U.S. patent application number 10/483260 was filed with the patent office on 2004-11-04 for aqueous paint composition of baking-drying type.
Invention is credited to Hiraki, Toshimichi, Nagaoka, Hidenori, Nonoyama, Akira, Ohashi, Yutaka, Suzuki, Haruhisa.
Application Number | 20040220314 10/483260 |
Document ID | / |
Family ID | 28449021 |
Filed Date | 2004-11-04 |
United States Patent
Application |
20040220314 |
Kind Code |
A1 |
Suzuki, Haruhisa ; et
al. |
November 4, 2004 |
Aqueous paint composition of baking-drying type
Abstract
To propose a baking-drying water damping paint composition from
which heavy film-thickness damping paint films can be obtained,
heavy film-thickness damping paint films in which an inorganic
filler is filled into the resinous component of paints to higher
extent, and which are free from the occurrence of cracks and
swelling in the paint films when the paint films are baked and
dried. The composition comprises a water emulsion including at
least one first granular resin selected from the group consisting
of styrene-butadiene copolymers, acrylic ester copolymers and
ethylene-vinyl acetate copolymers whose glass transition
temperature is from 0 to 20.degree. C. and gel ratio is from 60 to
80%, and an inorganic filler in an amount of 200 parts by weight or
more with respect to 100 parts by weight of said first granular
resin. By using water emulsion particles whose gel ratio is
controlled in the specific range, it is possible to obtain cured
paint films which are free from the occurrence of cracks and
swelling in the paint films and which exhibit a high damping effect
stably even when the inorganic filler is filled to higher extent
and the paint films are further dried at ordinary baking
temperatures.
Inventors: |
Suzuki, Haruhisa;
(Toyota-shi, JP) ; Hiraki, Toshimichi;
(NIshikasugai-gun, JP) ; Nonoyama, Akira;
(Chiryu-shi, JP) ; Ohashi, Yutaka; (Nisshin-shi,
JP) ; Nagaoka, Hidenori; (Toyota-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Family ID: |
28449021 |
Appl. No.: |
10/483260 |
Filed: |
March 23, 2004 |
PCT Filed: |
February 3, 2003 |
PCT NO: |
PCT/JP03/01085 |
Current U.S.
Class: |
524/425 ;
524/448; 524/450; 524/451 |
Current CPC
Class: |
C08L 23/0853 20130101;
C09D 7/61 20180101; C08L 53/02 20130101; C08L 2205/02 20130101;
C08K 3/26 20130101; C09D 135/06 20130101; C08K 3/013 20180101; C09D
133/08 20130101; C09D 125/10 20130101; C09D 7/69 20180101; C09D
131/04 20130101; C09D 5/022 20130101; C09D 123/0853 20130101; C08L
25/14 20130101; C09D 123/0853 20130101; C08L 2666/24 20130101; C08K
3/013 20180101; C08L 9/06 20130101; C09D 125/10 20130101; C08L
2666/06 20130101 |
Class at
Publication: |
524/425 ;
524/451; 524/448; 524/450 |
International
Class: |
C08K 003/26; C08K
003/34 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 4, 2002 |
JP |
2002/27281 |
Claims
1. A baking-drying water damping paint composition, comprising: a
water emulsion including at least one first granular resin selected
from the group consisting of styrene-butadiene copolymers, acrylic
ester copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature is from 0 to 20.degree. C. and gel ratio is
from 60 to 80%; and an inorganic filler in an amount of 200 parts
by weight or more with respect to 100 parts by weight of said first
granular resin.
2. The baking-drying water damping paint composition set forth in
claim 1, wherein a drying temperature of a paint film falls in a
range of from 70 to 160.degree. C.
3. The baking-drying water damping paint composition set forth in
claim 1 comprising said inorganic filler in an amount of 600 parts
by weight or less with respect to 100 parts by weight of said first
granular resin.
4. The baking-drying water damping paint composition set forth in
claim 1, wherein said inorganic filler is at least one member
selected from the group consisting of calcium carbonate, talc,
diatomaceous earth, barium sulfate, zeolite, magnesium carbonate
and mica.
5. The baking-drying water damping paint composition set forth in
claim 4, wherein said inorganic filler has an average particle
diameter of 50 .mu.m or less.
6. The baking-drying water damping paint composition set forth in
claim 1, wherein said inorganic filler includes inorganic short
fibers whose fibrous length is from 100 .mu.m to 1 mm.
7. A baking-drying water damping paint composition, comprising: a
water emulsion including at least one first granular resin selected
from the group consisting of styrene-butadiene copolymers, acrylic
ester copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature is from 0 to 20.degree. C. and gel ratio is
from 60 to 80%, and at least one second granular resin selected
from the group consisting of styrene-butadiene copolymers, acrylic
ester copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature is from 25 to 60.degree. C.; and an
inorganic filler in an amount of 200 parts by weight or more with
respect to the sum of said first granular resin and said second
granular resin taken as 100 parts by weight.
8. The baking-drying water damping paint composition set forth in
claim 7, wherein a drying temperature of a paint film falls in a
range of from 70 to 160.degree. C.
9. The baking-drying water damping paint composition set forth in
claim 7 comprising said inorganic filler in an amount of 600 parts
by weight or less with respect to the sum of said first granular
resin and said second granular resin taken as 100 parts by
weight.
10. The baking-drying water damping paint composition set forth in
claim 7, wherein said inorganic filler is at least one member
selected from the group consisting of calcium carbonate, talc,
diatomaceous earth, barium sulfate, zeolite, magnesium carbonate
and mica.
11. The baking-drying water damping paint composition set forth in
claim 10, wherein said inorganic filler has an average particle
diameter of 50 .mu.m or less.
12. The baking-drying water damping paint composition set forth in
claim 7, wherein said inorganic filler includes inorganic short
fibers whose fibrous length is from 100 .mu.m to 1 mm.
13. The baking-drying water damping paint composition set forth in
claim 7, wherein said first granular resin is included in an amount
of from 40 to 85 parts by weight with respect to the sum of said
first granular resin and said second granular resin taken as 100
parts by weight.
14. The baking-drying water damping paint composition set forth in
claim 7, wherein said first granular resin is included in an amount
of from 50 to 85 parts by weight with respect to the sum of said
first granular resin and said second granular resin taken as 100
parts by weight.
Description
TECHNICAL FIELD
[0001] The present invention relates to a baking-drying water
damping paint composition which is a water paint composition into
which an inorganic filler is filled to higher extent, and which can
form stable and heavy thickness cured paint films by baking.
