Industrial Field of Application
[0001] This invention concerns slurry compositions for especially cast molding purposes,
a method of molding cast moldings wherein these slurry compositions are used, and
sinters wherein these molding have been fired.
Prior Art
[0002] Conventionally, with cast molding in the molding of porcelain and ceramics, the cast
moldings have been formed by adding suitable amounts of water and deflocculating agents,
for example, to the prescribed base materials and preparing a slurry, pouring this
into a casting mold, such as a plaster mold which takes up water, thickening the slurry
along the inner surface of the mold by the uptake of water by the mold, and removing
the cast molding from the mold after thickening. The final molding has then been obtained
from the cast molding by processes such as drying, pre-baking, glazing, firing and
cutting etc., but when such a method is used the cast molding itself must have a mechanical
strength such that it can be handled in the finishing process and in transportation,
for example, and it must also be easily removed from the mold.
[0003] For this reason, when manufacturing porcelain in the past, the mechanical strength
needed for processing has been imparted by including kawazume clay or kibushi clay,
for example, in the base material. However, the mechanical strength of the moldings
has been inadequate in large and thin moldings with the conventional base for porcelain
purposes, and manufacture has been very difficult.
[0004] Furthermore, it has not been possible to mold cast moldings of adequate mechanical
strength with just the base for ceramic purposes in practice when manufacturing ceramics.
[0005] A method wherein aqueous resin emulsions are added to the porcelain base material
or ceramic base material and a ceramic slurry is prepared and cast molded has been
proposed as means of resolving these past difficulties (see Japanese Patent H3-64465),
and methods wherein water-soluble binders or aqueous resin emulsions are added to
the ceramic base material and a ceramic slurry is prepared and cast molded have been
proposed (see Japanese Patent H4-32155 and Japanese Patent Kokai H5-104509).
Problems to be Resolved by the Invention
[0006] The methods of resolution mentioned above enable the strength of the cast moldings
to be increased by the addition of an aqueous resin emulsion or a water-soluble binder,
but they have the following disadvantages.
(1) Firstly, the aqueous resin emulsions and water-soluble binders have water, for
example, pre-added in view of their nature, and they are added to slurried base material
for porcelain purposes or base material for ceramic purposes to prepare the slurry,
and so foam is formed during stirring and mixing, and then the mechanical strength
of the slurry composition for cast molding is liable to be reduced.
(2) Secondly, the density difference between the base material for porcelain purpose
or the base material for ceramic purposes and the aqueous resin emulsion, for example,
is considerable and so separation is liable to occur, a uniformly dispersed slurry
is not formed and so cracks are liable to form in the cast molding.
(3) Thirdly, the aqueous resin emulsion or water-soluble binder permeates into the
casting mold itself when the slurry is being dewatered at the time of cast molding,
and separation from the mold becomes difficult.
(4) Fourthly, the resin fraction of the aqueous resin emulsion coagulates in the surface
layer part of the cast molding and it is liable to become tacky, and the surface finishing
properties with cast moldings such as wide flat plates become poor and, moreover,
when such cast moldings are being subjected to enforced drying, the drying of the
inner part is delayed by the formation of a film due to surface drying, and warping
and cracking, for example, are liable to occur.
[0007] As a result of thorough research carried out with a view to resolving the abovementioned
past problems, the inventors have discovered that cast moldings which have excellent
mechanical strength, thickening rate and mold release properties, for example, can
be obtained by adding redispersible resin powder to base material and water, and preparing
a slurry composition in which this is uniformly dispersed in a stable manner by mixing,
and the invention is based upon this discovery.
Means of Resolving These Problems
[0008] The first invention of this application is a slurry composition especially for cast
molding purposes, characterized in that 0.5 - 20 parts by weight of redispersible
resin powder, and water, are added to, and mixed with, 100 parts by weight of the
prescribed base material for cast molding purposes, such as porcelain base material
or ceramic base material.
[0009] The second invention of this application is a method of molding cast moldings, characterized
in that the abovementioned slurry composition is cast molded.
[0010] The third invention of this application is a sinter, characterized in that a molding
which has been cast molded according to the abovementioned method is fired.
[0011] The known porcelain raw materials, such as feldspar, silica, pottery stone, kaolin
and clay for example, can be used for the porcelain base material in this present
invention, and the known ceramic raw materials, such as alumina, zirconia, silica,
ferrite, silicon carbide, silicon nitride or saialon for example, can be used for
the ceramic base material. These porcelain base materials and ceramic base materials
can eachbe used individually, or they can be used in a suitable formulation, as required.
