Method of manufacturing display screen

There is disclosed a salt of a polymer having charged anionic functionalities used as a dispersant in a dispersion solution containing a pigment and used for forming a first pigment layer. A substance which forms a salt with a polymer having charged anionic functionalities is mixed into a solution applied on the pigment layer, and/or mixed into a developing solution. The formed layers are patterned and thus a display screen is obtained.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a method of manufacturing a display screen 
having a color filter, which is used in a cathode ray tube, a liquid 
crystal display element or the like. 
2. Description of the Related Art 
Conventionally, a filter pattern which is made by patterning a pigment 
layer into a predetermined pattern, is used in various fields. A color 
filter used in a liquid crystal display apparatus is a typical example of 
the filter pattern. 
Further, as disclosed in, for example, U.S. Pat. No. 2,959,484 or 
3,114,065, which is directed to a color cathode ray tube, a phosphor film 
with an optical filter which has a structure in which an optical filter of 
a color which corresponding to the color emitted by a phosphor film is 
provided in a front side of the phosphor film, that is, between the inner 
surface of the face plate of the panel and the phosphor film, is known. 
Usually, a plurality of phosphor films having emitting colors of red, blue 
and green are formed in a dot manner or a stripe manner on the inner 
surface of the face plate of a color cathode ray tube. As electron beams 
collide with these phosphor films, the phosphor films emit light, thus 
displaying an image. A filter-applied phosphor film is designed to achieve 
an improvement of image display characteristics such as contrast and color 
purity, and has a structure in which a filter pattern which transmits a 
light beam of the same color as the color emitted from the phosphor film 
itself, is provided between the face plate and the phosphor film. With 
this structure, of the external light made incident, the green and blue 
components can be absorbed by a red pigment film, the green and red 
components can be absorbed by a blue pigment film, and the blue and red 
components can be absorbed by a green pigment film. With use of 
filter-applied phosphor films, the contrast and the color purity of the 
display apparatus can be enhanced. For the formation of such a filter 
film, generally, a pigment film is applied on a substrate, and then an 
exposure and development are carried out on the film for patterning. 
During the patterning, a portion of the pigment film, which should remain 
as a desired pattern is required to have a sufficient adhesion property 
with respect to the substrate, whereas the other portion is required to 
have a sufficient removal property. Further, the pigment film is required 
to have a transparence, and it is required that pigment particles are 
dispersed uniformly without being gathered irregularly. 
However, the bond between pigment particles and that between the pigment 
and the substrate are, in practice, relatively strong, and therefore some 
excessive portions of the pigment film are, in many cases, not removed in 
the development step, but remain on the substrate as residues. In order to 
avoid this, the following attempt was made. That is, the development was 
carried out before the pigment film was dried. However, this attempt 
entails another problem in which a good patterning cannot be carried out. 
That is, a sharp-edged pattern cannot be obtained. In other words, the 
boundary between the portion to remain and the portion to be removed after 
an exposure cannot be formed sharp. 
In the case where such a filter is applied between a phosphor film and a 
substrate, first, a filter film is patterned as the exposure and 
development are repeated for each color by means of a slurry method. Then, 
on the filter film thus obtained, a phosphor which emit the same color as 
that of the filter film is patterned, as the exposure and development are 
repeated for each color by the slurry method. Thus, the above case 
involves a great number of production steps, making it complicated. 
Under such circumstances, a method in which a phosphor film is applied on a 
pigment film, and patterning of these two layers is carried out by one 
exposure, is conventionally proposed (Jap. Pat. Appln. KOKAI Publication 
No. 52-77578 or No. 5-266795). 
However, in the above-described method in which the patterning of the 
phosphor layer and the pigment layer is carried out by only one exposure, 
the phenomenon that the first film is dissolved while the second film is 
applied, easily occur. If the first layer is completely hardened in order 
to avoid the above drawback, the first film cannot be easily dissolved and 
removed by the development, which is carried out after the formation of 
the second layer. As a result, it is difficult to form the identical 
pattern in the pigment film and the phosphor film. Thus, in the case of 
the patterning by only one exposure, it is desirable that the two 
contradicting properties, namely, the dissolving property and the 
development property, be satisfied at the same time, and therefore this 
method involves a limited condition for work. As a result, phosphor layers 
with color filters, which have a uniform quality, cannot be obtained. 
SUMMARY OF THE INVENTION 
The present invention has been proposed in order to solve the 
above-described drawbacks of the conventional techniques, and the first 
object thereof is to form a filter layer having a good adhesion property 
with respect to a substrate screen, which can achieve a sharp edged and 
has a uniform composition, on a display screen, in a simple process. 
The second object of the present invention is to provide a method of 
manufacturing a display screen, which is capable of forming a filter layer 
having a good adhesion property with respect to a substrate screen, which 
can achieve a sharp edged pattern and has a uniform composition, on a 
display screen, by one exposure and one development, even in the case 
where a layer having a different composition from that of a filter layer 
is formed on the filter layer. 
According to the first aspect of the present invention, there is provided a 
method of manufacturing a display screen having a filter pattern, the 
method comprising the steps of: forming a two-layered film on a substrate, 
at least one of two layers containing a photoresist, and one of the two 
layers located on the substrate side, which is formed by applying a 
pigment dispersion solution containing at least pigment particles and 
solution of a salt of a polymer electrolyte, or polymer having charged 
anionic functionalities followed by drying; exposing the two-layered film 
via a certain mask pattern; and patterning the film by developing it by 
using a developing agent mainly made of water; wherein the upper layer of 
the two-layered film and/or the developing agent, contain a substance 
which forms a salt along with a polymer electrolyte. 
According to the second aspect of the present invention, which can be used 
for patterning of a single layer, there is provided a method of 
manufacturing a display screen having a filter pattern, comprising the 
steps of: forming a pigment layer by applying a pigment dispersion 
solution containing pigment particles, a photoresist and solution of salt 
of a polymer electrolyte, on a substrate, followed by drying; and 
patterning the layer by exposing it and developing it using a development 
agent containing a substance which forms a salt with the polymer 
electrolyte. 
The method of the present invention, in which a two-layered or 
single-layered film is patterned, can be divided into the following nine 
embodiments. 
According to the first embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte, on a 
substrate, followed by drying, thus forming a first layer; applying a 
solution containing a substance which forms the salt with the polymer 
electrolyte, on the first layer, followed by drying, thus forming a second 
layer, and patterning the first layer and the second layer by exposing 
them and developing them using a developing agent containing a substance 
which forms the salt with the polymer electrolyte. 
According to the second embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte, on a 
substrate, followed by drying, thus forming a first layer; applying a 
solution containing a substance which forms the salt with the polymer 
electrolyte, on the first layer, followed by drying, thus forming a second 
layer, and patterning the first layer and the second layer by exposing 
them and developing them using a developing agent. 
According to the third embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte, on a 
substrate, followed by drying, thus forming a pigment layer; and 
patterning the pigment layer by exposing it and developing it using a 
developing agent containing a substance which forms the salt with the 
polymer electrolyte. 
According to the fourth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles 
and a solution of a salt of a polymer electrolyte, on a substrate, 
followed by drying, thus forming a first layer; applying a solution 
containing a photoresist and a substance which forms the salt with the 
polymer electrolyte, on the first layer, followed by drying, thus forming 
a second layer, and patterning the first layer and the second layer by 
exposing them and developing them using a developing agent containing a 
substance which forms the salt with the polymer electrolyte. 
According to the fifth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, 
and a solution of a salt of a polymer electrolyte, on a substrate, 
followed by drying, thus forming a first layer; applying a solution 
containing a photoresist and a substance which forms the salt with the 
polymer electrolyte, on the first layer, followed by drying, thus forming 
a second layer, and patterning the first layer and the second layer by 
exposing them and developing them using a developing agent. 
According to the sixth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles 
and a solution of a salt of a polymer electrolyte, on a substrate, 
followed by drying, thus forming a first layer; applying a solution 
containing a photoresist on the first layer, followed by drying, thus 
forming a second layer, and patterning the first layer and the second 
layer by exposing them and developing them using a developing agent 
containing a substance which forms the salt with the polymer electrolyte. 
According to the seventh embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte, on a 
substrate, followed by drying, thus forming a first layer; applying a 
solution containing a photoresist and a substance which forms the salt 
with the polymer electrolyte, on the first layer, followed by drying, thus 
forming a second layer, and patterning the first layer and the second 
layer by exposing them and developing them using a developing agent 
containing a substance which forms the salt with the polymer electrolyte. 
According to the eighth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte, on a 
substrate, followed by drying, thus forming a first layer; applying a 
solution containing a photoresist and a substance which forms the salt 
with the polymer electrolyte, on the first layer, followed by drying, thus 
forming a second layer, and patterning the first layer and the second 
layer by exposing them and developing them using a developing agent. 
According to the ninth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte, on a 
substrate, followed by drying, thus forming a first layer; applying a 
solution containing a photoresist, followed by drying, thus forming a 
second layer, and patterning the first layer and the second layer by 
exposing them and developing them using a developing agent containing a 
substance which forms the salt with the polymer electrolyte. 
According to the present invention, a solution of a salt of a polymer 
electrolyte is used for the first layer containing pigments, so as to make 
the first layer insoluble to a solvent in a simple way. Thus, the adhesion 
property of the layer with respect to the substrate screen can be 
improved. Further, by adding a substance which forms the salt with the 
polymer electrolyte, of the first layer, to at least the second layer or 
the developing agent, the first layer can be made soluble to the solvent, 
and therefore undesired portions of the first and second layers can be 
easily peeled and removed from the substrate in the development step, 
while achieving a sharp pigment layer. 
Further, according to the present invention, a solution of a salt of a 
polymer electrolyte and a substance which forms the salt with the polymer 
electrolyte is used in combination, thereby making it possible to control 
the hardening, peeling and removal of the pigment layer. Consequently, the 
amount of the photoresist used in the patterning can be reduced. With an 
decrease in the photoresist amount, the maintenance of the solution used 
to form the display screen, can be facilitated, thus improving the 
productivity. 