BACKGROUND ART
[0002] Conventionally, sheet-shaped damping members, such as
asphalt sheets, have been used in automotive body floors, doors,
dashboards, and the like, in order to give them a damping property.
Moreover, coating water damping paints, which are adapted for
automatically coating with robots and so forth, have been developed
recently. However, in the case of ordinary damping paints, since
the specific gravity of the resulting paint films is smaller than
that of asphalt sheets, it is necessary to further thicken the film
thickness, and accordingly there is fear that such problems might
arise in that they interfere with the other component parts, form
steep irregularities on body floors, and so on. In addition,
damping paints are yet highly expensive at present.
[0003] As a method to solve the problems, it is possible to think
of enhancing the specific gravity of paints by heightening the
filling ratio of inorganic fillers into paints, however, when
inorganic fillers are filled to higher extent, cracks are likely to
occur in the resulting paint films in baking and drying. As a
result, there is a problem in that the paint films come off from
the substrates to be coated because of the poor adhesion to the
substrates to be painted, and it is thus impossible at present to
fully effect the performance of paint films with inorganic fillers
filled to higher extent.
[0004] In Japanese Unexamined Patent Publication (KOKAI) No. 8-209,
056, there is a disclosure on an ordinary-temperature drying water
emulsion paint which is good in terms of the adhesion to
undercoatings and the damping property. In the paint, 3 kinds of
denatured resins, such as (a) a partially cross-linked acrylic
resin whose gel ratio is from 10 to 90% by weight, (b) a carboxyl
denatured styrene-butadiene rubber and (c) a styrene denatured
acrylic resin, are mixed to use them at the same time, and it is
considered preferable to compound an inorganic filler in an amount
of from 150 to 250 parts with respect to 100 parts of the resinous
content.
[0005] The paint is an ordinary-temperature drying one, and
requires drying at room temperature for 72 hours in order to obtain
a paint film whose film thickness is 5,000 .mu.m in the examples.
When it is baked at higher temperatures in order make the drying
faster., it is assumed that a drawback arises in that no normal
paint films can be obtained because cracks, swelling and the like
occur.
[0006] In Japanese Unexamined Patent Publication (KOKAI) No.
9-151,335, a water damping paint is disclosed which includes an
inorganic filler in an amount of from 250 to 550 parts by weight
and both or either one of a thickening agent and a dispersing agent
in an amount from 0.3 to 35 parts by weight with respect to 100
parts by weight of the solid content of a synthetic resin emulsion
whose major component is a synthetic resin exhibiting a glass
transition temperature of from -50.degree. C. to 5.degree. C. The
paint was dried at room temperature in the examples. Nothing is set
forth on the gel ratio of the synthetic resin.
[0007] In Japanese Unexamined Patent Publication (KOKAI) No.
5-194,906, there is a disclosure on a composition for water
coating, composition which comprises polymer fine particles,
dispersed in a water medium, and an inorganic filler. The polymer
fine particles are made of two kinds of polymer fine particles,
i.e., synthetic rubber emulsion polymer particles whose glass
transition temperature is 0.degree. C. or less and emulsion polymer
particles whose glass transition temperature is 20.degree. C. or
more. Regarding the compounding amount of the inorganic filler into
the paint resin, a possibility of such a high compounding amount is
disclosed that it can preferably fall in a range of from 120 to 380
parts by weight with respect to 100 parts by weight of the resinous
content. However, it is considered appropriate that the thickness
of the paint falls in a range of from 200 to 800 .mu.m, and when it
is adapted for compositions to be baked at elevated temperatures,
it is recommended to carry out 2-stage drying in which it is dried
preliminarily at a temperature of from 60 to 100.degree. C. and is
thereafter baked at a temperature of from 120 to 160.degree. C.
[0008] With the composition for water coating, it is difficult to
overcome the drawback that cracks and swelling are likely to occur
when paint films, which are applied in a heavy thickness, are baked
and dried at high temperatures in one stage. The swelling limit of
the paint films obtained in the examples was as thin as from 400 to
1,200 .mu.m, and accordingly it is not possible to obtain heavy
thickness paint films which are needed to obtain a damping
property.
[0009] In Japanese Unexamined Patent Publication (KOKAI) No.
2000-160,059, there is a disclosure on a water emulsion paint which
comprises a water emulsion resin whose gel ratio is from 93 to 97%
in an amount of from 20 to 50 parts by weight, and whose a baking
temperature is from 70 to 130.degree. C. However, in the paint,
since the resin is used which exhibits such a high gel ratio, an
inorganic filler is compounded so that calcium carbonate, a filler,
is compounded in an amount of 40% by weight at the highest with
respect to 30% by weight of the resin as set forth in the examples,
and thus the content of the inorganic filler is about 1.3 times the
content of the resin at the highest. Since the resinous content
exhibits a high gel ratio so that the cross-linking density is
enhanced therein, it is impossible to hold the filler in the resin
when the inorganic filler is filled in the resin in a double amount
or more of the resin, and accordingly cracks, swelling, and the
like, occur, and consequently it is difficult to obtain
satisfactory paint films.
[0010] When inorganic fillers are compounded in baking-drying water
paints as described above, in the water paints disclosed
conventionally, since there is a fear for cracked paints which are
caused by the volumetric contraction of paint films, volumetric
contraction which is accompanied by the evaporation of the water
content within paints under baking-temperature conditions where the
drying of ordinary paint films is carried out, it has been usual
practices to dry paints mostly in a low temperature range to make
cured paint films, or to decrease the compounding amount of
inorganic fillers, or further to simultaneously use special
denatured resins in combination. In particular, when inorganic
fillers are filled to higher extent in order to reduce costs
involved, there is a problem in that the phenomena, such as cracked
paint films and swollen paint films, arise remarkably in drying the
aforementioned resinous components.
[0011] The present invention has been done in view of the
aforementioned circumstances, and it is an assignment to propose a
baking-drying water damping paint composition, in which an
inorganic filler is filled into the resinous component of paints to
higher extent, and from which heavy thickness paint films being
free from the occurrence of cracks and swelling in baking and
drying the paint films can be obtained, in the field of
baking-drying water paints.
SUMMARY OF THE INVENTION
[0012] A baking-drying water damping paint composition according to
the present invention comprises: a water emulsion including at
least one first granular resin selected from the group consisting
of styrene-butadiene copolymers, acrylic ester copolymers and
ethylene-vinyl acetate copolymers whose glass transition
temperature is from 0 to 20.degree. C. and gel ratio is from 60 to
80%; and an inorganic filler in an amount of 200 parts by weight or
more with respect to 100 parts by weight of said first granular
resin.