Below, the prescribed base materials for cast molding purposes, such as porcelain
base materials and ceramic base materials for example, are referred to simply as the
base material.
[0012] Furthermore, a so-called redispersible resin powder which has been obtained by spray
drying for example a poly(vinyl acetate), vinyl acetate copolymer or acrylic resin-based
emulsion is used for the redispersible resin powder. The glass transition temperature
of this redispersible resin powder is preferably -5°C or above, from the viewpoint
of ideal film formation on molding, and in those cases where it is below -5°C it is
liable to undergo cohesion and attachment and, conversely, if the glass transition
temperature is too high then the film formation on molding is liable to become inadequate,
and so a glass transition temperature of 0 - 20°C is preferred. Moreover, in those
cases where a redispersible resin which has a high glass transition temperature is
used, the drying temperature may be raised or the time may be increased, or a plasticizer
or a film forming promoter may be added. Furthermore, the amount of redispersible
resin powder which is added to the base material differs according to the type of
base material, the type of redispersible resin powder and the characteristics of the
sinter which is to be manufactured, for example, but it is generallY 0.5 - 20 parts
by weight. In those cases where the amount of redispersible resin powder which is
added is less than 0.5 parts by weight with respect to the base material, the mechanical
strength of the moldings becomes inadequate, and in those cases where it exceeds 20
parts by weight the mechanical strength is good, but the shrinkage on firing is considerable,
and not only is the fall in the strength of the sinter considerable and removal from
the mold when carrying out the cast molding treatment difficult, but the characteristics
of the base material are liable to be diminished.
[0013] These redispersible resin powders are available commercially with trade names such
as, for example, Sumikafurekksu (registered trademark) RP-100S and RP-110 (manuf actured
by Sumitomo Kagaku Kogyo K.K., Akuronarru (registered trademark) DS-6029 and DS-6031
manufactured by the Mitsubishi Yuka Baadeisshe K.K., and Movinyl (registered trademark)
DM200, DM289, 843, SA and E45 manufactured by Hoechst Kasei K.K.
[0014] Furthermore, in addition, water is preferably added as a dispersing agent in such
a way that the slurry solid fraction content is 65 - 80 percent by weight. Moreover,
apart from water, inorganic deflocculating agents such as caustic soda, sodium silicate
and water glass, organic deflocculating agents such as diethylamine, di-n-propylamine
and pyridine, protective colloids such as humic acid, tannic acid and lignin, and
pulverization promoters such as stearic acid, oleic acid and naphthenic acid, can
be added, as required.
[0015] The slurry is prepared by adding the prescribed amount of redispersible resin powder
to the base material and adding the water and deflocculating agent, as required, and
pulverizing with a known type of pulverizing machine, such as a ball mill or a tube
mill for example, to 0.1 - 10 um. At this time, the redispersible resin powder is
a powder and so when compared with a conventional aqueous resin emulsion, foaming
does not occur, and the separation which accompanies any difference in density from
the base material, and re-coagulation, do not occur, and it is uniformly dispersed
in a very stable manner, and a slurry of the correct viscosity is prepared ideally.
Furthermore, the redispersible resin powder is uniformly dispersed in a stable manner
and so the prepared slurry can be stored as a slurry. Moreover, the base material
and water may be formed into a slurry and the redispersible resin powder may be added
to, and mixed with, this slurry, but since it is difficult to disperse, much time
is required for dispersion, and warping and cracking are liable to occur at the time
of casting, and so the base material and the redispersible resin powder are preferably
formed into a slurry at the same time.
[0016] The slurry obtained is poured into a casting mold, such as a plaster mold for example,
using the known method, and a casting mold is molded and, after thickening along the
inner surface of the mold by the mold taking up water, it is removed from the mold.
At this time, as has been described above, a slurry of this present invention is such
that, because the redispersible resin powder is uniformly dispersed in a very stable
manner, the mechanical strength of the cast molding is of course considerable, and
the thickening rate is also appropriate, and the molding can be removed from the mold
very smoothly and easily. An especially marked effect is seen in the mold release
of thin moldings. Furthermoree thin, light and large cast moldings can be molded easily
and not just the cast moldings of the conventional forms.
[0017] The casting mold which has been removed from the mold is subjected to an appropriate
drying treatment and then fired using the known methods, and a sinter is formed. At
this time, the slurry which forms the cast molding has a form in which the redispersible
resin powder is uniformly dispersed in a stable manner and so there is no risk at
all of warping or cracking occurring during the drying treatment or during the firing
treatment.
Illustrative Examples
[0018] Examples of the invention are described below, but the invention is not limited by
these examples.
