrylate; aromatic
hydrocarbon base vinyl compounds such as styrene,
.alpha.-methylstyrene, chlorostyrene and vinyltoluene; vinyl esters
or allyl compounds such as vinyl acetate, vinyl propionate and
diallyl phthalate; vinyl ethers such as ethyl vinyl ether, normal
propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl
ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal
octyl vinyl ether, 2-ethylhexyl vinyl ether, methyl vinyl ether and
cyclohexyl vinyl ether; vinyl chloride; vinylidene chloride;
chloroprene; propylene; butadiene; isoprene; and
fluoroolefinmaleimide.
[0034] A method for synthesizing the copolymer of the present
invention includes an emulsion polymerization method, a suspension
polymerization method, a solution polymerization method and a bulk
polymerization method. Conventional azo base polymerization
initiators and peroxides are used as an initiator for carrying out
the polymerization.
[0035] Capable of being used as a method for introducing a
trimethylsilyl group into the copolymer is a method in which
polymerization reaction is carried out and then reactive silane
having a trimethylsilyl group is added or condensed.
[0036] The present invention relates to the functions of the
copolymer and therefore shall by no means be restricted by the
synthetic process of the copolymer.
[0037] Addition of the flow-and-leveling agent for a water base
coating according to the present invention to coatings to which
high appearance is required, for example, waterborne basecoatings
for automobiles, waterborne primer coatings for automobiles,
waterborne monocoat for automobiles and waterborne coatings for
high grade furnitures makes it possible to provide the coated
surface with a sufficiently high flow-and-leveling property in
applying these coatings and prevent cissing and craters from being
produced.
[0038] Timing for adding the flow-and-leveling agent for a water
base coating according to the present invention is optional, and it
can be added in the course of grinding a pigment or after producing
the coating.
[0039] An addition amount of the flow-and-leveling agent for a
water base coating according to the present invention is varied
depending on the kind of the resins for the coating and the blend
compositions of the pigments and is usually 0.01 to 5% by weight,
preferably 0.05 to 2% by weight based on the coating vehicles in
terms of the solid matters. If the addition amount is smaller than
0.01% by weight, the coated surface can not be provided with a
sufficiently high flow-and-leveling property. On the other hand, if
it is more than 5% by weight, various adverse effects are more
likely to be exerted in recoating.
[0040] Effects of the Invention
[0041] The flow-and-leveling agent for a water base coating
according to the present invention is a novel acryl silicone base
copolymer and makes it possible to provide such a good
flow-and-leveling property as has so far never been obtained.
EXAMPLES
[0042] Next, the present invention shall be explained in further
details with reference to examples, but the present invention shall
not be restricted to these examples.
[0043] "Parts" and "%" in the following mean "parts by weight" and
"% by weight" respectively.
Production Example 1
[0044] A reactor of 1000 ml equipped with a stirrer, a reflux
condenser, a dropping funnel, a thermometer and a nitrogen
gas-introducing port was charged with 150 parts of propylene glycol
monopropyl ether (hereinafter abbreviated as PFG) and heated to
120.degree. C. while introducing nitrogen gas. Then, the following
solution (a-1) was dropwise added at a constant rate through the
dropping funnel in 2 hours.
1 Solution (a-1) Tertiary butyl acrylate 75 parts [(meth)acrylic
acid ester (C)] Methoxypolyethylene glycol methacrylate 75 parts
(the number (m) of the ethylene glycol units is 23) [(meth)acrylic
acid ester (F)] 3-Methacryloxypropyltris(trimethylsiloxy)- 50 parts
silane [monomer (B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate
7.5 parts
[0045] After one hour since finishing dropwise adding the solution
(a-1), 2 parts of t-butyl peroxy-2-ethylhexanoate was added, and
the reaction was further continued for 2 hours while keeping a
temperature of 120.degree. C. After finishing the reaction, the
reaction solution was adjusted to a concentration of 30% by PFG to
obtain an additive [A-1]. The synthesized acryl silicone base
copolymer had a number average molecular weight of 5000 in terms of
polystyrene, which was determined by gel permeation
chromatography.
