Paint resembling stained glass

Disclosed herein are paints comprising 100 parts by weight of a paint composition composed of as main ingredients 4 to 17% by weight of an urethane resin, 0.1 to 17% by weight of a coloring agent, and the balance of an acrylic ester based resin, the ratio (% by weight) of said acrylic ester based resin to said urethane resin being 83-95: 17-5; and 90 to 150 parts by weight of water.

BACKGROUND OF THE INVENTION 
The present invention relates to paints comprising an acrylic ester based 
resin as a base. More particularly, the present invention relates to 
paints specifically designed to be used for making artistic plastic 
objects or products a la stained glass, which won't cause elution and 
elimination of coloring agents from the artistic plastic objects even when 
immersed in hot water. 
Generally, the paints such as "Stained Color", are a colored composition 
with which it is possible to make artistic plastic objects or products 
with coloration a la stained glass by merely applying the paint on a 
transparent plate such as a glass plate or transparent synthetic resin 
plate. The paints are commercially sold in many brands, especially for 
juvenile or infant users in recent years. 
The aqueous emulsion of an acrylic ester based resin which is the main 
ingredient of the paints, is capable of forming a very beautiful 
transparent film, so that even children can easily create a beautiful 
stained glass-like artistic object with these paints. Further, it is 
possible to make any desired coloration by simply mixing the paints. Thus, 
the demand for these paints is steadily increasing. 
However, from the artistic plastic objects obtained by using not only the 
paints containing an acrylic ester based resin as a base but also the 
paints containing other resins as a base, a substantial amount of the 
coloring agents contained therein is eluted when immersed in hot water of 
40.degree. C. for a certain period of time such as 10 minutes, and the 
eluted coloring agents tend to be released from the surface of the 
artistic plastic objects, so that these paints have the problem that they 
are liable to stain the clothes of the juvenile or infant users, not to 
mention the sanitary problem. 
As a result of the present inventor's earnest studies for overcoming the 
above problems, it has been found that paints obtained by adding pertinent 
coloring agents to an aqueous emulsion of a resinous mixture composed of 
an acrylic ester based resin as base and an urethane resin, won't cause 
elusion of coloring agents even when artistic plastic objects formed by 
applying the paints on a transparent plate are immersed in hot water, and 
are also safe in terms of sanitation. The present invention has been 
attained on the basis of this finding. 
SUMMARY OF THE INVENTION 
The object of present invention is to provide paints usable for forming 
artistic plastic objects a la stained glass, which won't cause elusion of 
coloring agents from the artistic plastic objects even when immersed in 
hot water, are free of sanitary problems and also have no possibility of 
staining the clothes of the juvenile or infant users. 
In a first aspect of the present invention, there is provided paints 
comprising 100 parts by weight of a paint composition composed of as main 
ingredients 4 to 17% by weight of an urethane resin, 0.1 to 10% by weight 
of a coloring agent and the balance of an acrylic ester based resin, the 
ratio (% by weight) of said acrylic ester based resin to said urethane 
resin being 83-95: 17-5; and 90 to 150 parts by weight of water. 
In a second aspect of the present invention, there is provided paints 
comprising 100 parts by weight of an aqueous emulsion of an acrylic ester 
based resin, 7 to 20 parts by weight of an aqueous dispersion of a 
colloidal or semicolloidal urethane resin and a coloring agent. 
In a third aspect of the present invention, there is provided artistic 
plastic objects a la stained glass obtained by applying the paints of 
first aspect or second aspect on a transparent base plate.