With use of the present invention method, excellent effects can be obtained 
even in the case where multiple layers comprising a pigment layer and an 
upper layer having different compositions from that of the pigment layer 
are formed, and these layers are patterned by only one exposure and one 
development. For example, an excellent adhesion between the substrate 
screen and the pigment layer can be achieved. Further, since the pigment 
layer is made sufficiently insoluble, it will not be dissolved out even if 
a layer having a different composition is formed thereon. Furthermore, the 
substances which can make the pigment layer soluble to a solvent are 
applied in the layers having different compositions and/or in a developing 
agent, and therefore the pigment layer and the layers having different 
compositions from that of the pigment layer can be easily peeled and 
removed from the substrate by a development. Thus, according to the 
present invention, a pigment layer having a good adhesion property with 
respect to the substrate screen, which has a sharp pattern and a uniform 
composition, can be easily formed by only one exposure and one 
development, and the condition for work can be sufficiently widened. 
Additional objects and advantages of the invention will be set forth in the 
description which follows, and in part will be obvious from the 
description, or may be learned by practice of the invention. The objects 
and advantages of the invention may be realized and obtained by means of 
the instrumentalities and combinations particularly pointed out in the 
appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
In the present invention method, a solution of a salt of a polymer 
electrolyte which is made insoluble to a solvent when it is dried, and a 
substance which forms the salt with the polymer electrolyte are used in 
combination. The solution of the salt of the polymer electrolyte is added 
as a dispersant into the dispersion solution containing pigments. In the 
solution of the salt of the polymer electrolyte, pigment particles are 
dispersed uniformly without being coagulated, and such a solution is 
applied on a substrate, followed by drying. As a result, the group which 
forms the salt of the polymer electrolyte is partially dissociated, making 
a polymer film insoluble to a solvent. Further, according to the present 
invention, a solution containing a substance which can form a salt along 
with a partially dissociated polymer electrolyte salt, is applied on the 
pigment layer and in a developing agent. Therefore, the polymer 
electrolyte contained in the pigment layer is made soluble, thus improving 
the peeling property in the development. 
The present invention has been proposed under the above-described 
circumstances, and provides a method of forming a pigment layer, which is 
designed to uniformly disperse pigment particles and to achieve both the 
insoluble property which is requisite to the portion so as to remain as a 
pattern, and the peeling property which is requisite to the other portion 
which is not exposed during the development, at the same time. 
The present invention can be divided into nine respects. 
According to the first aspect of the present invention, there is provided a 
method of manufacturing a display screen, comprising the steps of: 
applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte having a 
group which vaporizes as the group is partially dissociated when dried, on 
a substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a substance which 
forms the salt with the polymer electrolyte, on the first layer, followed 
by drying, thus forming a second layer, and patterning the first layer and 
the second layer by exposing them and developing them using a developing 
agent containing a substance which forms the salt with the polymer 
electrolyte. 
In the first layer, the group which can form the salt of the polymer 
electrolyte, is partially dissociated, and the dissociated group is 
volatilized during drying process, thus forming a polymer film which is 
insoluble to the solvent. In the case where the second layer is applied on 
the first layer formed by the above-described manner, the substance of the 
second layer, which forms the salt with the polymer electrolyte, is 
diffused in the first layer without having pigments dissolved into the 
second layer, thus making it possible to form a water-soluble salt in the 
first layer. 
A predetermined region of the first layer is fixed by an exposure of the 
photoresist. The first and second layers other than the fixed area can be 
removed by use of a developing agent, due to the presence of the salt 
soluble to the solvent. In this method, the substance which forms the salt 
with the polymer electrolyte is added to both the solution used to form 
the second layer and the developing agent, and therefore the removal of 
these layers can be further effectively carried out. 
According to the second embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte having a 
group which volatilizes as the group is partially dissociated when dried, 
on a substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a substance which 
forms the salt with the polymer electrolyte, on the first layer, and 
forming a salt soluble to the solvent in the first layer, followed by 
drying, thus forming a second layer; and patterning the first layer and 
the second layer by exposing them and developing them using a developing 
agent. 
In the method according to the second embodiment of the present invention, 
the substance which forms the salt with the polymer electrolyte is not 
added to the developing agent unlike in the first embodiment of the 
invention. However, since the substance which forms a salt with the 
polymer electrolyte in the second layer is diffused in the first layer, 
the first layer is made soluble to the solvent and therefore is dissolved 
into the solvent contained in the developing agent, making it possible to 
sufficiently remove the first layer. The method according to the second 
embodiment of the present invention is similar to that of the first aspect 
of the invention except that the substance which forms the salt with the 
polymer electrolyte is not added to the developing agent. 
According to the third embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte having a 
group which volatilizes as the group is partially dissociated when dried, 
on a substrate, followed by drying, thus forming a pigment layer which is 
insoluble to a solvent; and patterning the pigment layer by exposing it 
and developing it using a developing agent containing a substance which 
forms the salt with the polymer electrolyte. 
The method according to the third embodiment of the present invention is 
similar to that of the first embodiment of the invention except that the 
second layer is not applied. Usually, in patterning by use of a 
photoresist and a developing agent, the pigment layer cannot be 
sufficiently hardened or made insoluble unless a very large amount of 
photoresist is added. However, with the method according to the third 
aspect of the invention, the solution of the salt of the polymer 
electrolyte is added to the first layer, and therefore the pigment layer 
can be sufficiently hardened and made insoluble even if the amount of 
photoresist is decreased. Further, in this method, the substance which 
forms the salt with the polymer electrolyte is added to the developing 
agent, and therefore the unnecessary portion can be effectively removed by 
patterning. As is well-known, a photoresist becomes very unstable when 
mixed with some other component, for example, pigment dispersion solution. 
The larger the amount of photoresist, the more difficult to control the 
dispersion solution containing the photoresist in a stable state, 
increasing the cost. However, with use of the present invention, the 
amount of photoresist can be decreased, and the photoresist-containing 
dispersion solution is made relatively stable. Therefore, the maintenance 
of the photoresist-containing dispersion solution, which takes much labor, 
can be reduced to a minimum level. 
According to the fourth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles 
and a solution of a salt of a polymer electrolyte having a group which 
volatilizes as the group is partially dissociated when dried, on a 
substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a photoresist and a 
substance which forms the salt with the polymer electrolyte, on the first 
layer, followed by drying, thus forming a second layer, and patterning the 
first layer and the second layer by exposing them and developing them 
using a developing agent containing a substance which forms the salt with 
the polymer electrolyte. 
With regard to the fourth embodiment of the present invention, in the first 
layer, the group which can form the salt of the polymer electrolyte, is 
partially dissociated, and the dissociated group is volatilized during 
drying process, thus forming a polymer film which is insoluble to the 
solvent. In the case where the second layer is applied on the first layer 
formed by the above-described manner, the substance of the second layer, 
which forms the salt with the polymer electrolyte, is diffused in the 
first layer without having pigments dissolved into the second layer, thus 
making it possible to form a water-soluble salt in the first layer. 
In this method, a photoresist is mixed in the second layer, and the second 
layer is fixed by exposure, so as to protect the first layer from the 
developing agent, thus patterning the layer. The portions of the first and 
second layers other than the area fixed by the exposure of the photoresist 
can be removed by use of a developing agent, due to the presence of the 
salt soluble to the solvent. Further, in this method, the substance which 
forms the salt with the polymer electrolyte is added to both the solution 
used to form the second layer and the developing agent, and therefore the 
removal of these layers can be further effectively carried out. 
According to the fifth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, 
and a solution of a salt of a polymer electrolyte having a group which 
volatilizes as the group is partially dissociated when dried, on a 
substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a photoresist and a 
substance which forms the salt with the polymer electrolyte, on the first 
layer, followed by drying, thus forming a second layer, and patterning the 
first layer and the second layer by exposing them and developing them 
using a developing agent. 
In the method according to the fifth embodiment of the present invention, a 
photoresist is added to the second layer, and the second layer is fixed by 
exposure, so as to protect the first layer from the developing agent, thus 
patterning the layer, in similar to the case of the fourth embodiment of 
the invention. Although the substance which forms the salt with the 
polymer electrolyte is not added to the developing agent as so in the 
fourth embodiment of the invention, the first layer which was made 
insoluble to the solvent by drying, forms a salt which is soluble to a 
solvent as the second layer is applied, and therefore the it can be 
removed sufficiently by the developing agent. 
According to the sixth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles 
and a solution of a salt of a polymer electrolyte having a group which 
volatilizes as the group is partially dissociated when dried, on a 
substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a photoresist on 
the first layer, followed by drying, thus forming a second layer, and 
patterning the first layer and the second layer by exposing them and 
developing them using a developing agent containing a substance which 
forms the salt with the polymer electrolyte. 
In the method according to the sixth embodiment of the present invention, a 
photoresist is added to the second layer, and the second layer is fixed by 
exposure, so as to protect the first layer from the developing agent, thus 
patterning the layer, in similar to the case of the fourth embodiment of 
the invention. Although the substance which forms the salt with the 
polymer electrolyte is not contained in the second layer as so in the 
fourth aspect of the invention, the portions other than that fixed by 
first layer can be sufficiently removed in the development since the 
developing agent contains the substance which forms the salt with the 
polymer electrolyte. 
According to the seventh embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte having a 
group which volatilizes as the group is partially dissociated when dried, 
on a substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a photoresist and a 
substance which forms the salt with the polymer electrolyte, on the first 
layer, followed by drying, thus forming a second layer, and patterning the 
first layer and the second layer by exposing them and developing them 
using a developing agent containing a substance which forms the salt with 
the polymer electrolyte. 
With regard to the seventh embodiment of the present invention, both the 
first and second layers contain a photoresist. In the first layer, the 
group which can form the salt of the polymer electrolyte is partially 
dissociated, and the dissociated group is volatilized during drying 
process, thus forming a polymer film which is insoluble to the solvent. In 
the case where the second layer is applied on the first layer, the 
substance of the second layer, which forms the salt with the polymer 
electrolyte, can be diffused in the first layer without having pigments 
dissolved into the second layer since the first layer was made insoluble 
to the solvent, thus making it possible to form a water-soluble salt in 
the first layer. 