Production Example 2
[0046] An additive [A-2] was obtained in the same manner as in
Production Example 1, except that the following solution (a-2) was
substituted for the solution (a-1) used in Production Example
1.
2 Solution (a-2) Isobutyl acrylate 75 parts [(meth)acrylic acid
ester (C)] N-Tertiary butylacrylamide 75 parts [acrylamide (E)]
3-Methacryloxypropyltris(trimethylsiloxy)- 50 parts silane [monomer
(B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate 10 parts
[0047] The synthesized acryl silicone base copolymer had a number
average molecular weight of 1500 in terms of polystyrene, which was
determined by gel permeation chromatography.
Production Example 3
[0048] An additive [A-3] was obtained in the same manner as in
Production Example 1, except that the following solution (a-3) was
substituted for the solution (a-1) used in Production Example
1.
3 Solution (a-3) 2-Methoxyethyl acrylate 40 parts [(meth)acrylic
acid ester (D)] N,N-Dimethylacrylamide [acrylamide (E)] 30 parts
Isononyl acrylate 40 parts [(meth)acrylic acid ester (C)] Tertiary
butyl vinyl ether [monomer (H)] 40 parts
3-Methacryloxypropyltris(trimethylsiloxy)- 50 parts silane [monomer
(B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate 10 parts
[0049] The synthesized vinyl silicone base copolymer had a number
average molecular weight of 2500 in terms of polystyrene, which was
determined by gel permeation chromatography.
Production Example 4
[0050] An additive [A-4] was obtained in the same manner as in
Production Example 1, except that the following solution (a-4) was
substituted for the solution (a-1) used in Production Example
1.
4 Solution (a-4) N,N-Dimethylacrylamide [acrylamide (E)] 100 parts
2-Butoxyethyl acrylate 100 parts [(meth)acrylic acid ester (D)]
3-Methacryloxypropyltris(trimethylsiloxy)- 100 parts silane
[monomer (B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate 15
parts
[0051] The synthesized acryl silicone base copolymer had a number
average molecular weight of 2000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Production Example 5
[0052] An additive [A-5] was obtained in the same manner as in
Production Example 1, except that the following solution (a-5) was
substituted for the solution (a-1) used in Production Example
1.
5 Solution (a-5) Lauroxypolyethylene glycol acrylate 80 parts (the
number (m) of the ethylene glycol units is 10) [(meth)acrylic acid
ester (F)] Tertiary butyl acrylate 80 parts [(meth)acrylic acid
ester (C)] Acrylic acid [(meth)acrylic acid (G)] 80 parts
3-Methacryloxypropyltrimethylsilane 80 parts [monomer (A)] PFG 150
parts t-Butyl peroxy-2-ethylhexanoate 3.2 parts
[0053] The synthesized acryl silicone base copolymer had a number
average molecular weight of 10000 in terms of polystyrene, which
was determined by gel permeation chromatography.
Production Example 6
[0054] An additive [A-6] was obtained in the same manner as in
Production Example 1, except that the following solution (a-6) was
substituted for the solution (a-1) used in Production Example
1.
6 Solution (a-6) Ethyl acrylate 140 parts [(meth)acrylic acid ester
(C)] N,N-Dimethylacrylamide [acrylamide (E)] 145 parts
3-Methacryloxypropyltris(trimethylsiloxy)- 15 parts silane [monomer
(B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate 15 parts
[0055] The synthesized acryl silicone base copolymer had a number
average molecular weight of 3000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Production Example 7
[0056] An additive [A-7] was obtained in the same manner as in
Production Example 1, except that the following solution (a-7) was
substituted for the solution (a-1) used in Production Example
1.