DETAILED DESCRIPTION OF THE INVENTION 
The acrylic ester based resin used as base in the present invention is a 
resin of an acrylic ester or a derivative thereof. Examples of such 
acrylic ester based resin include polymers (homopolymers or copolymers) of 
acrylic esters or derivatives thereof (refer to as "acrylic ester resins") 
, copolymers of acrylic esters or derivatives thereof and other monomers 
such as styrene or derivatives thereof (refer to as "acrylic ester-styrene 
copolymer") , and mixtures of the said polymers and/or copolymers. More 
specifically, as the acrylic ester resins, polymethylacrylate, 
polyethylacrylate, polybutylacrylate, poly(2-ethyl) hexylacrylate, 
polymethylmethacrylate, polyehtylmethacrylate, polybutylmethacrylate, 
poly(2-ethyl) hexylmethacrylate, acrylic ester-methacrylic ester copolymer 
and methyl methacrylate-2-ethylhexyl acrylate copolymer may be 
exemplified. As the acrylic ester-styrene copolymer, methyl 
acrylate-styrene copolymer, ethyl acrylate-styrene copolymer, butyl 
acrylate-styrene copolymer, methyl methacrylate-styrene Copolymer, ethyl 
methacrylate-styrene copolymer and butyl methacrylate-styrene copolymer 
may be exemplified. 
The molecular weight (weight-average molecular weight) of the acrylic ester 
based resins usable in the present invention is in the range of 50,000 to 
500,000. In case of using an acrylic ester resin, a polymer having a 
weight-average molecular weight of 50,000 to 300,000 is preferred, and in 
case of using the acrylic ester-styrene copolymer, a copolymer having a 
weight-average molecular weight of 100,000 to 500,000 is preferred. 
In the present invention, the acrylic ester based resin is used in the form 
an aqueous emulsion. 
The urethane resins usable in the present invention include soap-dispersion 
type ones and non-soap-dispersion type ones obtainable from reaction of 
aliphatic, alicyclic or aromatic diisocyanates and polyhydric alcohols. 
Especially, urethane resins obtained by using polyhydric alcohols with not 
less than trivalent hydroxyl value are preferred. Also, ether-type 
urethane resins are usable. 
The urethane resin used in the present invention is preferably the one 
having a molecular weight (weight-average molecular weight) in the range 
of 50,000 to 200,000, preferably 70,000 to 100,000. 
In the present invention, the urethane resin is used in the form of a 
colloidal or semicolloidal aqueous dispersion in which the urethane resin 
particles are uniformly dispersed in colloidal or semicolloidal form using 
if necessary, emulsifying agents. 
As the coloring agent used in the present invention, pigments and dyes are 
usable. As for pigments, fine particle pigments (the pigments with an 
average particle size of not more than 2 .mu.m, preferably 0.1 to 2 .mu.m) 
may be exemplified. As for dyes usable here, alcoholic dyes and acid dyes 
may be exemplified. 
Specifically, the fine particle pigments usable in the present invention 
include the following commercial products. CARBON BLACK (produced by Toyo 
Ink Co., Ltd.), HI-MICRON COLOR, PSM Blue HB (phthalocyanine based 
pigment) and PSM Pink KR (quinacridone based pigment) (both produced by 
Mikuni Color Works Ltd.). 
As the alcoholic dyes usable in the present invention, WOOD STAIN (produced 
by Washin Chemical Industry Co., Ltd.) may be exemplified. As the acid 
dyes usable here, LANYL BRILLIANT RED (produced by Sumitomo Chemical Co., 
Ltd.) may be exemplified. 
In order to produce the paints of the present invention, an aqueous 
emulsion of acrylic ester based resins, a colloidal or semicolloidal 
aqueous dispersion of urethane resins and coloring agents are mixed at a 
mixing ratio of 100 parts by weight of the aqueous emulsion of acrylic 
ester based resins, 7 to 20 parts by weight of the colloidal or 
semicolloidal aqueous dispersion of urethane resins and 0.08 to 9.0 parts 
by weight of coloring agents. The solid content of the said aqueous 
emulsion of acrylic ester based resins used in the present invention is 
preferably 40 to 50% by weight and the solid content of the said colloidal 
or semicolloidal aqueous dispersion of urethane resins is preferably 28 to 
40% by weight. The ratio (% by weight) of the solid content of the aqueous 
emulsion of acrylic ester based resins to the solid content of the 
colloidal or semicolloidal aqueous dispersion of urethane resins is 
preferably 83-95: 17-5. 