[0013] Another baking-drying water damping paint composition
according to the present invention comprises: a water emulsion
including at least one first granular resin selected from the group
consisting of styrene-butadiene copolymers, acrylic ester
copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature is from 0 to 20.degree. C. and gel ratio is
from 60 to 80%, and at least one second granular resin selected
from the group consisting of styrene-butadiene copolymers, acrylic
ester copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature is from 25 to 60.degree. C.; and an
inorganic filler in an amount of 200 parts by weight or more with
respect to the sum of said first granular resin and said second
granular resin taken as 100 parts by weight.
[0014] The present inventors found out that cracks occur in baking
and drying so that it is less likely to obtain heavy thickness
paint films whose thickness is 3 mm or more when the gel ratio of
the water emulsion including at least one first granular resin
selected from the group consisting of styrene-butadiene copolymers,
acrylic ester copolymers and ethylene-vinyl acetate copolymers is
higher beyond 80%, and that swelling occurs in baking and drying so
that it is less likely to obtain heavy thickness paint films whose
thickness is 3 mm or more when the gel ratio of the water emulsion
is less than 50% contrarily. Moreover, the inventors found out
that, even when the gel ratio falls in a range of from 60 to 80%,
cracks or swelling occurs in baking and drying so that it is less
likely to obtain heavy thickness paint films whose thickness is 3
mm or more when the glass transition temperature of the first
granular resin is lower than 0.degree. C. or when it is higher
beyond 20.degree. C. contrarily.
[0015] In addition, when a water emulsion is used which includes at
least one first granular resin selected from the group consisting
of styrene-butadiene copolymers, acrylic ester copolymers and
ethylene-vinyl acetate copolymers whose glass transition
temperature is from 0 to 20.degree. C. and gel ratio is from 60 to
80%, and at least one second granular resin selected from the group
consisting of styrene-butadiene copolymers, acrylic ester
copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature is from 25 to 60.degree. C., the present
inventors found out that it is possible to obtain paint films which
have a heavy thickness equal to or more than the instance that a
water emulsion is formed of the first granular resin alone.
[0016] The present baking-drying water damping paint composition
has been completed based on the discoveries and knowledge.
[0017] Said inorganic filler can preferably be at least one member
selected from the group consisting of calcium carbonate, talc,
diatomaceous earth, barium sulfate, zeolite, magnesium carbonate
and mica.
[0018] It comprises said inorganic filler in an amount of 200 parts
by weight or more with respect to 100 parts by weight of said first
granular resin. The upper limit can preferably be 600 parts by
weight approximately.
[0019] Moreover, the present baking-drying water damping paint
composition can preferably be such that the drying-and-baking
temperature falls in a range of from 70 to 160.degree. C.
[0020] In the present invention, by using water emulsion particles
whose gel ratio is controlled in the specific range, it is possible
to obtain stable cured paint films which are free from the
occurrence of cracks and swelling even when the inorganic filler is
filled to higher extent and further the paint films are dried at
ordinary baking temperatures.
[0021] Moreover, since the paint composition can enhance the
specific gravity of paint films by enlarging the compounding amount
of the inorganic filler, the thickness can be reduced compared with
that of conventional damping paints. In addition, since it is
possible to utilize inexpensive inorganic fillers, it is possible
to achieve reducing the costs of damping paints so that it becomes
a useful baking-drying water paint composition.
MODE FOR CARRYING OUT THE INVENTION
[0022] The present baking-drying water damping paint composition is
characterized in that it can be baked and cured, and in that the
inorganic filler can be compounded to higher extent. And, the first
granular resin, water emulsion particles making the resinous
component of the paint composition, is composed of at least one
member selected from the group consisting of styrene-butadiene
copolymers, acrylic ester copolymers and ethylene-vinyl acetate
copolymers whose glass transition point (Tg) falls in a range of
from 0 to 20.degree. C. Then, the first granular resin is
characterized in that it is the resinous component whose gel ratio,
an index of the cross-linking density, falls in a range of from 60
to 80%.
[0023] Moreover, the other present baking-drying water damping
paint composition uses a water emulsion in which the first granular
resin is mixed with the second granular resin selected from the
group consisting of styrene-butadiene copolymers, acrylic ester
copolymers and ethylene-vinyl acetate copolymers whose glass
transition temperature (Tg) falls in a range of from 25 to
60.degree. C.
[0024] It is necessary for the gel ratio to fall in a range of from
60 to 80% in order that the inorganic filler is filled into the
paint composition to higher extent so as to form satisfactory dried
paint films under ordinary baking temperature conditions. When the
gel ratio exceeds 80%, and when the inorganic filler is filled in a
greater amount, it is not preferable because cured paint films are
brittle so that cracks occur in paint films. On the other hand,
when the gel ratio is less than 60%, it is not preferable because
the strength of paint films is not sufficient in baking and drying
so that they cannot withstand the rapid evaporation of the water
and swelling occurs in paint films.
[0025] Moreover, when the second granular resin whose glass
transition temperature (Tg) falls in a range of from 25 to
60.degree. C. is mixed in an amount of from 15 to 60% with respect
to the first granular resin, it is possible to promote the
evaporation of the water content in initial baking and drying so
that the swelling of paint films is improved more in baking and
drying, and accordingly it is possible to obtain cured paint films
provided with a good damping property and free from the occurrence
of cracks and swollen paint films even in baking and drying paint
films with such an extremely heavy thickness as 8 mm in thickness.
Note that the mixing of the first granular resin and second
granular resin can be prepared with ease by mixing each one of
first granular resin emulsions and second granular resin
emulsions.
[0026] When the mixing amount of the second granular resin exceeds
60% of the sum of the first granular resin and second granular
resin taken as 100%, or when the glass transition temperature (Tg)
of the second granular resin exceeds 60.degree. C., the formation
of paint films is slow in baking and drying so that paint films
become brittle and cracks are likely to occur. Moreover, when the
compounding proportion of the second granular resin is less than
20%, or when the glass transition temperature. (Tg) is less than
25.degree. C., the action of promoting the evaporation of the water
content is insufficient in initial baking and drying so that the
swelling of paint films is likely to occur in paint films with such
an extremely heavy thickness as 8 mm in thickness.
[0027] The first granular resin and second granular resin can be
such that at least one or two members of styrene-butadiene
copolymers, acrylic ester copolymers and ethylene-vinyl acetate
copolymers are mixed to use, or, depending on cases, three of them
are mixed to use. The styrene-butadiene copolymers can preferably
contain butadiene in an amount of from 30 to 40% by weight at
least. As for the acrylic ester copolymers, it is possible to
utilize copolymers which are made from two or more monomers
selected from the group consisting of methyl acrylate, ethyl
acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acryalte,
2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate,
glycidyl acrylate, and the like. The ethylene-vinyl acetate
copolymers can preferably be such that vinyl acetate is included in
an amount of from 40 to 50% by weight at least.