7 Solution (a-7) 2-Ethoxyethyl acrylate 25 parts [(meth)acrylic
acid ester (D)] N,N-Dimethylacrylamide [acrylamide (E)] 25 parts
3-Methacryloxypropyltris(trimethylsiloxy)- 250 parts silan PFG 100
parts t-Butyl peroxy-2-ethylhexanoate 6 parts
[0057] The synthesized acryl silicone base copolymer had a number
average molecular weight of 8000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Production Example 8
[0058] The reaction was carried out in the same manner as in
Production Example 1, and then the following (a-8b) was added
thereto to obtain an additive [A-8], except that the following
solution (a-8a) was substituted for the solution (a-1) used in
Production Example 1.
8 Solution (a-8a) Tertiary butyl acrylate 75 parts [(meth)acrylic
acid ester (C)] N,N-Dimethylacrylamide [acrylamide (E)] 75 parts
2-Isocyanatoethyl methacrylate 50 parts [multifunctional monomer]
PFG 100 parts t-Butyl peroxy-2-ethylhexanoate 15 parts (a-8b)
3-Aminopropyltris(trimethylsiloxy)silane 150 parts [tris(trimethy
siloxy)silylgroup-containing compound]
[0059] After one hour since finishing dropwise adding the solution
(a-8a), 3 parts of t-butyl peroxy-2-ethylhexanoate was added, and
the reaction was further continued for 2 hours while keeping a
temperature of 120.degree. C. After finishing the reaction, the
solution was cooled down to a room temperature, and (a-8b) was
dropwise added thereto in one hour. After left standing for 24
hours, the non-volatile matter content was adjusted to 30% by PFG
to obtain an additive [A-8].
[0060] The synthesized acryl silicone base copolymer had a number
average molecular weight of 3000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Production Example 9
[0061] The reaction was carried out in the same manner as in
Production Example 1, and then the following (a-9b) was added
thereto to obtain an additive [A-9], except that the following
solution (a-9a) was substituted for the solution (a-1) used in
Production Example 1.
9 Solution (a-9a) 2-Methoxyethyl acrylate 100 parts [(meth)acrylic
acid ester (D)] Tertiary butyl vinyl ether [monomer (H)] 100 parts
Tertiary butylacrylamide [acrylamide (E)] 50 parts
2-Isocyanatoethyl methacrylate 50 parts [multifunctional monomer]
Toluene 50 parts t-Butyl peroxy-2-ethylhexanoate 15 parts (a-9b)
3-Aminopropyltris(trimethylsiloxy)silane 150 parts [tris(trimethy
siloxy)silylgroup-containing compound]
[0062] After one hour since finishing dropwise adding the solution
(a-9a), 3 parts of t-butyl peroxy-2-ethylhexanoate was added, and
the reaction was further continued for 2 hours while keeping a
temperature of 120.degree. C. After finishing the reaction, the
solution was cooled down to a room temperature, and (a-9b) was
dropwise added in one hour. After left standing for 24 hours, the
non-volatile matter content was adjusted to 30% by PFG to obtain an
additive [A-9].
[0063] The synthesized vinyl silicone base copolymer had a number
average molecular weight of 2500 in terms of polystyrene, which was
determined by gel permeation chromatography.
Comparative Production Example 1
[0064] An additive [N-1] was obtained in the same manner as in
Production Example 1, except that the following solution (n-1) was
substituted for the solution (a-1) used in Production Example
1.
10 Solution (n-1) Ethyl acrylate 200 parts [(meth)acrylic acid
ester (C)] 3-Methacryloxypropyltris(trimethylsiloxy)- 100 parts
silane [monomer (B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate
7.5 parts
[0065] The synthesized acryl silicone base copolymer had a number
average molecular weight of 6000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Comparative Production Example 2
[0066] An additive [N-2] was obtained in the same manner as in
Production Example 1, except that the following solution (n-2) was
substituted for the solution (a-1) used in Production Example
1.