Namely, in the paints of the present invention, the content of the urethane 
resin is 4 to 17% by weight, preferably 4 to 12% by weight, more 
preferably 4.3 to 8.0% by weight, the content of the coloring agent is 0.1 
to 10% by weight, preferably 0.1 to 5% by weight, and the content of the 
acrylic ester based resin is the balance, preferably 73.0 to 95.9% by 
weight, more preferably 78.0 to 95.9% by weight, still more preferably 
87.0 to 95.6. Further the ratio (% by weight) of the acrylic ester based 
resin to the urethane resin is 83-95: 17-5. 
The paints according to the present invention comprise 100 parts by weight 
of a paint composition composed of an acrylic ester based resin, an 
urethane resin and a coloring agent, and 90 to 150 parts by weight, 
preferably 95 to 120 parts by weight of water. 
When the content of the urethane resin in the paint composition is less 
than 4% by weight, the elution of the coloring agent from the artistic 
plastic objects occurs. When the content of the urethane resins in the 
paint composition exceeds 17% by weight, the production cost increases, 
the long drying time of the artistic plastic objects is required and the 
obtained artistic plastic object become fragile. 
If the content of the urethane resin in the ratio (% by weight) of the 
acrylic ester based resin to the urethane resin is less than 5% by weight, 
there may take place elution and elimination (separation) of the coloring 
agent from the artistic plastic objects. If the content of the urethane 
resin in the ratio (% by weight) of the acrylic ester based resin to the 
urethane resin exceeds 17% by weight, the production cost increases, the 
long drying time of the artistic plastic objects is required and the 
obtained artistic plastic object become fragile. Therefore, it is 
essential in the paint composition of the present invention that the 
contents of the acrylic ester based resin and the urethane resin are in 
the above-defined ranges, and that the ratio (% by weight) of the acrylic 
ester based resin to the urethane resin is within the range of 83-95 to 
17-5. 
Then the content of the coloring agent in the paint composition exceeds 10% 
by weight, the bleeding of the coloring agent may take place. 
The paints according to the present invention are to provide low-viscosity 
type paints and high-viscosity type paints . 
The low-viscosity type paints are preferred for use as ordinary paints for 
stained glass, while the high-viscosity type paints are preferred for use 
as framer for stained glass . 
In case of making a seal a la stained glass, the framer which is the 
boundary of paint or the boundary between the paints is required to have a 
certain height for preventing diffusion or mixing of paints. Use of 
high-viscosity type paints is favorable for forming a framer with such a 
height. 
The low-viscosity type paints according to the present invention are of a 
viscosity of not more than 600 cps, preferably 40 to 500 cps (measured at 
a temperature of 20.degree. C. by B-type viscometer with No. 1 rotor 
rotated at 5 r.p.m.). The low-viscosity type paints are composed of 100 
parts by weight of the said paint composition which is composed of 4 to 
17% by weight of an urethane resin, 0.1 to 10% by weight of a coloring 
agent and 73.0 to 95.9% by weight of an acrylic ester based resin, the 
ratio (% by weight) of said acrylic ester based resin to said urethane 
resin being 83-95: 17-5; and 90 to 150 parts by weight of water as 
described above. 
The high-viscosity type paints are of a viscosity of not less than 10,000 
cps, preferably 40,000 to 80,000 cps (measured at a temperature of 
20.degree. C. by B-type viscometer with No. 5 rotor rotated at 5 r.p.m.). 