[0028] Moreover, in order to compound the inorganic filler to
higher extent, it is preferred that the resinous component can be
included in the emulsion in a concentration of from 40 to 60% by
weight because the paintability is sustained and paint films which
exhibit satisfactory paint-film physical properties are formed
after painting.
[0029] Since the resinous component in the water emulsions is
provided with the characteristics described above, it is possible
to hold the inorganic filler even when the inorganic filler is
compounded in the water emulsions abundantly, and to let the
sufficient paint-film performance reveal under ordinary
baking-temperature conditions, namely, at a baking temperature of
from 70 to 160.degree. C.
[0030] The gel ratio designates the cross-linking density in resin,
is a measured value which designates how much insoluble components
exist when resin is immersed in solvent, and can be calculated by
the following equation.
((Weight of Dried Resin after being Extracted with Solvent)/(Weight
of Resin before being Extracted with Solvent)).times.100
[0031] Specifically, the weight of the paint film which forms the
dried paint film of the water emulsion resin is measured, the paint
film is immersed in a solvent (for example, toluene), which can
solve the resin, for a predetermined period of time, and the
resinous paint film is thereafter dried at a predetermined
temperature to measure the weight, and then the gel ratio is
calculated by the above-describe equation.
[0032] In the present paint composition, the water emulsion resin
whose gel ratio is from 60 to 80% can be prepared in general in the
following manner. For example, when SBR is exemplified, SBR can be
obtained generally by subjecting styrene (S), butadiene (B),
unsaturated carboxylic acid and the other monomers to emulsion
polymerization in the presence of an emulsifier. In the course of
the emulsion polymerization, the water emulsion resin whose gel
ratio is from 60 to 80% can be prepared by adding a chain transfer
agent (underwater addition).
[0033] Note that it is possible to control the gel ratio by
adjusting the content of a cross-linking agent or a polymerization
initiator along with the addition of a chain transfer agent. The
water emulsion resin, the present first granular resin, exhibits a
glass transition point (Tg) falling in a range of from 0 to
20.degree. C. Moreover, the water emulsion resin, the present
second granular resin, exhibits a glass transition point (Tg)
falling in a range of from 25 to 60.degree. C.
[0034] Regarding the Tg as well, when SBR is exemplified likewise,
it is possible to obtain resins having a desired Tg by adjusting
the contents of styrene and butadiene.
[0035] In the case where a styrene-butadiene copolymer, an acrylic
ester copolymer and an ethylene-vinyl acetate copolymer are used in
combination, it is possible to carry out the forming by mixing
their water emulsions which are synthesized independently.
[0036] As for the inorganic filler to be compounded, at least one
or more members selected from the group consisting of calcium
carbonate, talc, diatomaceous earth, barium sulfate, zeolite,
magnesium carbonate and mica are used. The compounding proportion
into the paint composition is 200 parts by weight or more,
preferably from 200 parts by weight to 600 parts by weight, further
preferably from 200 to 400 parts by weight, with respect to 100
parts by weight of the resinous content.
[0037] When the compounding proportion of the inorganic filler is
less than 200 parts by weight, it is not preferable because it
cannot be turned into the present paint films in which the
inorganic filler is filled to higher extent. The upper limit of the
compounding proportion of the inorganic filler can be allowed up to
600 parts by weight, however, can preferably be from 200 to 400
parts by weight approximately in order to make satisfactory paint
films.
[0038] Moreover, in order to uniformly disperse and fill the
inorganic filler to sustain the strength of paint films, it is
preferable to use the inorganic filler whose average particle
diameter is 50 .mu.m or less. When the average particle diameter is
50 .mu.m or less, the dispersibility is enhanced in paint films to
heighten the strength of paint films in baking so that it is
possible to inhibit the occurrence of cracks and swelling.
[0039] In addition, when inorganic short fibers, such as
wollastonite and whisker-shaped calcium carbonate, for example,
whose fibrous length is from 100 .mu.m to 1 mm are filled as the
inorganic filler in an amount of from 30 to 100 parts by weight, it
is possible to obtain satisfactory paint films which are free from
cracks and swelling, however, it is necessary to care in order that
clogged nozzles do not occur in discharging.
[0040] It is possible to adjust the qualities, such as the
viscosity, for painting operations by compounding the paint
composition with the other known additives, such as a defoaming
agent, a dispersing agent, a thickening agent and a running
inhibitor agent.
[0041] The mixing of the paint composition can be carried out with
high-speed dispersers which can stir and disperse it at a high
speed, and accordingly it is possible to make pints having a
viscosity and concentration which are appropriate for painting
operations.
[0042] The painting can be carried out with spraying guns for
ordinary spray painting, or by airless spraying methods.
[0043] Depending on the thickness, paint films coated on substrates
to be painted are usually baked and cured at a temperature of from
70.degree. C. to 160.degree. C. for from 5 to 30 minutes. Even when
being dried under the baking-temperature condition, no cracks,
swelling, and the like, occur in the relatively heavy thickness
paint films so that it is possible to form paint films, in which
the inorganic filler is filled to higher extent, with ease. Note
that the thickness of wet paint films before baking and the
thickness of dried pained films after baking are identical
substantially. The lower the baking temperature is, the thinner the
thickness of dried paint films tends to be. It is believed that
fine bubbles are dispersed in paint films when being baked at
elevated temperatures.
[0044] The present dried paint films exhibit an enhanced specific
gravity because the filling extent of the inorganic filler is high,
and accordingly can be used as damping paint films. Moreover, it is
possible to reduce the costs as damping paints, because inexpensive
inorganic fillers can be compounded into paint films.
EXAMPLES
[0045] Hereinafter, it will be described specifically with
reference to examples.
Example No. 1
[0046] In the present example, a styrene-butadiene resin (SBR, Tg:
5.degree. C. and a gel ratio of 80%) whose butadiene content was
35% was used as a first granular resin, and an emulsion containing
the resin in amount of 55% by weight was used. Into the emulsion,
calcium carbonate (an average particle diameter of 20 .mu.m) as an
inorganic filler, and a dispersing agent, a running inhibitor
agent, and the like, were compounded as additives in a
predetermined amount, thereby preparing a paint composition recited
in Table 1. Note that, as for the inorganic filler (calcium
carbonate), those into which it was compounded in an amount of 200
parts by weight and 400 parts by weight with respect to 100 parts
by weight of the granular resin were prepared.