Predetermined regions of the first and second layers are fixed by an 
exposure of the photoresist. The first and second layers other than the 
fixed area can be removed by use of a developing agent, due to the 
presence of the salt soluble to the solvent. In this method, the substance 
which forms the salt with the polymer electrolyte is added also to the 
developing agent, and therefore the removal of these layers can be further 
effectively carried out. 
According to the eighth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte having a 
group which volatilizes as the group is partially dissociated when dried, 
on a substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a photoresist and a 
substance which forms the salt with the polymer electrolyte, on the first 
layer, followed by drying, thus forming a second layer, and patterning the 
first layer and the second layer by exposing them and developing them 
using a developing agent. 
In the method according to the eighth embodiment of the present invention, 
the substance which forms the salt with the polymer electrolyte is not 
added to the developing agent, unlike in the seventh embodiment of the 
invention. However, in this method, the first layer is made soluble to a 
solvent, and therefore it can be removed sufficiently in the development. 
This method is similar to the seventh embodiment of the invention except 
that the substance which forms the salt with the polymer electrolyte is 
not added to the developing agent. 
According to the ninth embodiment of the present invention, there is 
provided a method of manufacturing a display screen, comprising the steps 
of: applying a pigment dispersion solution containing pigment particles, a 
photoresist and a solution of a salt of a polymer electrolyte having a 
group which volatilizes as the group is partially dissociated when dried, 
on a substrate, followed by drying, thus forming a first layer which is 
insoluble to a solvent; applying a solution containing a photoresist, 
followed by drying, thus forming a second layer, and patterning the first 
layer and the second layer by exposing them and developing them using a 
developing agent containing a substance which forms the salt with the 
polymer electrolyte. 
In the method according to the ninth embodiment of the present invention, a 
photoresist is mixed into the second layer, and the second layer is fixed 
by exposure, so as to protect the first layer from the developer, thus 
patterning the layer, in similar to the case of the seventh embodiment of 
the invention. Although the substance which forms the salt with the 
polymer electrolyte is not contained in the second layer as so in the 
seventh embodiment of the invention, the portions other than that fixed by 
the exposure of the photoresist can be sufficiently removed in the 
development since the developing agent contains the substance which forms 
the salt with the polymer electrolyte. 
The following is a description of the materials used in the present 
invention. 
Examples of the polymer electrolyte used in the present invention are those 
types each having a dissociation group in the structure unit of the 
polymer. In the present invention, the polymer electrolyte is used also as 
a dispersant for dispersing pigment particles. 
Preferable examples of the polymer electrolyte are anion polymer 
electrolytes. 
More preferable examples of the polymer electrolyte are sodium salts, 
ammonium salts, amine salts and the like, of the following compounds: 
acrylic acid type or acrylic acid-styrene type copolymers, polymer 
polycarboxylic acids, styrene-polycarboxylic acid copolymers, aromatic 
formalin sulfonate condensation product, polyoxyethylenealkylether 
sulfate, polyoxyethylene alkylphenylether sulfate and the like. More 
specific examples of the acrylic acid type compound, are Dispex N-40 
(tradename, of Allied Colloid Co.) (sodium salt) and Dispex A-40 
(tradename, of Allied Colloid Co.) (ammonium salt); those of the acrylic 
acid copolymers are Dispex G-40 (tradename, of Allied Colloid Co.) (sodium 
salt) and Dispex GA-40 (tradename, of Allied Colloid Co.) (ammonium salt); 
those of the polymer polycarboxylic acids are Poiz 520 (tradename, of Kao) 
(sodium salt) and Discoate N-14 (Dai-ichi Kogyo Seiyaku) (ammonium salt); 
those of styrene-polycarboxylic acid copolymer are Oxylac SH-101 (Nihon 
Shokubai Kagaku) and the like; those of the ammonium salt of 
polyoxyethylene alkylethersulfate are Hitenor 08 (Dai-ichi Kogyo Seiyaku 
Co. Ltd.) and the like; those of the ammonium salt of polyoxyethylene 
alkylphenylethersulfate are Hitenor N-08 (Dai-ichi Kogyo Seiyaku Co. Ltd.) 
and the like. These materials can be used solely or in combination. 
Of these materials, in order to form the first layer, an ammonium salt 
which can easily volatilize, is preferable, an ammonium salt of a 
polycarboxylic acid is more preferable, and an ammonium salt of an acrylic 
acid or an acrylic acid copolymer is further more preferable in order to 
achieve both good insoluble property and good peeling property. 
The solution containing a salt of the polymer electrolyte should be made by 
using water as the main solvent. 
The pigments which can be used in the present invention are of either type 
of inorganic or organic. Especially, the pigments which can be dispersed 
in the filter layer of the filter-applied phosphor film, so that the 
filter layer can achieve a sufficient transparency without having the 
scattering of light, should preferably used. The particle diameters of the 
pigments, which can maintain a good transparency, should be, preferably, 1 
.mu.m or less, and more preferably, 0.1 .mu.m. 
Further, in the case where the invention is applied to a color cathode ray 
tube which undergoes a high temperature step in the production process, 
inorganic pigments are preferable since they each have a high heat 
photoresistance. 
The following are specific examples of the pigments. 
Examples of the red pigment are Sicotrans Red L-2817 (particle diameter: 
0.01 .mu.m to 0.02 .mu.m, BASF Inc.) which is of the iron (II) oxide 
group, Cromophthal Red A2B (particle diameter: 0.01 .mu.m, CIBA GAIGY 
Inc.) which is of the anthraquinone type. Examples of the blue pigment are 
Cobalt Blue X (particle diameter: 0.01 .mu.m to 0.02 .mu.m, TOYO-GANRYO 
Inc.) which is of the cobalt aluminate (Al.sub.2 O.sub.3 -CoO), 
Ultramarine Blue No. 8000 (particle diameter: 0.3 .mu.m, DAI-ICHI KASEI 
Inc.) which is of the ultramarine blue group, Lionol Blue FG-7370 
(particle diameter: 0.01 .mu.m, TOYO INK) which is of the phthalocianine 
blue group. Examples of the green pigment are Dypyroxide TM-Green #3320 
(particle diameter: 0.01 .mu.m to 0.02 .mu.m, DAINICHI SEIKA Inc.) of the 
TiO.sub.2 -NiO-CoO-ZnO group, Dypyroxide TM-Green #3340 (particle 
diameter: 0.01 .mu.m to 0.02 .mu.m, DAINICHI SEIKA Inc.) of the 
CoO-Al.sub.2 O.sub.3 -Cr.sub.2 O.sub.3 -TiO.sub.2 group, Dypyroxide 
TM-Green #3420 (particle diameter: 0.01 .mu.m to 0.02 .mu.m, DAINICHI 
SEIKA Inc.) of the CoO-Al.sub.2 O.sub.3 -Cr.sub.2 O.sub.3 group, ND-801 
(particle diameter: 0.35 .mu.m, NIHON DENKO Inc.) of the Cr.sub.2 O.sub.3 
group, Fastogen Green S (particle diameter: 0.01 .mu.m, DAINIPPON INK) of 
the chlorinated phthalocyanine green group, Fastogen Green 2YK (particle 
diameter: 0.01 .mu.m, DAINIPPON INK) of the brominated phthalocyanine 
green group. 
The concentration of the pigment dispersed in the dispersion agent made of 
the polymer electrolyte should be in a range of 0.1 weight % to 50 weight 
%, preferably, 1 weight % to 50 weight %. If the pigment concentration is 
less than 0.1 weight %, the color of the pigment layer cannot be observed, 
whereas if it exceeds 1 weight %, the color can be clearly observed. Or if 
it exceeds 50 weight %, the viscosity of the dispersion solution is 
drastically increased, making it impossible to apply a uniform film. 
The ratio of the concentration of the polymer electrolyte (weight %) with 
respect to the pigment concentration (weight %) should be in a range of 
0.005 to 1, preferably, 0.01 to 0.5. If the ratio is less than 0.005, the 
dispersion force of the pigment particles becomes weak, and the irregular 
concentration of pigment particles easily occurs, whereas if the ratio 
exceeds 1, the coloring power becomes weak, and the devitrification occurs 
when baked. 
The above-described polymer electrolyte and pigment are mixed into pure 
water, followed by stirring, and thus a dispersion solution used to form a 
pigment layer can be obtained. As long as 10 weight % or less, a 
water-soluble organic solvent such as alcohol can be added to the pure 
water. 
Examples of the photoresist of the present invention are water-soluble 
photoresists such as ammonium bichrominate (ADC)/polyvinyl alcohol (PVA), 
sodium bichrominate (SDC)/PVA, diazonium salt or the like/PVA, stilbazole, 
ADC/casein. 
In the case where a photoresist is contained in a pigment dispersion 
solution, the ratio of the photoresist concentration to the polymer 
electrolyte concentration should be in a range of 0.005 to 100, more 
preferably, 0.03 to 30. If the ratio is 0.005 or less, the patterning 
property is deteriorated, decreasing the sensitivity in particular, 
whereas if the ratio is larger than 100, the devitrification occurs, 
deteriorating the filter characteristics. 
Next, the developing agent used in the development step will now be 
described. 
The developing agent should be of the type made by using water as a main 
solvent, and it is preferable that lukewarm water, more preferably, at a 
temperature of 35.degree. C., should be used. 
In order to achieve a good patterning property, an alkali solution having a 
pH value of 8.5 or higher, should preferably be used, and more preferably, 
an alkali solution having a pH value of 9.5 or higher, should be used. 
Further, an alkali solution which contains a substance capable of making 
the polymer electrolyte soluble, the polymer electrolyte having been made 
insoluble to a solvent such as water, as the substance can form a salt 
along with a partially dissociated polymer electrolyte salt, can be added 
to the developing agent. Examples of such a substance are salts of alkali 
metals, hydroxides of metals, and ammonium salts such as LiCl, LiNO.sub.3, 
NaCl, Na.sub.2 CO.sub.3, Na.sub.2 S.sub.2 O.sub.3, NaOH, sodium dichromate 
(SDC), ammonium dichromate (ADC). These substances can be used solely or 
in combination. Further, these substances can be mixed in the solution 
used for making the second layer, or in both of the developing agent and 
the solution used for making the second layer. The solution containing a 
substance which can form a salt along with a partially dissociated polymer 
electrolyte salt, should be of the type made by using water as a main 
solvent. 