The high-viscosity type paint is composed of 100 parts by weight of a 
paint composition which is composed of 4 to 17% by weight of an urethane 
resin, 0.1 to 10% by weight of a coloring agent, the balance of an acrylic 
ester based resin, the ratio (% by weight) of said acrylic ester based 
resin to said urethane resin being 83-95: 17-5, and appropriate amounts of 
thickeners and thixotropic improving agents for obtaining the viscosity of 
not less than 10,000 cps; and 90 to 150 parts by weight of water. The 
preferable amount of the thickeners in the paint composition of the 
high-viscosity type paint is 0.5 to 3% by weight and the preferable amount 
of the thixotropic improving agents in the paint composition of the 
high-viscosity type paint is 0.003 to 1% by weight. As the thickeners used 
in the present invention, HUX-TA (produced by Asahi Denka Kogyo Kabushiki 
Kaisha) may be exemplified. As the thixotropic improving agents used in 
the present invention, XanthanGum-RHODOPOL 23 (produced by RHONE-POULENC 
JAPAN, LTD.) may be exemplified. In the paint composition of the 
high-viscosity type paint, the acrylic ester-styrene copolymer is 
preferably used for obtaining the viscosity of not less than 20,000 cps . 
The paints of the present invention may contain the additives used in 
ordinary paints, such as film-forming auxiliaries, antiseptic, ultraviolet 
absorber, etc. 
A process for producing the paints according to the present invention is 
described below. 
An acrylic ester based resin is added to water using if necessary, 
emulsifier to prepare an emulsion (A). If necessary, film-forming 
auxiliaries may be added. The aqueous emulsion of acrylic ester based 
resin of the present invention is preferably the one having a solids 
content of 40 to 50% by weight, a viscosity (measured at 30.degree. C. by 
B-type viscometer with No. 1 rotor rotated at 10 r.p.m.) of 80 to 150 cps, 
a pH of 7.0 to 9.0 and a minimal film-forming temperature (MFT) of about 
0.degree. C. Also, the aqueous emulsion of acrylic ester-styrene copolymer 
is preferably the one having a solids content of 45 to 55% by weight, a 
viscosity (measured at 30.degree. C. by B-type viscometer with No. 1 rotor 
rotated at 2.5 r.p.m.) of 2,000 to 12,000 cps, a pH of 7.5 to 10 and a 
minimal film forming temperature (MFT) of about 30.degree. C. 
A typical example of the aqueous emulsions of acrylic ester based resins 
usable in the present invention is PEGAR 755 (a commercial product, 
produced by Koatsu Gas Kogyo Co., Ltd.), and a typical example of the 
aqueous emulsions of acrylic ester-styrene copolymers is POLYSOL AP-4710 
(produced by Showa Highpolymer Co., Ltd.). 
Then, an urethane resin is added to water using if necessary, dispersing 
agents to form a colloidal or semicolloidal dispersion, and the resultant 
dispersion is added with a coloring agent and if necessary, an antiseptic 
and an ultraviolet absorber, and stirred to prepared to a dispersion (B). 
The aqueous dispersion of the urethane resin used in the present invention 
is a colloidal or semicolloidal dispersion having a solids content of 28 
to 40% by weight, a pH of 7.8 to 8.2 and a viscosity (measured at 
25.degree. C. by B-type viscometer) of 15 to 65 cps. 
An example of the aqueous dispersion of the urethane. resins is 
ADEKA-BON-TIGHTER, HUX-232 and HUX-260 (produced by Asahi Denka Kogyo 
Kabushiki Kaisha). 
The above aqueous emulsion (A) and aqueous dispersion (B) are mixed and 
stirred, and the resultant mixture is left still for defoaming to obtain 
paints. 
The paints obtained in the manner described above are applied on a 
transparent base plate such as glass plate, transparent synthetic resin 
plate or the like to make a stained glass-like artistic plastic object. 
When the obtained artistic plastic object after drying for 24 hours are 
immersed in hot water of 45.degree. C. for 20 minutes, there is observed 
no elution of the coloring agent from the artistic plastic object, 
indicating very excellent coloring agent-eluting resistance of the 
coloring agent from the artistic plastic object in 45.degree. C. hot 
water. 
The artistic plastic objects show a beautiful surface, good transparency 
and high painting film strength and presented no sanitary problem. 