Examples 1 - 6 and Comparative Examples 1 - 4
[0019] Redispersible resin powder, or aqueous resin emulsion (represented as a solid fraction)
was added to a base material on the basis of the formulation proportions shown in
Table 1, sodium silicate was added along with the water, and the whole was mixed in
a ball mill to prepare a slurry.
[0020] The slurries which had been prepared were poured into plaster molds of two types
of length 500 mm and width 500 mm, and of depth 2 mm or 5 mm, and cast moldings were
obtained on standing for 1 hour, after which the moldings were removed from the mold
and dried for 24 hours at normal temperature and then for 24 hours at 110°C. An evaluation
of warping and cracking during this process was made on the basis of the standards
indicated below. The results are shown in Table 2.
Mold Release Properties
[0021]
- O:
- Released easily from the mold.
- A:
- Some sticking to the plaster mold but could be released.
- x:
- Stuck to the plaster, mold cracks etc. formed and it was difficult to remove from
the mold.
Warping and Cracking
[0022]
- O:
- No warping or cracking at all, or virtually none at all.
- x:
- Warping and cracking occurred.
[0023] Furthermore, cast moldings were obtained in the same way by pouring the abovementioned
slurries into plaster molds of length 110 mm, width 15 mm and depth 6 mm, leaving
to stand for 1 hour and removing the moldings from the molds, and then drying for
24 hours at 20°C and then for 24 hours at 110°C. Next, the cast moldings were heated
gradually to 1230°C over a period of 5 hours and then fired for 1 hour at 1230°C.
After this, they were left to stand and cooled for 4 hours and sinters were obtained.
The flex strengths after drying at 20°C before firing, after drying at 110°C and after
firing, and the shrinkage factors during firing and the water uptakes were measured
using the methods indicated below. The results are shown in Table 2.
[0024] Flex Strength: The flex strength was measured in accordance with JIS R1601-81.
Shrinkage Factor (Wt = weight)
[0025] 
Water Uptake
[0026] 
[0027] Moreover, the weight after 3 hours in water at 80°C was measured by removing the
sample from the water and wiping of the surface water. Furthermore, the weight after
drying was the weight after standing for 24 hours at 20°C - 65% after drying.
Effect of the Invention
[0028] According to this present invention, as indicated above, 0.5 - 20 parts by weight
of redispersible resin powder, and water, are added to, and mixed with, 100 parts
by weight of the prescribed base material for cast molding purposes, such as base
material forporcelain purposes and base material for ceramic purposes, and so a slurry
composition in which the redispersible resin powder is dispersed uniformly in a very
stable manner can be prepared. Furthermore, the slurry composition in which the redispersible
resin powder has been dispersed uniformly in a stable manner is cast molded and so
it is possible to mold cast moldings which have exceedingly good mechanical strength,
thickening rates and mold release properties for example. Furthermore, since it is
possible to mold cast moldings of which the mechanical- strength is greatly improved,
as mentioned above, it is possible to manufacture sinters which are thin, light or
large when compared to the products of the conventional form.
Table 2
|
|
1 |
1 |
1 |
1 |
1 |
1 |
2 |
2 |
2 |
2 |
3 |
2 mm* |
0 |
0 |
0 |
△ |
0 |
0 |
x |
x |
x |
x |
5 mm* |
0 |
0 |
0 |
△ |
0 |
0 |
0 |
x |
x |
△ |
5 |
2 mm* |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
x |
0 |
0 |
5 mm* |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
x |
0 |
0 |
6 |
7 |
30,1 |
40,2 |
77,3 |
95,6 |
64,5 |
30,5 |
23,9 |
33,5 |
109,9 |
20,8 |
8 |
34,2 |
45,7 |
91,1 |
121,5 |
72,5 |
- |
25,7 |
12 |
- |
- |
9 |
919 |
973 |
919 |
853 |
903 |
107 |
898 |
13 |
710 |
125 |
10 |
|
6,9 |
7,1 |
7,7 |
8,8 |
8,4 |
- |
7,5 |
- |
10,2 |
- |
11 |
|
6,3 |
6,2 |
6,2 |
7,3 |
6,6 |
- |
5,7 |
- |
8,3 |
- |
KEY 1: Example, 2: Comparative Example, 3: Mold Release Properties, 4: Thickness,
5: Warping and Cracking, 6: Mechanical Strength (kgf/cm²), 7: After drying at 20°C,
8: After drying at 110°C, 9: After firing, 10: Shrinkage Factor (%), 11: water Uptake
(%), 12: Cracks formed, confirmation impossible., 13: As above. |