With regard to the present invention, in the case where an ammonium salt of 
the acrylic acid or the acrylic acid copolymer is used as a dispersant in 
the first layer, a preferable substance for achieving a good peeling 
property and a good insoluble property of the pigment layer applied and 
dried, is an alkali metal salt, and a compound containing Li or Na ion 
which has a small ion diameter is more preferable, with sodium 
bichrominate, especially, being most preferable. 
The manufacturing method of the present invention proceeds in the following 
manner. 
The following description will be made in connection with a filter-applied 
phosphor screen used for a color cathode ray tube as an example of the 
display screen. 
First, a pigment dispersion solution containing as the pigment particles 
and the polymer electrolyte pigment dispersion solution as main contents, 
is applied on a substrate. An application method can be selected 
appropriately in accordance with the shape, size and the like of the 
substrate, and examples of such a method are a spin coat method, a roller 
method and an immersing method. The spin coat method is particularly 
preferable in order to obtain a predetermined uniform thickness. The 
application layer of the pigment dispersion solution is then dried. The 
drying method can be arbitrarily selected without any particular 
limitation as long as it can volatilize the moisture and partially 
dissociate a salt of a polymer electrolyte. For example, drying using a 
heater, drying with a heat wave, or a long term drying at room temperature 
or the like can be used in accordance with necessity. 
For the patterning which is carried out with only the pigment layer, it 
only-suffices if the pigment dispersion solution contains a photoresist. 
With application of a pigment layer containing the photoresist, the 
portion which is exposed by a high-pressure mercury lamp or the like, is 
hardened. After that, when a development is carried out with use of an 
alkali aqueous solution containing a substance capable of making the 
polymer electrolyte soluble, the polymer electrolyte having been made 
insoluble to a solvent such as water, as the substance can form a salt 
along with a partially dissociated polymer electrolyte salt, a 
predetermined filter pattern can be obtained. 
In the case where the photoresist is not contained in the pigment 
dispersion solution, but a photoresist layer is formed after application 
and drying of the pigment layer, and then the exposure and development are 
carried out, the time period required to the exposure can be shortened. 
Consequently, the sensitivity property can be improved. The filter layer 
formed in the above-described manner has good tightness with regard to a 
substrate, and the range of the thickness of the filter layer thus formed 
can be increased. The solution containing the photoresist should be of the 
type made by using water as a main solvent. 
In the case where a plurality of, usually, three color filter layers, 
namely, red, green and blue are formed, the above step should be repeated 
for each color. 
In the case where a color cathode ray tube having a filter-applied phosphor 
surface, which is made by coating a phosphor film on the filter layer, the 
filter layer is applied and dried, and then it can be exposed to a 
predetermined pattern with use of a shadow mask. After forming three color 
filter layers with shadow masks, a phosphor layer can be formed by a 
conventionally known method. 
In the exposure/development method for a photoresist layer which is 
laminated after the pigment layer is applied and dried, phosphor particles 
are added in the photoresist solution or the solution containing a 
substance which forms a salt with the polymer electrolyte. In this way, 
the pigment layer and the phosphor film can be patterned at the same time. 
The following is a brief description thereof. 
In the case where a filter-applied phosphor film is formed on the panel of 
a color cathode ray tube, such a procedure is as follows. 
First, a pigment dispersion solution is applied on the inner surface of a 
face plate, and dried. The application is carried out while fixing the 
inner surface of the face plate in a predetermined direction such as the 
upper, lateral or downward direction. The direction of the face plate can 
be selected so as to achieve a uniform application layer, in consideration 
of solid component, viscosity and irregular application of the pigment 
dispersion solution. 
Examples of the application method are the spin coat, the roller method and 
the immersing method. In order to achieve a predetermined uniform film 
thickness, the spin coat method is particularly preferable. 
The drying method can be arbitrarily selected without any particular 
limitation as long as it can volatilize the moisture and partially 
dissociate salt of a polymer electrolyte. For example, drying using a 
heater, drying with a heat wave, or a long term drying at room temperature 
or the like can be used for forming the first layer. It is also possible 
that a patterned light absorption layer is formed in advance on the inner 
surface of the face plate prior to the formation of the first layer. 
Next, a dispersion solution containing phosphorous substances is prepared, 
and this solution is applied by use of the same method as for the first 
layer, on the first layer, thus forming the second layer. 
Lastly, the layers are exposed by use of, for example, a high-pressure 
mercury lamp, via a shadow mask, thus they are patterned into a desired 
pattern. After that, a developing agent is sprayed thereon for the 
development. This operation is carried out for each color. 
In the case where a layer having phosphorous substances is formed as the 
second layer, the average particle diameter of the pigment should 
preferably be determined in consideration of the slurry containing the 
phosphorous substances, for the second layer. 
For example, the experimental results obtained by the inventors of the 
present invention indicate the following. That is, in the case where the 
phosphorous substances having an average particle diameter of about 5 to 
10 .mu.m are used, the average particle diameter of the pigment must be 1 
.mu.m or less. Otherwise, phosphorous substances enter gaps between 
pigment particles, making it difficult to form the two-layer structure. Or 
the average particle diameter of the pigment should preferably be 1 .mu.m 
or less, more preferably, 0.1 .mu.m or less, in order to maintain the 
transparency of the first layer. 
The concentration of the pigment dispersed in the dispersion agent mainly 
made of the polymer electrolyte should be in a range of 0.1 weight % to 50 
weight %, preferably, 1 weight % to 50 weight %. If the pigment 
concentration is less than 0.1 weight %, the color of the pigment layer 
cannot be observed, whereas if it exceeds 1 weight %, the color can be 
clearly observed. Or if it exceeds 50 weight %, the viscosity of the 
dispersion solution is drastically increased, making it impossible to 
apply a uniform film. 
In the present invention, the relationship between the concentration of the 
polymer electrolyte and the pigment concentration is very important. The 
ratio of the concentration, by weight %, of the polymer electrolyte with 
respect to the pigment concentration, which may be also expressed as 
polymer electrolyte concentration/pigment concentration, should be in a 
range of 0.005 to 1, preferably, 0.01 to 0.5. If the ratio exceeds 1, the 
first layer is made soluble before the completion of the drying of a 
solution, which is for example, a phosphor dispersion solution, used for 
the second layer, and therefore the first layer and second layer are mixed 
with each other, making it impossible to form the two-layer structure. Or, 
if the ratio is less than 0.005, the bonding force acting between pigment 
particles becomes strong, thereby deteriorating the peeling property. 
The above-described polymer electrolyte and pigment are mixed into pure 
water, followed by stirring, and thus a dispersion solution used to form a 
pigment layer can be obtained. As long as 5 weight % or less, a 
water-soluble organic solvent such as alcohol can be added to the pure 
water. 
In order to improve the peeling property, a nonion-based dispersant can be 
used along with the polymer electrolyte. Examples of the nonion-based 
dispersant are polyoxyethylene derivatives such as 
polyoxyethylenelaurylether, polyoxyethylenenonylphenylether, and 
polyoxyethylenesorbitanmonolaurate, and polyoxyalkylene derivatives such 
as polyoxyalkylenealkylether. Specific examples thereof are Noigen EA-140, 
Noigen EA-170 (both by DAI-ICHI KOGYO SEIYAKU), Emulgen 106, Emulgen 
A-500, Reodol TW-L120 (all by Kao). The mixture ratio of the nonion/anion 
NH.sub.4 salt, preferable for improving the peeling property is 1/30 to 
1/300. 
Next, a phosphor dispersion solution which can be applied for the 
application of the second layer will be described. 
The phosphorous substances contained in the phosphor dispersion solution 
may be red, blue and green phosphorous substances conventionally used in a 
cathode ray tube or a color image receiving apparatus. 
Examples of the red phosphor substance are Y.sub.2 O.sub.2 S:Eu, Y.sub.2 
O.sub.3 :Eu, (Zn, Cd)S:Ag, Zn.sub.3 (PO.sub.4).sub.2 :Mn; examples of the 
blue phosphor substance are ZnS:Ag, Cl, ZnS:Ag, Al, ZnS:Ag; and examples 
of the green phosphor substance are ZnS:Cu, Al, ZnS:Au, Al, ZnS:Cu, Au, 
Al, Zn.sub.2 SiO.sub.4 :Mn, As. 
Additives used in the second layer are used in the phosphor slurry and/or 
the developing agent. A substance capable of making the polymer 
electrolyte soluble, the polymer electrolyte having been made insoluble to 
a solvent such as water, as the substance can form a salt along with a 
partially dissociated polymer electrolyte salt, can be used as an 
additive. Further, a photoresist is added to the phosphor slurry. 
According to the present invention, a salt of a polymer electrolyte is used 
as a dispersant for making a pigment layer on a substrate, by application 
and drying. Thus, the salt of the polymer electrolyte is partially 
dissociated, making the pigment layer insoluble to a solvent such as 
water. For example, in the case of an ammonium polyacrylate salt, 
polyacrylic acid is made, thereby making the layer insoluble to water. 
On the other hand, in the case where substances such as Li ions or Na ions, 
which can form a salt along with a polymer electrolyte, are added to the 
solution for the second layer applied on the first layer, and/or the 
developing agent, these ions are diffused into the first layer, which is 
the pigment layer, and salts of polymer electrolytes are replaced by these 
ions, making the layer soluble to the solvent contained in the developing 
agent. For example, in the case of the above polyacrylic acid, it is 
formed eventually into sodium polyacrylate, making it soluble to water. 
Therefore, the peeling property in the patterning by development can be 
improved. The portion to remain as a pattern is not peeled by the 
development but remain on the substrate since the photoresist formed 
within or on the pigment layer has been hardened by exposure. For example, 
in the case where a pigment layer and a photoresist layer are formed, the 
pigment layer which was made soluble is patterned together with the 
photoresist layer. More specifically, in the case of a negative 
photoresist, an unexposed portion is developed together with the 
photoresist layer, and an exposed portion is covered by the photoresist 
layer and remains on the substrate as it is. With this method, a two-layer 
film pattern which cannot be dissolved or has an excellent development 
property, can be obtained at a low cost. 