The paints of the present invention are a mixture of an aqueous emulsion of 
an acrylic ester based resin with specified amounts of an aqueous 
dispersion of a colloidal or semicolloidal urethane resin and a coloring 
agent, and the coloring agent used therein has good compatibility with the 
urethane resin, so that the stained glass-like artistic plastic object 
made by applying such paints on a transparent base plate such as glass 
plate or transparent synthetic resin plate is proof against elution of the 
coloring agent, and therefore, has no possibility of staining the clothes 
of the user and is free of sanitary problem. Also, the artistic plastic 
objects can be kept for long with no fear of being disfigured. 
By selecting a transparent base plate having a smooth and releasable 
surface, it is possible to apply the paints on the base plate so as to 
copy faithfully the draft under the base plate. 
Also, since the drawing on the base plate can be easily separated from the 
base plate when dried, there can be obtained a seal of stained glass-like 
design faithful to the draft. 
As this seal is soft, it can be affixed and transferred to any smooth 
surface. Further, it is possible to draw a design not only on a curved 
surface but also at such a place where it is difficult to draw a design, 
such as the high portion of a glass window, demisted glass window of a 
bath room, tiles, toys with curvature, etc. 
Still further, as the paints of the present invention are capable of 
forming a film which can be freely varied in volume within the thickness 
of 3 mm, even a visually handicapped child can imagine the real entity of 
the drawn seal with a volume by hand touch. 
EXAMPLES 
The present invention will hereinafter be described with reference to the 
examples thereof, which examples, however, are merely intended to be 
illustrative and not to be construed as limiting the scope of the 
invention. 
Example 1 
82.4 g (solids: 38.3 g) of an acrylic ester based resin emulsion (PEGAR 
755, produced by Koatsu Gas Kogyo Co., Ltd., solids content: 46.5% by 
weight; viscosity (measured at a temperature of 30.degree. C. by B-type 
viscometer at No. 1 rotor speed of 10 r.p.m.): 130 cps; pH: 8.0; MFT: 
0.degree. C.) was weighed out by an electronic even balance (which has 
been used for weighing of the starting materials in this and following 
Examples) and supplied into a 300 cc beaker. Then 1 g of a film-forming 
auxiliary (EN-250, produced by Nippon Nyukazai Co., Ltd.) was added 
dropwise into the beaker and the resultant mixture therein was stirred 
slowly by a 9.3 mm.phi. glass rod for about 5 minutes. 
Meanwhile, 12 g (solids: 3.6 g; 14.5 parts by weight based on 100 parts by 
weight of the acrylic ester based resin emulsion) of an aqueous dispersion 
of an anion-type colloidal urethane resin (ADEKA-BON--TIGHTER, HUX 232, 
produced by Asahi Denka Kogyo Kabushiki Kaisha; solids content: 30% by 
weight; viscosity (measured at 25.degree. C. by B-type viscometer): 20 
cps; pH: 8.0) was weighed out and supplied into a 100 cc beaker, and then 
0.2 g of an antiseptics (PROXEL GXL, produced by ICI, Ltd.) , 0.4 g of an 
ultraviolet absorber (CIBATEX LFN, produced by Japan Ciba Geigy Corp. ) 
and 4 g of a coloring agent (WOOD STAIN (red) , an alcoholic dye, produced 
by Washin Chemical Industries Co., Ltd. ) were weighed out and added into 
the beaker, followed by stirring of the mixture in the beaker with a 9.3 
mm.phi. glass rod for about one minute. 
Then, the said urethane dispersion blended with the said antiseptics, 
ultraviolet absorber and coloring agent was added into the 300 cc beaker 
containing the said acrylic ester based resin emulsion mixed with the said 
film-forming auxiliaries, and the resultant mixture was stirred by a 
stirrer (TK HOMO DISPER, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 
about 300 r.p.m. for 20 minutes and then left still for about one hour for 
defoaming to obtain a paint (viscosity (measured at 20.degree. C. by 
B-type viscometer with No. 1 rotor rotated at 5 r.p.m.): 100-120 cps). 