11 Solution (n-2) Methoxypolyethylene glycol methacrylate 200 parts
(the number (m) of the ethylene glycol units is 23) [(meth)acrylic
acid ester (F)] 3-Methacryloxypropyltris(trimethylsiloxy)- 100
parts silane [monomer (B)] PFG 150 parts t-Butyl
peroxy-2-ethylhexanoate 10 parts
[0067] The synthesized acryl silicone base copolymer had a number
average molecular weight of 4000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Comparative Production Example 3
[0068] An additive [N-3] was obtained in the same manner as in
Production Example 1, except that the following solution (n-3) was
substituted for the solution (a-1) used in Production Example
1.
12 Solution (n-3) Ethyl acrylate [(meth)acrylic acid ester (C)] 150
parts Methoxypolyethylene glycol methacrylate 145 parts (the number
(m) of the ethylene glycol units is 23) [(meth)acrylic acid ester
(F)] 3-Methacryloxypropyltris(trimethylsiloxy)- 5 parts silane
[monomer (B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate 6
parts
[0069] The synthesized acryl silicone base copolymer had a number
average molecular weight of 7500 in terms of polystyrene, which was
determined by gel permeation chromatography.
Comparative Production Example 4
[0070] An additive [N-4] was obtained in the same manner as in
Production Example 1, except that the following solution (n-4) was
substituted for the solution (a-1) used in Production Example
1.
13 Solution (n-4) Ethyl acrylate [(meth)acrylic acid ester (C)] 6.5
parts Acrylic acid [(meth)acrylic acid (G)] 15.5 parts
3-Methacryloxypropyltris(trim- ethylsiloxy)- 278 parts silane
[monomer (B)] PFG 150 parts t-Butyl peroxy-2-ethylhexanoate 7.5
parts
[0071] The synthesized acryl silicone base copolymer had a number
average molecular weight of 5000 in terms of polystyrene, which was
determined by gel permeation chromatography.
Comparative Production Example 5
[0072] An additive [N-5] was obtained in the same manner as in
Production Example 1, except that the following solution (n-5) was
substituted for the solution (a-1) used in Production Example
1.
14 Solution (n-5) Tertiary butyl acrylate 150 parts [(meth)acrylic
acid ester (C)] Methoxypolyethylene glycol methacrylate 150 parts
(the number (m) of the ethylene glycol units is 23) [(meth)acrylic
acid ester (F)] 3-Methacryloxypropyltris(trimethylsiloxy)- 100
parts silane [monomer (B)] PFG 50 parts t-Butyl
peroxy-2-ethylhexanoate 0.5 part
[0073] The synthesized acryl silicone base copolymer had a number
average molecular weight of 45,000 in terms of polystyrene, which
was determined by gel permeation chromatography.
Comparative Production Example 6
[0074] An additive [N-6] was obtained in the same manner as in
Production Example 1, except that the following solution (n-6) was
substituted for the solution (a-1) used in Production Example
1.
15 Solution (n-6) Tertiary butyl acrylate 50 parts [(meth)acrylic
acid ester (C)] N-Tertiary butylacrylamide 50 parts [acrylamide
(E)] 3-Methacryloxypropyltris(trimethylsiloxy)- 50 parts silane
[monomer (B)] PFG 350 parts t-Butyl peroxy-2-ethylhexanoate 15
parts
[0075] The synthesized acryl silicone base copolymer had a number
average molecular weight of 400 in terms of polystyrene, which was
determined by gel permeation chromatography.
Comparative Production Example 7
[0076] AQ-200 (manufactured by Kusumoto Chemicals, Ltd.) was used
as a commercially available flow-and-leveling agent of an acryl
copolymer base. This was designated as an additive [N-7].
Comparative Production Example 8
[0077] Byk-348 (manufactured by Byk Chemie Co., Ltd.) was used as a
commercially available flow-and-leveling agent of a silicone base.
This was designated as an additive [N-8].