Example No. 2
[0047] Instead of the first granular resin of Example No. 1, a
styrene-butadiene resin whose Tg was 5.degree. C. and gel ratio was
70% was used. The other components are the same as those of Example
No. 1.
Example No. 3
[0048] Instead of the first granular resin of Example No. 1, a
styrene-butadiene resin whose Tg was 5.degree. C. and gel ratio was
60% was used. The other components are the same as those of Example
No. 1.
Comparative Example No. 1
[0049] Instead of the first granular resin of Example No. 1, a
styrene-butadiene resin whose Tg was 5.degree. C. and gel ratio was
90% was used. The other components are the same as those of Example
No. 1.
Comparative Example No. 2
[0050] Instead of the first granular resin of Example No. 1, a
styrene-butadiene resin whose Tg was 5.degree. C. and gel ratio was
50% was used. The other components are the same as those of Example
No. 1.
[0051] Table 1 sets forth the compounding composition of the
respective paint compositions. Note that, in Table 1, they are
designated as parts by weight of the water emulsion including water
in an amount of 45%.
[0052] After the aforementioned respective compositions thus
compounded were mixed by a high-speed stirrer to disperse, they
were stirred to defoam, and were used as paints for
application.
[0053] The paints were applied to a 70.times.150.times.0.8 (mm)
electrode position-coated steel plate so as to be
50.times.150.times.3.0 (mm), immediately after the application,
they were put in a drying oven, whose temperature was controlled at
140.degree. C., for 30 minutes to carry out baking and drying.
After the drying, the appearance of the paint films was observed,
and the paint films free from cracks and swelling were regarded as
being passed (.largecircle.). Table 1 sets forth the results.
[0054] As recited in Table 1, in Example Nos. 1 through 3 whose
water emulsion particles (first granular resin) exhibited a gel
ratio falling in a range of from 80% to 60%, paint films in which
the inorganic filler was compounded in an amount of 200 parts by
weight and 400 parts by weight with respect to 100 parts by weight
of the water emulsion (55 parts by weight of the first granular
resin) could form normal paint films when being baked at such a
high temperature as 140.degree. C.
[0055] However, in Comparative Example No. 1 whose water emulsion
particles exhibited such a high a gel ratio as 90%, cracks occurred
in both cases where the inorganic filler amount was 400 parts by
weight and 200 parts by weight. In Comparative Example No. 2 whose
water emulsion particles exhibited such a low a gel ratio as 50%,
the strength of the paint films was not sufficient so that swelling
occurred in both cases where the inorganic filler amount was 400
parts by weight and 200 parts by weight, and they thus did not
become normal paint films.
[0056] Therefore, when the gel ratio of the water emulsion
particles falls in a range of from 80% to 60%, it is understood
that, in paint films in which an organic filler is filled to higher
extent and whose thickness is 6 mm (after being dried), paints can
withstand the high-temperature baking at 140.degree. C. for 30
minutes.
[0057] Moreover, on the samples from which the normal paint films
were obtained, the damping property (loss factor) by means of a
cantilever method was measured. As for the measurement of the
damping property (loss factor), they were applied to a 10.times.220
X 0.8 (mm) steelplate so as to be 1.times.200.times.3.0 in
superficial density (after being dried), and were put in a drying
oven, whose temperature was controlled at 140.degree. C., for 30
minutes to carry out baking and drying. After drying, the coated
plates were used as test plates for assessment, and were examined
by a cantilever method so as to calculate the loss factor at the
secondary resonance point by a half-width method. Table 1 sets
forth the results together with the measurement conditions. Since
all of the paint films exhibited a loss factor of 0.1 or more, it
is understood that they were good as a paint film and could secure
stable performance at a measurement temperature of from 20.degree.
C. to 40.degree. C.
[0058] From the results, in the present water paint composition, it
is possible to confirm that heavy thickness paint films can be
obtained even under the high-temperature baking-drying
condition.
Comparative Example No. 3
[0059] In the comparative example, a styrene-butadiene resin whose
glass transition temperature Tg was -5.degree. C., gel ratio was
90% and butadiene content was 43% was used, and an emulsion
containing the resin in amount of 55% by weight was used. Into the
emulsion, calcium carbonate (an average particle diameter of 20
.mu.m) as an inorganic filler, and a dispersing agent, a running
inhibitor agent, and the like, were compounded as additives in a
predetermined amount, thereby preparing a paint composition recited
in Table 2. Note that, as for the inorganic filler (calcium
carbonate), those into which it was compounded in an amount of 200
parts by weight and 400 parts by weight with respect to 100 parts
by weight of the SBR were prepared.
Comparative Example No. 4
[0060] Instead of the SBR of Comparative Example No. 3, a
styrene-butadiene resin whose Tg was -5.degree. C., gel ratio was
80% and butadiene content was 43% was used. The other components
are the same as those of Comparative Example No. 3. Table 2 sets
forth the specific composition.
Comparative Example No. 5
[0061] Instead of the SBR of Comparative Example No. 3, a
styrene-butadiene resin whose Tg was -5.degree. C., gel ratio was
60% and butadiene content was 43% was used. The other components
are the same as those of Comparative Example No. 3. Table 2 sets
forth the specific composition.
Comparative Example No. 6
[0062] Instead of the SBR of Comparative Example No. 3, a
styrene-butadiene resin whose Tg was 30.degree. C., gel ratio was
80% and butadiene content was 28% was used. The other components
are the same as those of Comparative Example No. 3. Table 2 sets
forth the specific composition.
Comparative Example No. 7
[0063] Instead of the SBR of Comparative Example No. 3, a
styrene-butadiene resin whose Tg was 30.degree. C., gel ratio was
60% and butadiene content was 28% was used. The other components
are the same as those of Comparative Example No. 3. Table 2 sets
forth the specific composition.
Comparative Example No. 8
[0064] Instead of the SBR of Comparative Example No. 3, a
styrene-butadiene resin whose Tg was 30.degree. C., gel ratio was
50% and butadiene content was 28% was used. The other components
are the same as those of Comparative Example No. 3. Table 2 sets
forth the specific composition.
[0065] After the aforementioned respective compositions thus
compounded were mixed by a high-speed stirrer to disperse, they
were stirred to defoam, and were used as paints for
application.
[0066] The paints were applied to a 70.times.150.times.0.8 (mm)
electrode position-coated steel plate so as to be
50.times.150.times.3.0 (mm), immediately after the application,
they were put in a drying oven, whose temperature was controlled at
140.degree. C., for 30 minutes to carry out baking and drying.