Examples 2 and 3 
Paints were obtained by following the same procedure as Example 1 except 
that the amounts of the components were changed as shown in Table 1. The 
amount of the aqueous dispersion of colloidal urethane resin was 10.5 
parts by weight in Example 2 and 8.0 parts by weight in Example 3 based on 
100 parts by weight of the aqueous emulsion of acrylic ester based resin. 
Comparative Examples 1-4 
Paints were obtained according to the same procedure as Example 1 except 
that the amounts of the components were changed as shown in Table 2. The 
amount of the aqueous dispersion of colloidal urethane resin was 6.7 parts 
by weight in Comparative Example 1, 5.5 parts by weight in Comparative 
Example 2, 3.2 parts by weight in Comparative Example 3 and 2.1 parts by 
weight in Comparative Example 4 based on 100 parts by weight of the 
aqueous emulsion of acrylic ester based resin. 
Visual Observation 
The paints obtained in the above Examples and Comparative Examples were 
subjected to the tests on coloring agent elution in 45.degree. C. hot 
water, coating film transparency and film state of the artistic plastic 
objects obtained by drying for 24-hour. As shown in Tables 1 and 2, the 
paints obtained in Examples 1 to 3 all showed the good test results on 
each test item, while the paints obtained in Comparative Examples 1-4 gave 
a poor showing in all the test results. The paints of Examples ]to 3 were 
easy to apply because of good fluidity, and also the coating film thereof 
after dried was beautiful in the surface, had good transparency and high 
strength, and arose no problem relating to sanitation. 
For judgment of coloring agent elution in 45.degree. C. hot water, each 
product obtained by drying for 24-hour, was immersed in 45.degree. C. hot 
water for 20 minutes and judgment was conducted on the basis of whether a 
coloration of supernatant was visually observed or not after immersion for 
20 minutes. In rating the result, "C" mark was given when a coloration of 
supernatant was observed, "B" mark was given when a slight coloration of 
supernatant was observed, and "A" mark was given when no coloration of 
supernatant was observed. The mark "A" is required for putting to 
practical use. 
In the evaluation of film transparency, "A" mark was given when the film 
formed by applying a paint on a transparent plate was transparent, "B" 
mark was given when the film was slightly cloudy, and "C" mark was given 
when the film was cloudy. The mark "A" is required for putting to 
practical use. 
As for the film state, "C" mark was given when the formed film had cracks 
or wrinkles, "B" mark was given when the film had slight cracks or 
wrinkles, and "A" mark was given when the film was free of cracks and 
wrinkles. The mark "A" is required for putting to practical use. 
Example 4 
63 g (solids: 31.5 g) of an aqueous emulsion of an acrylic ester-styrene 
copolymer (POLYSOL AP4710, produced by Showa Polymer Co., Ltd.; solids 
content: 50% by weight; viscosity (measured at 30.degree. C. by B-type 
viscometer at No. 1 rotor speed of 2.5 r.p.m.): 6,000 cps; pH: 9; MFT: 
30.degree. C.) was weighed out and supplied into a 300 cc beaker. Then, 2 
g of a film-forming auxiliary (EN-250, produced by Nippon Nyukazai Co., 
Ltd.) was added dropwise into the beaker, and the resultant mixture was 
stirred slowly by a 9.3 mm.phi. glass rod for about 5 minutes. 
Meanwhile, 6 g of a tacking regulator (butyl cellulose) and 6 g of water 
were weighed out, added into a test tube with an inner diameter of 13 mm 
and a length of 150 mm, and mixed up by shaking well the test tube. 
Further, 9 g (solids: 2.7 g) of the aqueous dispersion of a colloidal 
urethane resin (HUX 232, produced by Asahi Denka Kogyo Kabushiki Kaisha) 
used in Example 1 was weighed out and supplied into a 100 cc beaker, 
followed by dropwise addition thereto of weighed-out 9 g of water, 0.2 g 
of the antiseptics, 0.2 g of the ultraviolet absorber and 4.6 g of the 
coloring agent (alcoholic dye) used in Example 1, and the resultant 
mixture was stirred with a 9.3 mm.phi. glass rod for about one minute. 