EXAMPLES 
Examples of the present invention will now be described with reference to 
accompanying figures. 
TABLES 1 and 2 provided below each list embodiments of the present 
invention, and the composition of the application solution used in each of 
the first and second layers. Example of the upper section of each table 
corresponds to the nine embodiments of the present invention. In each 
table, mark .largecircle. indicates that the material listed in the 
extreme left section is contained, whereas mark x indicates that the 
material is not contained. The compositions 1B, 1G, 1R and the like of the 
first layer in each column were as listed in TABLE 3, the compositions 1U, 
2U and the like of the second layer were as listed in TABLE 4, and the 
compositions 1D, 2D and the like, of the developing solutions, were as 
listed in TABLE 5. Further, the term "salt forming material" used in the 
TABLES means a substance which forms a salt along with a polymer 
electrolyte. 
TABLE 1 
__________________________________________________________________________ 
Examples 1 2 3 4-1 
4-2 
5-1 5-2 
__________________________________________________________________________ 
Composition 
of solution 
First layer 
Pigment o o o o o o o 
Salt of polymer electrolyte 
o o o o o o o 
Photoresist o o o x x x x 
Second layer 
Photoresist x x -- o o o o 
Salt forming substance 
o o -- o o o o 
Phosphor substance 
x x -- x x x x 
Developing agent 
Salt forming substance 
o x o o o x x 
Solution 
First layer 
B 1B 1B 1B 2B 2B 2B 2B 
G 1G 1G 1G 2G 2G 2G 2G 
R 1R 1R 1R 2R 2R 2R 2R 
Second layer 
B 1U 1U -- 3U 4U 3U 4U 
G 1U 1U -- 3U 4U 3U 4U 
R 1U 1U -- 3U 4U 3U 4U 
Developing solution 
B 1D water 
1D 1D 1D water 
water 
G 2D water 
2D 2D 2D water 
water 
R 3D water 
3D 3D 3D water 
water 
__________________________________________________________________________ 
TABLE 2 
__________________________________________________________________________ 
Examples 6-1 
6-2 7-1 
7-2 
8-1 
8-2 9 
__________________________________________________________________________ 
Composition 
of solution 
First layer 
Pigment o o o o o o o 
Salt of polymer electrolyte 
o o o o o o o 
Photoresist x x o o o o o 
Second layer 
Photoresist o o o o o o o 
Salt forming substance 
x x o o o o x 
Phosphor substance 
x o x x x x x 
Developing agent 
Salt forming substance 
o o o o x x o 
Solution 
First layer 
B 2B 2B 1B 1B 1B 1B 1B 
G 2G 2G 1G 1G 1G 1G 1G 
R 2R 2R 1R 1R 1R 1R 1R 
Second layer 
B 2U 5B 3U 4U 3U 4U 2U 
G 2U 5G 3U 4U 3U 4U 2U 
R 2U 5R 3U 4U 3U 4U 2U 
Developing solution 
B 1D 1D 1D 1D water 
water 
1D 
G 2D 2D 2D 2D water 
water 
2D 
R 3D 3D 3D 3D water 
water 
3D 
__________________________________________________________________________ 
TABLE 3 
__________________________________________________________________________ 
Composition of pigment dispersion solution which is used for first layer 
Pigment 
dispersion 
solution Composition 
__________________________________________________________________________ 
Blue 1B Blue pigment: Cobalt blue X (cobalt aluminate, TOYO GANRYO 
Inc.) 30 g 
pigment Salt of polymer electrolyte: Dispex GA-40 
0.7 g 
dispersion 
(Ammonium salt of polyacrylic acid 
solution copolymer.Allid Colloid Inc.) 
Photoresist: ADC 0.03 g + PVA 0.47 g 
0.5 g 
Water: 68.8 g 
Blue 2B Blue pigment: Cobalt blue X (cobalt aluminate, TOYO GANRYO 
30 g) 
pigment Salt of polymer electrolyte: Dispex GA-40 
0.7 g 
dispersion 
(Ammonium salt of polyacrylic acid 
solution copolymer.Allid Colloid Inc.) 
Water: 69.3 g 
Green 1G Green pigment: Dypyroxide TM-Green #3320 (TiO.sub.2 --NiO--CoO--Z 
nO, 30 g 
pigment DAINICHI SEIKA Inc.) 
dispersion 
Salt of polymer electrolyte: Dispex Ga-40 
0.44 g 
solution (Ammonium salt of polyacrylic acid 
copolymer.Allid Colloid Inc.) 
Dispex N-40 0.26 g 
(Sodium salt of polyacrylic acid 
copolymer.Allid Colloid Inc.) 
Photoresist: ADC 0.12 g + PVA 1.88 g 
2.0 g 
Water: 67.3 g 
Green 2G Green pigment: Dypyroxide TM-Green #3320 (TiO.sub.2 --NiO--CoO--Z 
nO, 30 g 
pigment DAINICHI SEIKA Inc.) 
dispersion 
Salt of polymer electrolyte: Dispex Ga-40 
0.44 g 
solution (Ammonium salt of polyacrylic acid 
copolymer.Allid Colloid Inc.) 
Dispex N-40 0.26 g 
(Sodium salt of polyacrylic acid 
copolymer.Allid Colloid Inc.) 
Water: 69.3 g 
Red 1R Red pigment: Sicotrans Red L-2817 (Fe.sub.2 O.sub.3, BASF 
30 g) 
pigment Salt of polymer electrolyte: Hitenor08 
0.7 g 
dispersion 
(Ammonium salt of polyoxyethylene- 
solution alkylethersulfate, 
DAIICHI KOGYO SEIYAKU Co. Ltd.) 
Photoresist: ADC 0.12 g + PVA 1.88 g 
2.0 g 
Water: 67.3 g 
Red 2R Red pigment: Sicotrans Red L-2817 (Fe.sub.2 O.sub.3, BASF 
30 g) 
pigment Salt of polymer electrolyte: Hitenor08 
0.7 g 
dispersion 
(Ammonium salt of polyoxyethylene- 
solution alkylethersulfate, 
DAIICHI KOGYO SEIYAKU Co. Ltd.) 
Water: 69.3 g 
__________________________________________________________________________ 
TABLE 4 
______________________________________ 
Composition of solution used for forming 2nd layer 
Solution for 
forming 2ad 
layer Composition 
______________________________________ 
1U Salt forming substance: Sodium dichromate 
0.1 g 
Water: 49.9 g 
2U Photoresist: ADC 0.2 g + PVA 3.0 g 
3.2 g 
Surfactant: 0.1 g 
Water: 96.7 g 
3U Photoresist, Salt forming substance: 
SDC 0.2 g + PVA 3.0 g 3.2 g 
Surfactant: 0.1 g 
Water: 96.7 g 
4U Photoresist: ADC 0.2 g + PVA 3.0 g 
3.2 g 
Salt forming substance: Na.sub.2 CO.sub.3 
0.2 g 
Surfactant: 0.1 g 
Water: 96.7 g 
5B Blue phosphor: ZnS:Ag, Cl 
100 g 
Photoresist: ADC 0.3 g + PVA 5.0 g 
5.3 g 
Surfactant: 0.01 g 
Water: 140 g 
5G Green phosphor: ZnS:Cu, Al 
100 g 
Photoresist: ADC 0.4 g + PVA 8.0 g 
8.4 g 
Surfactant: 0.01 g 
Water: 160 g 
5R Red phosphor: Y.sub.2 O.sub.2 S:Eu 
100 g 
Photoresist: ADC 0.5 g + PVA 10.0 g 
10.5 g 
Surfactant: 0.01 g 
Water: 190 g 
______________________________________ 
TABLE 5 
______________________________________ 
Composition of developing agent 
Developing agent Composition 
______________________________________ 
1D Aqueous solution of 
0.2 weight % of Na.sub.2 CO.sub.3 
2D Aqueous solution of 
0.2 weight % of NaOH 
3D Aqueous solution of 
0.2 weight % of NaOH and 
0.1 weight % of LiCl 
______________________________________ 
The following are descriptions of specific manufacturing methods, which are 
made on the basis of some of the examples. 
Example 3 
An example of the method of manufacturing a display screen, according to 
the third embodiment of the present invention will now be described. In 
this example, the description will be made in connection with the case 
where a filter pattern is formed by exposing and developing the pigment 
layer itself, and a patterned phosphor film is formed thereon, thus 
manufacturing a filter-applied phosphor surface used in a color cathode 
ray tube. 
FIG. 1 is a flow diagram illustrating steps in an example of the method of 
manufacturing a display screen, according to the third embodiment of the 
present invention. FIGS. 2A to 2F are explanatory diagrams each showing a 
step in the above method. Basically, a filter pattern for one color can be 
formed by a set of the steps shown in FIGS. 1A to 1E. In order to form a 
plurality of filter patterns, a set of the steps 1A to 1E should be 
repeated for each color. 
First, as shown in FIG. 2A, on an inner surface of a panel 10 of a color 
cathode ray tube, that is, a substrate made of, for example, glass, a 
light absorption layer 12 having a predetermined pattern and serving as a 
black matrix, is formed. The light absorption layer can be formed by a 
conventionally known method. More specifically, a photoresist is applied 
on the substrate, and the photoresist is exposed via a shadow mask, 
followed by development and drying. Thus, a stripe-shaped or dot-shaped 
light hardening film is made to remain in a section in which a pigment 
layer and a phosphor layer are supposed to be formed. A light absorption 
material, for example, graphite, is applied and adhered on the light 
hardening film, and then cleaned with hydrogen peroxide solution so as to 
dissolve the light hardening film. Further, the undesired portion of the 
light absorption layer is removed together with the light absorption 
material, and a hole section in which the pigment layer and the phosphor 
layer are to be formed, is exposed, thus forming a patterned light 
absorption layer 12. 
Next, in order to form blue, green and red filters, pigment dispersion 
solutions 1B, 1G and 1R having the following compositions were prepared. 