16TABLE 1 Polymers used in production examples Number average
Active Sample name molecular weight Ingredient (%) Production A-1
5000 30 Example 1 Production A-2 1500 30 Example 2 Production A-3
2500 30 Example 3 Production A-4 2000 30 Example 4 Production A-5
10000 30 Example 5 Production A-6 3000 30 Example 6 Production A-7
8000 30 Example 7 Production A-8 3000 30 Example 8 Production A-9
2500 30 Example 9
[0078]
17TABLE 2 Polymers used in comparative production examples Number
average Active Sample name molecular weight Ingredient (%)
Comparative N-1 6000 30 Production Example 1 Comparative N-2 4000
30 Production Example 2 Comparative N-3 7500 30 Production Example
3 Comparative N-4 5000 30 Production Example 4 Comparative N-5
45000 30 Production Example 5 Comparative N-6 400 30 Production
Example 6 Comparative N-7 -- 20 Production Example 7 Comparative
N-8 -- 100 Production Example 8
[0079] Coating Test Example 1 (Flow-and-leveling Property Test with
Waterborne Base Coating)
[0080] Waterborne base coating composition having proportions shown
in Table 3 was tested for a flow-and-leveling property.
[0081] [Preparation of Metallic Base Coating]
[0082] A composition A, a composition B and a composition C each
shown in Table 3 were homogeneously mixed in this order while
stirring by means of a disper to prepare an acryl melamine base
aqueous metallic base coating. The resulting coating was controlled
to a pH of 7.8 by dimethylethanolamine and then diluted with
distilled water so that the viscosity was 30 seconds (20.degree.
C.) in terms of Ford cup #4. An additive shown in table 1 or Table
2 was added to the waterborne base coating thus prepared so that
the ingredient content was 0.3% based on the coating, and the
mixture was homogeneously stirred by means of the disper.
[0083] [Preparation of Soleventborne Prinmercoat Plate]
[0084] The viscosity of an soleventborne primer coating having a
composition shown in Table 5 was controlled with a diluent solvent
so that the viscosity was 18 seconds in terms of Ford cup #4, and
then the coating was applied on a tin plate (0.3 mm.times.200
mm.times.300 mm) by means of an air spray and baked in an oven at
140.degree. C. for 20 minutes. Three soleventborne primercoat
plates were prepared for each test sample. After cooled down to a
room temperature, a waterdrop was fallen on one soleventborne
primercoat plate and dried at 80.degree. C. After the waterdrop was
dried, the additive stayed in the state that it was put together
and concentrated. Further, a machine oil was adhered as a
contaminant on another soleventborne primercoat plate. The
remaining one soleventborne primercoat plate was used as it was for
coating the waterborne base coating.
[0085] [Test of Flow-and-leveling Property]
[0086] The metallic base coating prepared above was left standing
for 24 hours and then coated on the soleventborne primercoat plate
by means of an air spray so that the film thickness after being
dried was 15.mu.. After drying the film in an oven of 80.degree. C.
for 10 minutes, flow-and-leveling property of the metallic base
coating surface was visually evaluated. Then a top clear coating
shown in Table 4 was applied thereon by means of the air spray so
that the film thickness after being dried was 40.mu., and after
setting for 10 minutes, it was baked in an oven of 140.degree. C.
for 20 minutes. Cooling the baked product off to room temperature,
flow-and-leveling property of the top clear coating-applied surface
was visually observed for evaluating the top coating property.
[0087] [Evaluation of Flow-and-leveling Property]
[0088] The flow-and-leveling property of the waterborne coating
itself and the surface state after applying the top clear coating
were visually observed respectively to evaluate them according to
the five grades of "best" (5) to "worst" (1). (The differences in
the top coating proper grades among those top coating-applied
surfaces were significantly relevant to the kind of
flow-and-leveling agents added to the metallic base coating.)
Further, the numbers of ruptures and craters observed on the
coating film which was coated on the contaminant were visually
counted to evaluate them according to the five grades of "best" (5)
to "worst" (1). The results thereof are shown in Table 6.
[0089] Coating Test Example 2 (Evaluation with Waterborne Primer
Coating)
[0090] [Test of Flow-and-leveling Property]
[0091] The additives shown in Table 1 or Table 2 were added to a
waterborne primer coating having a composition shown in Table 7,
and the mixture was homogeneously stirred by means of a disper.