After the drying, the appearance of the paint films was observed,
and the paint films free from cracks and swelling were regarded as
being passed (.largecircle.). Table 2 sets forth the results.
[0067] As recited in Table 2, when the SBRs making the water
emulsion particles exhibited a glass transition temperature Tg of
-5.degree. C. or 30.degree. C., no paint films which were free from
defects and whose thickness was as heavy as 5.0 mm were not
obtained in all of the SBRs. In Comparative Example No. 4,
Comparative Example No. 5 and Comparative Example No. 8, 3.0 mm and
4.0 mm paint films which were free from defects were obtained. Even
when the glass transition temperature Tg of the SBRs was -5.degree.
C. or 30.degree. C., outside the range of from 0 to 20.degree. C.,
it is understood that satisfactory paint films whose thickness was
from 3 to 4 mm approximately were obtained if the gel ratio was
appropriate or if the compounding proportion of the inorganic
filler was less.
[0068] On the samples from which the normal paint films were
obtained, the damping property (loss factor) by means of the
cantilever method was measured. Table 2 sets forth the results
together with the measurement conditions. Since all of the paint
films exhibited a loss factor of 0.1 or less depending on the
measurement temperatures, it is understood that they could not
secure stable performance as a paint film.
[0069] From the results, even when the gel ratio of the water
emulsion particles falls in a range of from 60% to 80%, it is
understood that, if the glass transition temperature falls outside
the range of from 0 to 20.degree. C., not only it is less likely to
obtain satisfactorily heavy thickness paint films, but also the
temperature range in which a good damping property is exhibited is
narrow even if they should be obtained.
Example No. 4
[0070] A water emulsion was obtained by mixing a water emulsion,
containing a styrene-butadiene resin (SBR and Tg: 5.degree. C.)
whose gel ratio was 80% and butadiene content was 35% in an amount
of 55% by weight, in an amount of 80 parts by weight as a granular
resin with another water emulsion, containing a styrene-acrylic
ester copolymer whose gel ratio was 10% and Tg was 50.degree. C.,
in an amount of 20 parts by weight as another granular resin. A
paint composition was labeled as Example No. 4 in which an
inorganic filler (calcium carbonate) was compounded in an amount of
400 parts by weight and a dispersing agent and a running inhibitor
agent were compounded in a summed amount of 20 parts by weight into
the resulting water emulsion.
Example No. 5
[0071] The compounding proportions of the granular resins of
Example No. 4 were changed so that an emulsion was used which was
obtained by mixing a water emulsion, containing a styrene-butadiene
resin (SBR and Tg: 5.degree. C.) whose gel ratio was 80% and
butadiene content was 35% in an amount of 55% by weight, in an
amount of 50 parts by weight as a granular resin with another water
emulsion of a styrene-acrylic ester copolymer whose gel ratio was
10% and Tg was 50.degree. C. in an amount of 50 parts by weight as
another granular resin. The other compositions are the same as
those of Example No. 4. The resulting paint composition was labeled
as Example No. 5.
Example No. 6
[0072] Instead of the water emulsion of Example No. 4, an emulsion
was used which was obtained by mixing a water emulsion, containing
a styrene-butadiene resin (SBR and Tg: 5.degree. C.) whose gel
ratio was 60% and butadiene content was 35% in an amount of 55% by
weight, in an amount of 80 parts by weight as a granular resin with
another water emulsion of a styrene-acrylic ester copolymer whose
gel ratio was 8% and Tg was 25.degree. C. in an amount of 20 parts
by weight as another granular resin. The other compositions are the
same as those of Example No. 4. The resulting paint composition was
labeled as Example No. 6.
Example No. 7
[0073] The compounding proportions of the water emulsion particles
of Example No. 4 were changed so that an emulsion was used which
was obtained by mixing a water emulsion, containing a
styrene-butadiene resin (SBR and Tg: 5.degree. C.) whose gel ratio
was 60% and butadiene content was 35% in an amount of 55% by
weight, in an amount of 50 parts by weight as a granular resin with
another water emulsion of a styrene-acrylic ester copolymer whose
gel ratio was 8% and Tg was 25.degree. C. in an amount of 50 parts
by weight as another granular resin. The other compositions are the
same as those of Example No. 4. The resulting paint composition was
labeled as Example No. 7.
Example No. 8
[0074] Instead of the water emulsion of Example No. 4, an emulsion
was used which was obtained by mixing a water emulsion, containing
a styrene-butadiene resin (SBR and Tg: 5.degree. C.) whose gel
ratio was 80% and butadiene content was 35% in an amount of 55% by
weight, in an amount of 80 parts by weight as a granular resin with
another water emulsion of a styrene-acrylic ester copolymer whose
gel ratio was 12% and Tg was 55.degree. C. in an amount of 20 parts
by weight as another granular resin. The other compositions are the
same as those of Example No. 4. The resulting paint composition was
labeled as Example No. 8.
Example No. 9
[0075] Instead of the water emulsion of Example No. 4, an emulsion
was used which was obtained by mixing a water emulsion, containing
a styrene-butadiene resin (SBR and Tg: 5.degree. C.) whose gel
ratio was 80% and butadiene content was 35% in an amount of 55% by
weight, in an amount of 90 parts by weight as a granular resin with
another water emulsion of a styrene-acrylic ester copolymer whose
gel ratio was 10% and Tg was 50.degree. C. in an amount of 10 parts
by weight as another granular resin. The other compositions are the
same as those of Example No. 4. The resulting paint composition was
labeled as Example No. 9.
Example No. 10
[0076] Instead of the water emulsion of Example No. 4, an emulsion
was used which was obtained by mixing a water emulsion, containing
a styrene-butadiene resin (SBR and Tg: 5.degree. C.) whose gel
ratio was 60% and butadiene content was 35% in an amount of 55% by
weight, in an amount of 40 parts by weight as a granular resin with
another water emulsion of a styrene-acrylic ester copolymer whose
gel ratio was 10% and Tg was 50.degree. C. in an amount of 60 parts
by weight as another granular resin. The other compositions are the
same as those of Example No. 4. The resulting paint composition was
labeled as Example No. 10.
Comparative Example No. 9
[0077] An emulsion was used which was obtained by mixing a water
emulsion, containing a styrene-butadiene resin (SBR and Tg:
5.degree. C.) whose gel ratio was 90% and butadiene content was 35%
in an amount of 55% by weight, in an amount of 80 parts by weight
as a granular resin with another water emulsion of a
styrene-acrylic ester copolymer whose gel ratio was 8% and Tg was
25.degree. C. in an amount of 20 parts by weight as another
granular resin. The other compositions are the same as those of
Example No. 4. The resulting paint composition was labeled as
Comparative Example No. 9.