A blue pigment dispersion solution 1B, as shown in TABLE 3, was prepared by 
dispersing 30 weight % of cobalt aluminate (Cobalt Blue X (particle 
diameter: 0.01 .mu.m to 0.02 .mu.m, TOYO GANRYO Inc.) as blue pigment 
particle, 0.5 weight % of ammonium dichromate (ADC)+polyvilylalcohol 
(PVA), as a photoresist, and 0.7 weight % of ammonium salt of polyacrylic 
acid copolymer (Dispex GA-40, Allied Colloid Inc.) as polymer electrolyte, 
into pure water. The ratio of the polymer electrolyte concentration/the 
pigment concentration was set to 0.023, the ratio of the photoresist 
concentration/the polymer electrolyte concentration was set to 0.714, and 
the ratio of the photoresist concentration/the pigment concentration was 
set to 0.017. 
A green pigment dispersion solution 1G was prepared by dispersing 30 weight 
% of TiO.sub.2 -NiO-CoO-ZnO (Dypyroxide TM-Green #3320 (particle diameter: 
0.01 .mu.m to 0.02 .mu.m, DAINICHI SEIKA Inc.)) as green pigment particle, 
2 weight % of ADC+PVA, as a photoresist, and 0.44 weight % of ammonium 
salt of polyacrylic acid (Dispex GA-40, Allied Colloid Inc.) and 0.26 
weight % of sodium salt of polyacrylic acid (Dispex N-40, Allied Colloid 
Inc.) as polymer electrolyte into pure water. The ratio of the polymer 
electrolyte concentration/the pigment concentration was set to 0.023, the 
ratio of the photoresist concentration/the polymer electrolyte 
concentration was set to 2.857, and the ratio of the photoresist 
concentration/the pigment concentration was set to 0.067. 
A red pigment dispersion solution 1R was prepared by dispersing 30 weight % 
of fine particles of Fe.sub.2 O.sub.3 as red pigment particle, 2 weight % 
of ADC+PVA, as a photoresist, and 0.7 weight % of ammonium salt of 
polyoxyethylenealkylethersulfate (Hitenor 08 of Daiichi Kogyo Seiyaku Co. 
Ltd.) as polymer electrolyte, into pure water. The ratio of the polymer 
electrolyte concentration/the pigment concentration was set to 0.023, the 
ratio of the photoresist concentration/the polymer electrolyte 
concentration was set to 2.857, and the ratio of the photoresist 
concentration/the pigment concentration was set to 0.067. 
The application step A and the drying step B were carried out in the 
following manners. 
While maintaining the temperature of the panel 10 of the color cathode ray 
tube, serving as a substrate, at 30.degree. C., the above-described blue 
pigment dispersion solution 1B was applied. Then, the panel 10 was rotated 
at 100 to 150 rpm so as to shake off the excessive portion of the pigment 
dispersion solution, thus forming an application layer having a constant 
thickness. After that, the application layer was dried by a heater at a 
temperature of 120.degree. C. for 3 to 4 minutes, thus obtaining a blue 
pigment application layer as can be seen in FIG. 2B. 
The pattern exposure step C was carried out in the following manner. 
As shown in FIG. 2C, the layer was exposed into a predetermined pattern via 
a shadow mask (not shown) by use of a high-pressure mercury lamp. 
The developing step D and the drying step E were carried out in the 
following manners. 
A developing agent 1D, that is, an alkali solution, for example, having a 
pH value of 9 and containing Na.sub.2 CO.sub.3, is sprayed at a developing 
agent pressure of 2 to 10 kg/cm.sup.2 in a mist fashion, thus performing a 
development, and a blue pigment layer 30B having a predetermined pattern 
was formed as shown in FIG. 2D. 
Next, as in a similar manner to that of the above process for forming a 
blue pigment layer, a green pigment layer and a red pigment layer were 
formed. With regard to the developing agent, the developing agent 2D shown 
in TABLE 5 was used for the green pigment layer, and the developing agent 
3D was used for the red. 
As shown in FIG. 2E, a filter pattern consisting of the blue pigment layer 
30B, the green pigment layer 30G and the red pigment layer 30R was formed 
on the inner surface of the panel 10. 
Next, by means of a regular method, as shown in FIG. 2F, the blue phosphor 
layer 40B, a green phosphor layer 40G and a red phosphor layer 40R were 
formed to correspond respectively to the blue pigment layer 30B, the green 
pigment layer 3OG and the red pigment layer 30R. 
It should be noted that phosphor suspension solutions having the following 
compositions were used. A blue phosphor suspension solution was prepared 
by mixing 100 g of blue phosphorous substances (ZnS:Ag, Cl), 5 g of 
polyvinylalcohol, 0.30 g of ammonium dichromate, 0.01 g of surface active 
agent and 140 g of pure water, all together with stirring. A green 
phosphor suspension solution was prepared by mixing 100 g of green 
phosphorous substances (ZnS:Cu, Al), 8 g of polyvinylalcohol, 0.40 g of 
ammonium dichromate, 0.01 g of surface active agent and 160 g of pure 
water, all together with stirring. A red phosphor suspension solution was 
prepared by mixing 100 g of red phosphorous substances (Y.sub.2 O.sub.2 
S:Eu), 10 g of polyvinylalcohol, 0.50 g of ammonium dichromate, 0.01 g of 
surface active agent and 190 g of pure water, all together with stirring. 
In the above-described method, a desired filter-tipped phosphor film, 
having the pigment layer and the phosphor layer on the substrate 10, was 
obtained. A color cathode ray tube which was made by use of the desired 
phosphor film exhibited an excellent contrast and a good colorimetric 
purity. Further, a filter pattern was formed at a predetermined position, 
for example, a position in which a blue phosphor layer should be formed, 
and a blue filter was formed at that position. Thus, the pigment particles 
of a blue filter did not remain as a residue in the position for a 
different color. Consequently, a mixture of color was not observed in the 
filter, achieving a high calorimetric purity. 
The following is a specific example of the method in which a two-layer film 
is formed, followed by exposure and development, which is made on the 
basis of Example 4. 
Example 4-2 
An example of the method of manufacturing a display screen, according to 
the fourth embodiment of the present invention will now be described. 
FIG. 3 is a flow diagram illustrating steps of the example, in which a 
two-layer film is formed, and then it is patterned by exposure and 
development. In order to form a plurality of filter patterns, a set of the 
steps shown in FIG. 3 should be repeated for each color. 
First, as in the case of Example 3, a panel in which a black matrix was 
formed, was prepared. 
A pigment dispersion solution application step F and a drying step B were 
carried out in the following manners. 
In order to form blue, green and red filters, pigment dispersion solutions 
2B, 2G and 2R having the compositions listed in TABLE 3 were prepared. 
These solutions were different from the pigment dispersion solutions used 
in the above Example 3, in respect that these solutions did not contain 
photoresists. 
A blue pigment dispersion solution 2B was prepared by dispersing 30 weight 
% of cobalt aluminate (Cobalt Blue X (particle diameter: 0.01 .mu.m to 
0.02 .mu.m, TOYO GANRYO Inc.) as blue pigment particle, and 0.7 weight % 
of ammonium salt of polyacrylic acid copolymer (Dispex GA-40, Allied 
Colloid Inc.) as polymer electrolyte, into pure water. The ratio of the 
polymer electrolyte concentration/the pigment concentration was set to 
0.023. 
A green pigment dispersion solution 2G was prepared by dispersing 30 weight 
% of TiO.sub.2 -NiO-CoO-ZnO (Dypyroxide TM-Green #3320 (particle diameter: 
0.01 .mu.m to 0.02 .mu.m, DAINICHI SEIKA Inc.)) as green pigment particle, 
and 0.44 weight % of ammonium salt of polyacrylic acid (Dispex GA-40, 
Allied Colloid Inc.) and 0.26 weight % of sodium salt of polyacrylic acid 
(Dispex N-40, Allied Colloid Inc.) as polymer electrolyte, into pure 
water. The ratio of the polymer electrolyte concentration/the pigment 
concentration was set to 0.023. 
A red pigment dispersion solution 2R was prepared by dispersing 20 weight % 
of fine particles of Fe.sub.2 O.sub.3 as red pigment particle, and 0.7 
weight % of ammonium salt of polyoxyethylenealkylethersulfate (Hitenor 08 
of Daiichi Kogyo Seiyaku Co. Ltd.) as polymer electrolyte, into pure 
water. The ratio of the polymer electrolyte concentration/the pigment 
concentration was set to 0.035. 
FIGS. 4A to 4F are cross sections illustrating the steps of FIG. 3. 
First, as shown in FIG. 4A, on an inner surface of a panel 10 of a color 
cathode ray tube, that is, a substrate made of, for example, glass, a 
light absorption layer 12 having a predetermined pattern and serving as a 
black matrix, is formed in a similar manner to that of the Example 3. 
As in the Example 3, while maintaining the temperature of the panel 10 at 
30.degree. C., the above-described blue pigment dispersion solution 2B was 
applied. Then, the panel 10 was rotated at 100 to 150 rpm so as to shake 
off the excessive portion of the pigment dispersion solution. After that, 
the application layer was dried by a heater at a temperature of 
120.degree. C. for 3 to 4 minutes, thus obtaining a blue pigment 
application layer. 
The photoresist solution application step G1 and the drying step H were 
carried out in the following manner. 
That is, a photoresist solution 2U having a composition of 3 weight % of 
polyvinylalcohol, 0.20 weight % of ammonium dichromate, 0.01 weight % of 
surface activating agent, and a balance of pure water, as shown in TABLE 
4, was prepared. The solution was applied and dried in a similar manner to 
the formation of the pigment layer, and a photoresist layer 24 was 
laminated on a blue pigment layer 22B as shown in FIG. 4B. 
The pattern exposure step C was carried out in the following manner. 
As shown in FIG. 4C, the layer was exposed into a predetermined pattern via 
a shadow mask (not shown) by use of a high-pressure mercury lamp. In this 
example, the exposure time was shortened to only 1/5 of that of the 
Example 3, in which a pigment and a photoresist were mixed together. 