Three cationically electrodeposited plates (0.8 mm.times.200
mm.times.300 mm) were prepared for each test sample. A fingerprint
was put on the first cationically electrodeposited plate with a
finger on which hand cream was applied. A machine oil was adhered
as a contaminant on another cationically electrodeposited plate. A
waterborne primer coating for investigation was applied on the
remaining one cationically electrodeposited plate as it was. After
24 hours since adding the additive for test, a waterborne primer
coating was diluted with distilled water so that the viscosity was
25 seconds in terms of Ford cup #4. This waterborne primer coating
was applied on the cationically electrodeposited plate for test by
means of the air spray so that the film thickness after dried was
30.mu.. After setting for 10 minutes, it was dried in an oven of
80.degree. C. for 10 minutes and further baked in an oven of
160.degree. C. for 25 minutes.
[0092] The recoatability was tested in the following manner. The
flow-and-leveling property of the waterborne primer coating applied
on the cationically electrodeposited plate was evaluated, and then
a solventborne primer coating shown in Table 5 was applied thereon
by means of the air spray so that the film thickness after dried
was 30.mu.. After setting for 5 minutes, it was baked in an oven of
140.degree. C. for 20 minutes. Cooling the baked product off to
room temperature, flow-and-leveling property of the top clear
coating-applied surface was visually observed for evaluating the
solventborne primer coating property.
[0093] [Evaluation of Flow-and-leveling Property]
[0094] The surface state was visually observed to evaluate the
flow-and-leveling property according to the five grades of "best"
(5) to "worst" (1). (The differences in the top coating proper
grades among those top coating-applied surfaces were significantly
relevant to the kind of flow-and-leveling agents added to the
waterborne primer coating.) Further, the numbers of ruptures and
craters observed on the coating film which was coated on the
contaminant were visually counted to evaluate them according to the
five grades of "best" (5) to "worst" (1). The results thereof are
shown in Table 8.
[0095] [Evaluation of Layer-to-layer Adhesive Property]
[0096] The solventborne primer coating was applied on a plate
coated with the waterborne primer coating, and it was used for
testing a layer-to-layer adhesive property. Hundred cross cut
blocks having an equal width of 1 mm were produced in a square of
10 mm.times.10 mm on the coated plate by means of a cutter to carry
out a peeling test with a cellophane adhesive tape, and the number
of the remaining blocks of the above primer coating film was
counted. The results thereof are shown in Table 8.
18TABLE 3 Composition of aqueous metallic base coating Amount Raw
material name (parts) Manufacturer of raw material Composition A
Setalux 6801 AQ-24 480 AKZO NOBEL Setamine MS-155 AQ-80 47 AKZO
NOBEL 2-Butoxyethanol 41 Kyoei solvent Co., Ltd. Distilled water
255 Dimethylethanolamine 10 10% aqueous solution Composition B
Aluminum paste: 37.5 Asahi Chemical Ind. Co., Ltd. AW-7000R#
2-Butoxyethanol 33.0 Kyoei solvent Co., Ltd. Setal 6306 SS-66 31.5
AKZO NOBEL Dimethylethanolamine 1.0 Kanto Chemical Ind. Co., Ltd.
Composition C Setal 6407 SQ-26 64 AKZO NOBEL
[0097]
19TABLE 4 Composition of top coat clear coating Amount Raw material
name (parts) Manufacturer of raw material Jhoncryl 500 203.6
Jhonson Polymer Co., Ltd. Cymel 325 69.7 Mitsui Cytec Co., Ltd.