The said tacking regulator was added dropwise into the beaker containing 
the said acrylic emulsion mixed with the said film-forming auxiliary, and 
the resultant mixture was stirred well with a 9.3 mm.phi. glass rod for 
about three minutes. 
Thereafter, the said aqueous dispersion of the colloidal urethane resin 
mixed with the said antiseptics, ultraviolet absorber and coloring agent 
was added into the beaker containing the said acrylic emulsion mixed with 
the said film-forming auxiliary and tacking regulator, and the resultant 
mixture was stirred in the same way as Example 1 and put into a 100 cc 
polyethylene container, followed by the same treatment as in Example 1 to 
obtain paints (viscosity (measured at 20.degree. C. by B-type viscometer 
with No. 2 rotor rotated at 100 r.p.m. ): 52 cps) . 
When a product was made by using this paint and the physical properties 
were examined, the following results were obtained: coloring agent elution 
in 45.degree. C. hot water: "A"; film transparency: "A"; state of the 
film: "A". 
Example 5 
Paints were obtained in the same way as Example 1 except that an ultrafine 
particle pigment (HI-MICRON PAINT (red), produced by Mikuni Pigment Co. , 
Ltd. ) was used as coloring agent. The viscosity (measured at 20.degree. 
C. by B-type viscometer with No. 1 rotor rotated at 5 r.p.m.) of the thus 
obtained paint is 120 cps. 
The obtained paints were subjected to the tests on coloring agent (pigment) 
elution in 45.degree. C. hot water, film transparency and film state 
thereof, all after 24-hour drying. The following result was obtained: 
elution in 45.degree. C. hot water: "A". 
Elution Test 
The paints obtained in Examples 1 and 5, and Comparative Example 1 were 
applied respectively to an area of 1 cm .times.1 cm on a polypropylene 
sheet. The applied paints (0.04 g) were dried well by leaving them in a 
low-humidity place (40.degree. C. and RH:40%) for 24 hours for the paint 
in Example 1 and Comparative Example 1, and 4 hours for the paint in 
Example 5. The applied paints alone were separated and put into the 
respective plastic cup. Then, 10 cc of water of 45.degree. C. was added 
into each plastic cup, and 15 minutes thereafter, each supernatant was 
taken out of the plastic cup, cooled to an ordinary temperature, and put 
into a glass cell. Light with a wavelength of 562 nm was applied to the 
glass cell and light absorbance was measured by using self-recording 
spectrophotometer UV 20Ci (manufactured by Shimazu Seisakusho Ltd.). 
The light absorbance at 562 nm of the supernatant concerning obtained 
paints in Example 1 and 5 was 0 (zero), respectively, and there was 
observed almost no elution of coloring agent therefrom. 
Also, the light absorbance at 562 nm of the supernatant concerning obtained 
paints in Comparative Example 1 was 0.012, and there was observed an 
elution of coloring agent therefrom. 
Example 6 
74 g (solids: 37 q) of an aqueous emulsion of an acrylic ester-styrene 
copolymer (POLYSOL AP4710, produced by Showa Highpolymer Co., Ltd.; solids 
content: 50% by weight; viscosity (measured at 30.degree. C. by B-type 
viscometer at No. 1 rotor speed of 2.5 r.p.m.): 6,000 cps; pH: 9; MFT: 
30.degree. C.) was weighed out and supplied into a 300 cc beaker. Then 3 g 
of a film-forming auxiliary (EN-250, produced by Nippon Nyukazai Co., Ltd. 
) was added dropwise into the beaker and the resultant mixture therein was 
stirred slowly by a 9.3 mm.phi. glass rod for about 5 minutes. 