The developing step D was carried out in the following manners. 
A developing agent 1D, that is, an alkali solution, for example, having a 
pH value of 9 and containing Na.sub.2 CO.sub.3 which serves as a material 
which forms a salt with a polymer electrolyte, is sprayed at a developing 
agent pressure of 2 to 10 kg/cm.sup.2 in a mist fashion, thus performing a 
development, and a pattern in which a blue pigment layer 22B and a 
photoresist layer 24 were laminated, was formed as can be seen in FIG. 4D. 
Next, as in a similar manner to that of the above process for forming a 
blue pigment layer, a green pigment layer and a red pigment layer were 
formed. The developing agent 2D shown in TABLE 5 was used for the green 
pigment layer, whereas the developing agent 3D was used for the red 
pigment layer. 
As shown in FIG. 4E, a filter pattern consisting of the blue pigment layer 
22B, the green pigment layer 22G and the red pigment layer 22R was formed 
on the inner surface of the panel 10. 
Next, the photoresist layers 24 on each of the blue, green and red pigment 
layers was removed, and then phosphor layers 42B, 42G and 42R were formed 
by means of a regular method, as shown in FIG. 4F. It should be noted that 
the phosphor suspension solutions used in this example were similar to 
those used in the Example 3. 
In this method, a desired filter-applied phosphor film having the pigment 
layer and the phosphor layer on the inner surface of the panel 1, was 
obtained. A color cathode ray tube which was made by use of the phosphor 
film exhibited an excellent contrast and a good calorimetric purity. 
Further, a filter pattern was formed at a predetermined position, for 
example, a position in which a blue phosphor layer should be formed, and a 
blue filter was formed at that position. Thus, the pigment particles of a 
blue filter did not remain as a residue in the position for a different 
color. Consequently, a mixture of color was not observed in the filter, 
achieving a high calorimetric purity. 
In the case of the Example 3, if the sensitivity with regard to the 
exposure should be improved, the ratio of the amount of the photoresist 
with respect to that of the pigment should be increased, which may cause a 
deterioration of the transparency. In this example, a photoresist layer is 
separately provided, and therefore the exposure sensitivity can be greatly 
improved without adversely affecting the transparency of the pigment 
layer. The portion of the pigment layer, which was made insoluble as it 
was dried, to remain, was not made soluble by the developing agent, and 
therefore the patterning property was not affected. 
Example 6-2 
An example of the method of manufacturing a display screen, according to 
the sixth embodiment of the present invention will now be described. 
In the above-described Example 4, photoresist layers are formed on pigment 
layers, and after patterning the pigment layers for the colors, phosphor 
layers of the respective colors are formed. However, if the phosphorous 
substances are added in advance in the photoresist layers, the pigment 
layers and the phosphor layers can be patterned at the same time. FIG. 5 
is a flow diagram illustrating steps in an example of the method of 
manufacturing a display screen, according to the sixth embodiment of the 
present invention. FIGS. 6A to 6E are cross sections each showing a step 
in the example shown in FIG. 5. In this example, a filter pattern for one 
color can be formed by a set of the steps F, B, G2, H, C, D and E shown in 
FIG. 5. In order to form a phosphorous surface of a color display, it only 
suffices if a set of the steps illustrated in FIG. 5 are repeated for each 
color. Therefore, the number of steps for exposure and development can be 
reduced to a half of the case of the Example 4. 
The pigment layer application step F and the drying step B were carried out 
in the following manner. 
First, pigment dispersion solutions 2B, 2G and 2R similar to those used in 
the Example 4 and phosphor suspension solutions 5B, 5G and 5R listed in 
TABLE 4 were prepared. 
Next, in a manner similar to the method used in FIG. 6A, a blue pigment 
dispersion layer 2B was formed on an inner surface of a panel 10 on which 
light absorption layers 12 were formed as shown in FIG. 6A. 
The phosphor-containing photoresist application step G2 and the drying step 
H were carried out in the following manner. 
That is, the blue phosphor suspension solution 5B was applied on the 
substrate on which the blue pigment layer was formed, followed by drying, 
and then a phosphor-containing photoresist layer 42B was laminated on the 
pigment layer 22B as shown in FIG. 6B. 
The pattern exposure step H was carried out in the following manner. 
As shown in FIG. 6C, the layers were exposed into a predetermined pattern 
via a shadow mask, by use of a high-pressure mercury lamp. 
The development step D was carried out in the following manner. 
A developing agent 1D, that is, an alkali solution, for example, having a 
pH value of 9 and containing NaOH serving as a material which forms a salt 
with a polymer electrolyte, is sprayed at a developing agent pressure of 2 
to 10 kg/cm.sup.2 in a mist fashion, thus performing a development, and a 
laminate pattern consisting of a blue pigment layer 22B and a blue 
phosphor layer 42B was formed as shown in FIG. 6D. 
Next, as in a similar manner to that of the above process for forming a 
blue pigment layer, a green pigment layer/phosphor layer and a red pigment 
layer/phosphor layer were formed. 
The developing agent 2D was used for the green pigment layer, whereas the 
developing agent 3D was used for the red pigment layer. 
With the above-described constitution, the number of the exposure steps can 
be reduced as compared to those of the Examples 3 and 4, and therefore 
this example is advantageous in terms of facilities. 
The above-described example was described in connection with the case where 
a filter-applied phosphor surface used for a color cathode ray tube is 
manufactured; however the present invention is not limited to the above 
example, but can be applied to the cases where a filter layer patterned 
into a predetermined pattern, is manufactured. 
In this example, the substance which can form a salt along with a partially 
dissociated polymer electrolyte salt, is added to the developing agent, in 
order to improve the patterning characteristics. In the case where a 
photoresist-containing layer is laminated on a pigment layer as in the 
Example 4, the substance which can form a salt with a polymer electrolyte, 
may be added to the photoresist-containing film. However, if the substance 
is added to the photoresist-containing film and the film is laminated on 
the pigment layer, the pigment layer, which is the underlayer, may be made 
soluble to the solvent before the photoresist layer is hardened by 
irradiation of light by exposure. Therefore, it is preferable that the 
substance which can form a salt with a polymer electrolyte should be added 
to the developing agent. 
In the above example, the developing agents 1D, 2D and 3D were respectively 
used for the blue, green and red pigment layers; however the combination 
of the developing agents is not limited to this. 
Further, in the examples so far explained, the pigment layer are formed in 
the order of blue, green and red; however, naturally, the order is not 
limited to this. The present invention may be used to form not only 
pigment layers, but also phosphor layers. Furthermore, whether or not the 
solution used for forming the second layer contains a phosphor substance, 
in the embodiments where pattering is carried out after the two-layer film 
is formed, is also arbitrary. 
In the above descriptions, only typical examples are specifically 
discussed. The examples shown in TABLES 1 to 3 exhibited excellent 
patterning properties. Thus, with the method of manufacturing a display 
screen, of the present invention, good patterning characteristics, which 
indicate how sharp is the edge of the boundary between a portion to remain 
as a pattern after exposure and an unexposed portion to be removed, can be 
achieved. Thus, the residue of the pigment can be cleanly removed. 
Consequently, an accurate predetermined pattern of a pigment layer can be 
obtained in simple steps as compared to those of the present invention. 
The display screen in which a phosphor layer is formed on a pigment layer 
as described above, can be used as a display screen of a color image 
receiving tube. FIG. 7 is a diagram illustrating an example of a color 
image receiving tube to which a display screen of the present invention 
can be applied. 
FIG. 7 is a partially cutaway side view showing a cathode ray tube 
manufactured on the basis of the present invention. A cathode ray tube 60 
has an airtight glass envelope 61 the interior of which is evacuated. The 
envelope 61 has a neck 62 and a cone 63 continuously extending from the 
neck 62. In addition, the envelope 61 has a faceplate 64 sealed by a first 
glass. An explosion-proof tension band 65 consisting of a metal is wound 
around the periphery of the side wall of the faceplate 64. An electron gun 
66 for emitting electron beams is arranged in the neck 62. A phosphor 
screen 67 is formed on the inner surface of the faceplate 64. The phosphor 
screen 67 is constituted by a pigment layer as an optical filter and a 
phosphor layer formed thereon, which is excited by electron beams from the 
electron gun 66 to emit light. A deflection unit (not shown) is arranged 
outside the cone 63. The deflection unit serves to deflect electron beams 
to scan over the phosphor screen. 
Evaluation of Dissolving Properties, Adhesion Properties and Peeling 
Properties: 
Next, the method of the present invention, in which exposure and 
development are carried out after forming a two-layer film, was examined 
in terms of dissolving out property, adhesion property and peeling 
property of the pigment layer, taking, particularly, the fourth embodiment 
of the present invention as an example. The evaluation methods and results 
were as described below. 
Example 10 
Of the filter-applied phosphor layers, the blue phosphor layer was formed 
on the inner surface of the face plate of a color cathode ray tube. 
The blue pigment dispersion solution was prepared by dispersing 30 weight % 
of cobalt aluminate (Cobalt Blue X (particle diameter: 0.01 .mu.m to 0.02 
.mu.m, TOYO GANRYO Inc.), and 0.3 weight % of ammonium salt of polyacrylic 
acid copolymer (Dispex GA-40, Allied Colloid Inc.), into pure water. The 
ratio of the polymer electrolyte concentration/the pigment concentration 
was set to 0.01. 
A phosphor suspension solution (phosphor slurry) was prepared by mixing 40 
g of blue phosphor substance (ZnS:Ag, Cl), 0.16 g of sodium dichromate 
(SDC), 1.4 g of polyvinyl alcohol (average molecular weight: 2400, 88% of 
saponification and the like) and 54 g of pure water, all of which were 
weighed). 
While maintaining the temperature of the panel 10 of the color cathode ray 
tube at 30.degree. C., the pigment dispersion solution was applied on the 
inner surface of the faceplate. Then, the panel 10 was rotated at 100 to 
150 rpm so as to shake off the excessive portion of the pigment dispersion 
solution. After that, the application layer was dried by a heater at a 
temperature of 120.degree. C. for 3 to 4 minutes, thus obtaining a blue 
pigment application layer. 