Nacure 5528 0.88 King Industries Flow-and-leveling agent: 0.7
Kusumoto Chemicals, Ltd. Disparlon LHP-90 Defoaming agent: 1.75
Kusumoto Chemicals, Ltd. Disparlon AP-10 Diluent solvent *) 97.7 *)
Diluent solvent: Solvesso #100/methyl isobutyl ketone/butyl alcohol
= 30/30/40
[0098]
20TABLE 5 Composition of solvent base intermediate coating Amount
Raw material name (parts) Manufacturer of raw material Becksol
EY-3002-65 15.0 Dainippon Ink & Chemicals, Inc. Becksol 57-1362
30.0 Dainippon Ink & Chemicals, Inc. Titanium dioxide CR-93
34.3 Ishihara Sangyo Kaisha., Ltd. Carbon black MA-100 0.7
Mitsubishi Chemical Corp. Super Becamine G-821-60 20.0 Dainippon
Ink & Chemicals, Inc. Diluent solvent *) 65.0 Disparlon
L-1984-50 0.45 Kusumoto Chemicals, Ltd. (leveling agent) Disparlon
AP-10 0.45 Kusumoto Chemicals, Ltd. (defoaming agent) *) Diluent
solvent: Solvesso #100/xylene/butyl cellosolve/butyl alcohol =
40/30/20/10
[0099]
21TABLE 6 Test results of flow-and-leveling agents for waterborne
base coating Flow-and- Coating leveling property Rupture caused by
property of of top contaminant Sample Addition waterborne coat
clear Waterdrop Machine name amount (%) base coating coating mark
oil A-1 1.0 5 5 5 5 A-2 1.0 5 5 5 5 A-3 1.0 5 5 5 5 A-4 1.0 4 5 3 3
A-5 1.0 5 5 5 5 A-6 1.0 3 5 3 3 A-7 1.0 4 3 5 5 A-8 1.0 5 5 5 5 A-9
1.0 4 5 4 5 N-1 1.0 -- -- -- -- N-2 1.0 2 5 1 1 N-3 1.0 1 5 1 1 N-4
1.0 2 1 3 5 N-5 1.0 -- -- -- -- N-6 1.0 1 5 1 1 N-7 1.5 4 5 4 1 N-8
0.3 5 3 3 1 *) The evaluation results marked by -- showed that the
additive could not homogeneously be dispersed and that the coating
film capable of being evaluated could not be formed.
[0100]
22TABLE 7 Composition of water base intermediate coating Amount Raw
material name (parts) Manufacturer of raw material Setal X11366
520.0 AKZO NOBEL Barium sulfate: W-1 160.9 Takehara chemical Co.,
Ltd. Titanium dioxide: JR-600A 160.9 Tayca Corporation Carbon
black: MA-100 1.2 Mitsubishi Chemical Corp. SetamineMS-155AQ-80
73.1 AKZO NOBEL Butyl carbitol 23.4 Kyoei Solvent Co., Ltd.
Distilled water 25.0
[0101]
23TABLE 8 Test results of flow-and-leveling agents for waterborne
primer coating Flow-and- leveling Coating Layer-to- Rupture caused
Addition property of property of layer by contaminant Sample amount
waterborne solventborne adhesive Hand Machine name (%) primer
coating primer coating property cream oil A-1 1.0 5 5 100/100 5 5
A-2 1.0 5 5 100/100 5 5 A-3 1.0 5 5 100/100 5 5 A-4 1.0 4 5 100/100
3 3 A-5 1.0 5 5 100/100 5 5 A-6 1.0 3 5 90/100 3 2 A-7 1.0 4 3
100/100 5 5 A-8 1.0 5 5 100/100 5 5 A-9 1.0 4 5 100/100 5 4 N-1 1.0
-- -- -- -- -- N-2 1.0 2 5 100/100 2 2 N-3 1.0 1 5 50/100 1 1 N-4
1.0 3 1 100/100 5 5 N-5 1.0 -- -- -- -- -- N-6 1.0 1 5 25/100 1 1
N-7 1.5 4 2 50/100 1 1 N-8 0.3 5 3 50/100 3 1 *) The evaluation
results marked by -- showed that the additive could not
homogeneously be dispersed and that the coating film capable of
being evaluated could not be formed.
* * * * *