Meanwhile, 6 g (solids: 1.8 g; 8.1 parts by weight based on 100 parts by 
weight of the acrylic ester based resin emulsion) of an aqueous dispersion 
of an anion-type colloidal urethane resin (ADEKA-BON-TIGHTER, HUX 232, 
produced by Asahi Denka Kogyo Kabushiki Kaisha; solids content: 30% by 
weight; viscosity (measured at 25.degree. C. by B-type viscometer): 20 
cps; pH: 8.0) was weighed out and supplied into a 100 cc beaker, and then 
0.2 g of an antiseptics (PROXEL GXL, produced by ICI, Ltd.), 2 g glycerol, 
0.3 g of a defoaming agent (FORMASTER VL, produced by San Nopco Limited), 
and 1 g of a coloring agent (LIOFAST BLACK, a pigment, TOYO INK CO., LTD.) 
were weighed out and added into the beaker, followed by stirring of the 
mixture in the beaker with a 9.3 mm.phi. glass rod for about 10 minutes. 
Then, the thus obtained urethane dispersion was supplied into the 300 cc 
beaker containing the said acrylic ester based resin emulsion and the 
mixture was stirred. Then, 1.5 g of the thickener (HUX-TA, produced by 
Asahi Denka Kogyo Kabushiki Kaisha), and 12 g of the thixotropic improving 
agents, (0.02% XanthanGum-RHODOPOL 23, produced by RHONE-POULENC. JAPAN, 
LTD. ) were added to the resultant mixture stirring for 20 minutes by 
manual, and then left still for about one hour for defoaming to obtain a 
paint (viscosity (measured at 20.degree. C. by B-type viscometer with No. 
5 rotor rotated at 0.5 r.p.m.): 64,000 cps). 
The obtained paints were subjected to the tests on coloring agent (pigment) 
elution in 45.degree. C. hot water, film transparency and film state 
thereof, all after 24-hour drying. The following results were obtained: 
elution in 45.degree. C. hot water: "A" . 
TABLE 1 
______________________________________ 
Example 1 Example 2 Example 3 
______________________________________ 
Aqueous 82.4 g 85.4 g 87.4 g 
emulsion of 
(38.3 g)* (39.7 g)* (40.6 g)* 
acrylic ester 
based resin 
Aqueous 12 g 9 g 7 g 
dispersion of 
(3.6 g)# (2.7 g)# (2.1 g)# 
urethane 
resin 
Film-forming 
1 g 1 g 1 g 
auxiliary 
Antiseptics 
0.2 g 0.2 g 0.2 g 
Ultraviolet 
0.4 g 0.4 g 0.4 g 
absorber 
Coloring 4 g 4 g 4 g 
agent 
Coloring A A A 
agent elution 
in 45.degree. C. hot 
mater 
Film A A A 
transparency 
Film state 
A A A 
______________________________________ 
(Note) 
*: weight of the solids of the acrylic ester based resin emulsion. 
#: weight of the solids of the urethane resin dispersion. 
TABLE 2 
______________________________________ 
Comp. Comp. Comp. Comp. 
Example 1 
Example 2 Example 3 Example 4 
______________________________________ 
Aqueous 88.5 g 89.5 g 91.5 g 92.5 g 
emulsion of 
(41.2 g)* (41.6 
g)* (42.5 
g)* (43.0 
g)* 
acrylic ester 
based resin 
Aqueous 6 g 5 g 3 g 2 g 
dispersion of 
(1.8 g)# (1.5 g)# (0.9 g)# (0.6 g)# 
urethane 
resin 
Film-forming 
1 g 1 g 1 g 1 g 
auxiliary 
Antiseptics 
0.2 g 0.2 g 0.2 g 0.2 g 
Ultraviolet 
0.4 g 0.4 g 0.4 g 0.4 g 
absorber 
Coloring 4 g 4 g 4 g 4 g 
agent 
Coloring C C C C 
agent elution 
in 45.degree. C. hot 
mater 
Film C C C C 
transparency 
Film state 
C C C C 
______________________________________ 
(Note) 
*: weight of the solids of the acrylic ester based resin emulsion. 
#: weight of the solids of the urethane resin dispersion.