Comparative Example No. 10
[0078] The compounding proportions of the water emulsion particles
of Comparative Example No. 9 were changed so that an emulsion was
used which was obtained by mixing a water emulsion, containing a
styrene-butadiene copolymer (SBR and Tg: 5.degree. C.) whose gel
ratio was 90% and butadiene content was 35% in an amount of 55% by
weight, in an amount of 50 parts by weight as a granular resin with
another water emulsion of a styrene-acrylic ester copolymer whose
gel ratio was 8% and Tg was 25.degree. C. in an amount of 50 parts
by weight as another granular resin. The other compositions are the
same as those of Example No. 4. The resulting paint composition was
labeled as Comparative Example No. 10.
[0079] Table 3 sets forth the compounding composition of the
respective paint compositions of aforementioned Example No. 4
through Example No. 10 as well as Comparative Example Nos. 9 and
10. After the respective paint compositions were mixed by a
high-speed stirrer to disperse, they were stirred to defoam, and
were used as paints for application.
[0080] The paints were applied to a 70.times.150.times.0.8 (mm)
electrode position-coated steel plate so as to be
50.times.150.times.3.0 (mm), immediately after the application,
they Were put in a drying oven, whose temperature was controlled at
140.degree. C., for 30 minutes to carry out baking and drying.
After the drying, the appearance of the paint films was observed,
and the paint films free from cracks and swelling were regarded as
being passed (.largecircle.). Table 3 sets forth the results.
[0081] As recited in Table 3, in Example Nos. 4 through 7 in which
a water emulsion whose glass transition temperature (Tg) was
5.degree. C. and gel ratio was from 80 to 60% was mixed in an
amount of from 80 to 50 parts by weight as a granular resin with
another water emulsion whose glass transition point (Tg) was from
25.degree. C. to 50.degree. C. in an amount of from 20 to 50 parts
by weight as another granular resin, normal paint films which had
such a heavy thickness as 8.0 mm could be formed when paint films
in which the inorganic filler was compounded in an amount of 400
parts by weight with respect to 100 parts by weight of the granular
resins were baked at such a high temperature as 140.degree. C.
[0082] In Example No. 8 in which a water emulsion whose glass
transition temperature (Tg) was 5.degree. C. and gel ratio was 80%
was mixed in an amount of 80 parts by weight as a granular resin
with another water emulsion whose glass transition temperature (Tg)
was 55.degree. C. in an amount of 20 parts by weight as another
granular resin, a paint film which had a thickness of 5.0 mm could
be obtained, but cracks occurred in paint films which had such a
heavy thickness as 6.0 mm or more.
[0083] In Example No. 9 in which a water emulsion whose glass
transition temperature (Tg) was 5.degree. C. and gel ratio was 80%
was mixed in an amount of 90 parts by weight as a granular resin
with another water emulsion whose glass transition temperature (Tg)
was 50.degree. C. in an amount of 10 parts by weight as another
granular resin, a paint film which had a thickness of 6.0 mm could
be obtained, but swelling occurred in paint films which had such a
heavy thickness as 7.0 mm or more.
[0084] In Example No. 10 in which a water emulsion whose glass
transition temperature (Tg) was 5.degree. C. and gel ratio was 60%
was mixed in an amount of 40 parts by weight as a granular resin
with another water emulsion whose glass transition temperature (Tg)
was 50.degree. C. in an amount of 60 parts by weight as another
granular resin, a paint film which had a thickness of 5.0 mm could
be obtained, but cracks occurred in paint films which had such a
heavy thickness as 6.0 mm or more.
[0085] From the facts, when the mixing amount of the granular resin
of the water emulsion whose glass transition temperature (Tg) falls
in a range of from 25 to 50.degree. C. exceeds 50% of all the
water-emulsion granular resins, or when the water emulsion whose
glass transition temperature (Tg) exceeds 50.degree. C. is the
granular resin, paint films become brittle because the formation of
paint films is slow in baking and drying, and accordingly cracks
occur. Moreover, when it is less than 20% of all the water-emulsion
granular resins, or when the glass transition temperature (Tg) is
less than 25.degree. C., the action of promoting the evaporation of
water is insufficient in the initial period of baking and drying,
and consequently swelling occurs in paint films which have such a
heavy thickness as 8.0 mm.
[0086] Moreover, on the samples from which the normal paint films
were obtained, the damping property (loss factor) by means of a
cantilever method was measured. As for the measurement of the
damping property (loss factor), they were applied to a
10.times.220.times.0.8 (mm) steelplate so as to be
10.times.200.times.3.0 in superficial density (after being dried),
and were put in a drying oven, whose temperature was controlled at
140.degree. C., for 30 minutes to carry out baking and drying.
After drying, the coated plates were used as test plates for
assessment, and were examined by a cantilever method so as to
calculate the loss factor at the secondary resonance point by a
half-width method. Table 3 sets forth the results together with the
measurement conditions. Excepting the case where the paint film of
Example No. 10 was examined at a measurement temperature of
20.degree. C., since all of the paint films exhibited a loss factor
of 0.1 or more, it is understood that they were good as a paint
film and could secure stable performance at a measurement
temperature of from 20.degree. C. to 40.degree. C.
1TABLE 1 Gel Ratio Ex. No. 1 Ex. No. 2 Ex. No. 3 Comp. Ex. No. 1
Comp. Ex. No. 2 Water 90% 100* Emulsion 80% 100* Resin 70% 100*
(Styrene- 60% 100* Butadiene 50% 100* Copolymer) Tg: 5.degree. C.
(Resinous Content, 55%) Calcium Carbonate 400 200 400 200 400 200
400 200 400 200 Additives (Dispersing 20 20 20 20 20 Agent &
Running Inhibitor Agent) State of Dry 3.0 mm .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. X X X X Paint (Swollen) (Swollen) (Swollen) (Swollen)
Film after Dry 4.0 mm .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. -- -- -- -- Baking and
Dry 5.0 mm .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. X X X X Drying** (Cracked) (Cracked)
(Swollen) (Swollen) Dry 6.0 mm .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. -- -- -- --
Dry 7.0 mm X X X X X X X X X X (Cracked) (Cracked) (Cracked)
(Swollen) Swollen) (Swollen) (Cracked) (Cracked) (Swollen)
(Swollen) Dry 8.0 mm X X X X X X -- -- -- -- (Cracked) (Cracked)
(Cracked) (Swollen) (Swollen) (Swollen) Damping Measurement 0.15
0.14 0.14 0.15 0.14 0.15 -- -- -- -- Property Temp. 20.degree. C.
(Loss Measurement 0.14 0.12 0.14 0.14 0.15 0.13 -- -- -- --
Factor)*** Temp. 30.degree. C. Measurement 0.11 0.10 0.11 0.10 0.11
0.11 -- -- -- -- Temp. 40.degree. C. *Resinous Content (Parts by
Weight) **State of Pant Film: .largecircle., Free from Cracks and
Swelling & X, Cracks or Swelling Occurred ***Measurement
Conditions: Cantilever Method, Substrate 0.8t & Superficial
Density 3.0 kg/m.sup.2
[0087]
2TABLE 2 Gel Comp. Ex. Comp. Ex. Comp. Ex. Ratio No. 3 No. 4 No. 5
Water Emulsion 90% 100* Resin 80% 100* (Styrene- 60% 100* Butadiene
Copolymer) (Tg: -5.degree. C., Resinous Content: 55%) Water
Emulsion 80% Resin 60% (Styrene- 50% Butadiene Copolymer) (Tg:
30.degree. C., Resinous Content: 55%) Calcium Carbonate 400 200 400
200 400 200 Additives (Dispersing 20 20 20 Agent & Running
Inhibitor Agent) State of Paint Dry X X .largecircle. .largecircle.
.largecircle. .largecircle. Film after 3.0 mm (Cracked) (Swollen)
Baking and Dry X X .largecircle. X .largecircle. X Drying** 4.0 mm
(Cracked) (Swollen) (Swollen) (Swollen) Dry X X X X X X 5.0 mm
(Cracked & (Cracked & (Swollen) (Swollen) (Swollen)
(Swollen) Swollen) Swollen) Dry X X X X X X 6.0 mm (Cracked &
(Cracked & (Swollen) (Swollen) (Swollen) (Swollen) Swollen)
Swollen) Dry X X X X X X 7.0 mm (Cracked & (Cracked &
(Cracked & (Cracked & (Swollen) (Swollen) Swollen) Swollen)
Swollen) Swollen) Dry X X X X X X 8.0 mm (Cracked & (Cracked
& (Cracked & (Cracked & (Swollen) (Swollen) Swollen)
Swollen) Swollen) Swollen) Damping Measurement -- -- 0.14 0.14 0.14
0.13 Property (Loss Temp. Factor)*** 20.degree. C. Measurement --
-- 0.09 0.08 0.10 0.08 Temp. 30.degree. C. Measurement -- -- 0.04
0.03 0.05 0.04 Temp. 40.degree. C. Gel Comp. Ex. Comp. Ex. Comp.
Ex. Ratio No. 6 No. 7 No. 8 Water Emulsion 90% Resin 80% (Styrene-
60% Butadiene Copolymer) (Tg: -5.degree. C., Resinous Content: 55%)
Water Emulsion 80% 100* Resin 60% 100* (Styrene- 50% 100* Butadiene
Copolymer) (Tg: 30.degree. C., Resinous Content: 55%) Calcium
Carbonate 400 200 400 200 400 200 Additives (Dispersing 20 20 20
Agent & Running Inhibitor Agent) State of Paint Dry X X X X X
.largecircle. Film after 3.0 mm (Swollen) (Swollen) (Swollen)
(Swollen) (Swollen) Baking and Dry X X X X X X Drying** 4.0 mm
(Cracked) (Cracked) (Cracked) (Cracked) (Cracked & (Cracked
& Swollen) Swollen) Dry X X X X X X 5.0 mm (Cracked) (Cracked)
(Cracked) (Cracked) (Cracked & (Cracked & Swollen) Swollen)
Dry X X X X X X 6.0 mm (Cracked) (Cracked) (Cracked) (Cracked)
(Cracked & (Cracked & Swollen) Swollen) Dry -- -- -- -- --
-- 7.0 mm Dry -- -- -- -- -- -- 8.0 mm Damping Measurement -- -- --
-- -- 0.06 Property (Loss Temp. Factor)*** 20.degree. C.
Measurement -- -- -- -- -- 0.09 Temp. 30.degree. C. Measurement --
-- -- -- -- 0.15 Temp. 40.degree. C. *Resinous Content (Parts by
Weight) **State of Pant Film: .largecircle., Free from Cracks and
Swelling & X, Cracks or Swelling Occurred
[0088]
3 TABLE 3 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Comp. Comp. No. 4 No. 5 No. 6
No. 7 No. 8 No. 9 No. 10 Ex. 9 No. 10 Styrene- Gel Ratio, 90% 80*
50* Butadiene Gel Ratio, 80% 80* 50* 80* 90* Copolymer Gel Ratio,
60% 80* 50* 40* Tg: 5.degree. C. (Resinous Content, 55%) Styrene-
Glass 20* 50* 20* 50* Acrylic ester Transition Copolymer Temp.
(Tg), Gel Ratio, 25.degree. C. 10% Glass 20* 50* 10* 60* (Resinous
Transition Content, Temp. (Tg), 52%) 50.degree. C. Glass 20*
Transition Temp. (Tg), 55.degree. C. Calcium Carbonate 400 400 400
400 400 400 400 400 400 Additives (Dispersing 20 20 20 20 20 20 20
20 20 Agent & Running Inhibitor Agent) State of Dry 3.0 mm
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. X X Paint (Cracked)
(Cracked) Film after Dry 4.0 mm .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. X X Baking and (Cracked) (Cracked) Drying** Dry 5.0
mm .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. X X (Cracked) (Cracked)
Dry 6.0 mm .largecircle. .largecircle. .largecircle. .largecircle.
X .largecircle. X X X (Cracked) (Cracked) (Cracked) (Cracked) Dry
7.0 mm .largecircle. .largecircle. .largecircle. .largecircle. X X
X X X (Cracked) (Swollen) (Cracked) (Cracked) (Cracked) Dry 8.0 mm
.largecircle. .largecircle. .largecircle. .largecircle. X X X X X
(Cracked) (Swollen) (Cracked) (Cracked) (Cracked) Damping
Measurement 0.13 0.12 0.14 0.11 0.12 0.15 0.09 -- -- Property Temp.
20.degree. C. (Loss Measurement 0.17 0.15 0.18 0.14 0.16 0.15 0.12
-- -- Factor)*** Temp. 30.degree. C. Measurement 0.15 0.18 0.14
0.17 0.15 0.12 0.19 -- -- Temp. 40.degree. C. *Resinous Content
(Parts by Weight) **State of Pant Film: .largecircle., Free from
Cracks and Swelling & X, Cracks or Swelling Occurred
***Measurement Conditions: Cantilever Method, Substrate 0.8t &
Superficial Density 3.0 kg/m.sup.2
* * * * *