The phosphor slurry was applied on the inner surface of the faceplate, on 
which the blue pigment layer was formed in the same manner as above. Then, 
the panel 10 was rotated at 100 to 150 rpm so as to shake off the 
excessive portion of the pigment dispersion solution. After that, the 
application layer was dried by a heater at a temperature of 120.degree. C. 
for 3 to 4 minutes, thus obtaining a blue phosphor application layer on 
the blue pigment layer. 
The layers were exposed into a predetermined pattern via a shadow mask by 
use of a high-pressure mercury lamp. A developing agent was sprayed at a 
developing agent pressure of 2 to 10 kg/cm.sup.2 in a mist fashion, thus 
performing a development, and a blue phosphor layer with a blue filter, 
having a predetermined pattern was formed. The developing agent used here 
was pure water having a temperature of 40.degree. C. 
The filter-applied phosphor layer thus obtained was evaluated in terms of 
the following properties. 
The dissolving-out property: the dissolving-out means that a component of 
the first layer is dissolved by the solution for the second layer, and the 
component is mixed into the first layer. The evaluation as to the 
dissolving out property was made on the basis of how much the absorption 
of the absorption peak of the reflection of the first pigment layer, is 
deteriorated as compared to the case where the dissolving-out does not 
occur. In the case where the absorption was not at all deteriorated, it 
was judged as ".largecircle.", in the case where 80% or more of the 
absorption still remained as compared to that of the case where no 
dissolving out occurred, it was judged as ".DELTA.", and in the case where 
the absorption was less than 80%, it was judged as "x". 
The adhesion property: the adhesion property indicates the state in which 
the two-layered film remains at an exposed portion after development. In 
the case where 100% of the area of the exposed portion remained, it was 
judged as ".largecircle.", in the case where 80% or more and less than 
100% of the area still remained, it was judged as ".DELTA.", and in the 
case where the area was less than 80%, it was judged as "x". 
The peeling property: the peeling property indicates how much of the 
unexposed portion was removed. In the case where 100% of the area of the 
unexposed portion was removed, it was judged as ".largecircle.", in the 
case where 80% or more and less than 100% of the portion was removed, it 
was judged as ".DELTA.", and in the case where the area was less than 80%, 
it was judged as "x". The results of the evaluation were summarized in 
TABLE 7. 
Examples 11 to 16 
In each of these examples, a blue phosphor layer with a blue filter was 
prepared with the same materials and method used in Example 10 except that 
the mixture ratio in the pigment dispersion solution was changed. The 
mixture ratios of the pigment dispersion solutions used are specified in 
TABLE 6. 
Each of the filter-applied phosphor layers thus obtained was evaluated by 
the same method as of Example 10. The results of the evaluation are 
summarized in TABLE 7. 
Comparative Examples 1 and 2 
In each of these examples, a blue phosphor layer with a blue filter was 
prepared with the same materials and method used in Example 10 except that 
the mixture ratio between the polymer electrolyte and the pigment in the 
pigment dispersion solution was set to 0.0033 (in Comparative Example 1) 
and 1.5 (Comparative Example 2). The mixture ratios of the pigment 
dispersion solutions used are specified in TABLE 6. 
Each of the filter-applied phosphor layers thus obtained was evaluated by 
the same method as of Example 10. The results of the evaluation are 
summarized in TABLE 7. 
Comparative Examples 3 and 4 
The blue pigment dispersion solution was prepared by dispersing 30 weight % 
of cobalt aluminate (Cobalt Blue X (particle diameter: 0.01 .mu.m to 0.02 
.mu.m, TOYO GANRYO Inc.), and 1.5 weight % (Comparative Example 3) and 15 
weight % of (Comparative Example 4) of ammonium salt of polyacrylic acid 
copolymer (Dispex GA-40, Allied Colloid Inc.), into pure water. A 
blue-filter-applied blue phosphor layer was obtained using the same 
phosphor slurry and the method as those of Example 10. The mixture ratio 
of the pigment dispersion solution was described in TABLE 6. 
Each of the filter-applied phosphor layers thus obtained was evaluated by 
the same method as of Example 10. The results of the evaluation are 
summarized in TABLE 7. 
Comparative Examples 5 to 13 
In each of these examples, a blue phosphor layer with a blue filter was 
prepared with the same materials and method used in the respective one of 
the Examples 10 to 16, and the Comparative Examples 1 and 2 except that 
ammonium dichromate (ADC) was used in place of sodium dichromate (SDC). 
Each of the filter-applied phosphor layers thus obtained was evaluated by 
the same method as of Example 10. The results of the evaluation are 
summarized in TABLE 8. 
TABLE 6 
______________________________________ 
Dis- Dis- 
Blue persant persant Pure 
pigment 
1 2 water Ratio 
______________________________________ 
Examples 
10 30.0 0.3 -- 69.7 0.01 
11 30.0 0.15 -- 69.85 0.005 
12 30.0 1.5 -- 68.5 0.05 
13 30.0 10.0 -- 60.0 0.33 
14 30.0 15.0 -- 55.0 0.50 
15 20.0 16.0 -- 64.0 0.80 
16 20.0 20.0 -- 60.0 1.00 
Compara- 
1 30.0 0.1 -- 69.9 0.0033 
tive 2 20.0 30.0 -- 50.0 1.50 
Examples 
3 30.0 -- 1.5 68.5 0.05 
4 30.0 -- 15.0 55.0 0.50 
(in weight %) 
______________________________________ 
Blue pigment: cobalt aluminate 
Dispersant 1: ammonium salt of polyacrylic acid copolymer 
Dispersant 2: sodium salt of polyacrylic acid copolymer 
Ratio: Ratio between dispersant/blue pigment 
TABLE 7 
______________________________________ 
Dissolving-out 
Adhesion Peeling 
property property property 
______________________________________ 
Examples 10 .largecircle. 
.largecircle. 
.largecircle. 
11 .largecircle. 
.largecircle. 
.DELTA. 
12 .largecircle. 
.largecircle. 
.largecircle. 
13 .largecircle. 
.largecircle. 
.largecircle. 
14 .largecircle. 
.largecircle. 
.largecircle. 
15 .DELTA. .largecircle. 
.largecircle. 
16 .DELTA. .DELTA. 
.largecircle. 
Comparative 
1 .largecircle. 
.largecircle. 
.times. 
Examples 2 .times. .DELTA. 
.largecircle. 
3 .times. .DELTA. 
-- 
4 .times. .times. 
-- 
______________________________________ 
TABLE 8 
______________________________________ 
Composition 
of pigment 
Dis- adhe- Peeling 
dispersion 
solving sion prop- 
solution 
property property 
erty 
______________________________________ 
Compara- 
5 Same as .largecircle. 
.largecircle. 
.times. 
tive Example 10 
Examples 
6 Same as .largecircle. 
.largecircle. 
.times. 
Example 11 
7 Same as .largecircle. 
.largecircle. 
.times. 
Example 12 
8 Same as .largecircle. 
.largecircle. 
.times. 
Example 13 
9 Same as .largecircle. 
.largecircle. 
.times. 
Example 14 
10 Same as .largecircle. 
.largecircle. 
.times. 
Example 15 
11 Same as .largecircle. 
.largecircle. 
.times. 
Example 16 
12 Same as .largecircle. 
.largecircle. 
.times. 
Comparative 
Example 1 
13 Same as .DELTA. .largecircle. 
.times. 
Comparative 
Example 2 
______________________________________ 
As can be seen in TABLE 7, in the case where a sodium salt of a polyacrylic 
acid copolymer is added to the pigment dispersion solution (Comparative 
Examples 3 and 4), the dissolving-out property is deteriorated. In the 
case where the pigment layer is formed by the application/drying method, 
it is not preferable that a non-volatile or non-combustible salt be solely 
used. 
Comparative Example 1, where the ratio of the dispersant/pigment is 0.0033, 
exhibits a poor peeling property, and therefore there is a tendency that 
an excellent patterning is difficult to perform. This is considered 
because, due to an insufficient amount of polymer electrolyte, the pigment 
particles are made not easily soluble since the bonding force between 
pigment particles becomes strong even though the polymer electrolyte is 
made soluble by alkali metal ions contained in the phosphor slurry. 
Comparative Example 2, where the ratio of dispersant/pigment is 1.50, has a 
tendency that the dissolving out property is deteriorated. This is 
because, due to an excessive amount of polymer electrolyte, the pigment 
layer is made soluble prior to the completion of the drying of the 
phosphor slurry. 
As can be seen in TABLES 6 and 7, two-layer film patterns having an 
excellent dissolving out property, can be stably obtained in a wide range 
of the ratio of dispersant/pigment, from 0.005 to 1.00. 
Example 17 
In this example, a blue-filter-applied blue phosphor layer was prepared 
with the same materials and method as those of Example 10 except that 
ultramarine blue was used in place of cobalt aluminate in the pigment 
dispersion solution. 
The filter-applied phosphor layer thus obtained was evaluated by the same 
method as of Example 10, and substantially the same results as those of 
Example 10 were obtained. Further, blue-filter-applied blue phosphor 
layers were prepared with various amounts of dispersant as in Examples 11 
to 16, and they were evaluated. The results of the evaluation were the 
same as those summarized in TABLE 7. 
Example 18 
In this example, a blue phosphor layer with a blue filter was prepared with 
the same materials and method as those of Example 10 except that ZnS:Ag, 
Al was used as the blue phosphor substance. 
The filter-applied phosphor layer thus obtained was evaluated by the same 
method as of Example 10, and substantially the same results as those of 
Example 10 were obtained. Further, blue-filter-applied blue phosphor 
layers were prepared with various amounts of dispersant as in Examples 11 
to 16, and they were evaluated. The results of the evaluation were the 
same as those summarized in TABLE 7. 
Examples 19 to 60 
In each of the examples, a blue-filter-applied blue phosphor layer was 
obtained by the same method used in Example 10 except that a pigment 
dispersion solution shown in TABLE 9 and a phosphor slurry shown in TABLE 
10 were prepared, and they were combined as listed in TABLES 11 and 12. In 
Examples 19 to 37, the temperature of the developing agent was set to 
25.degree. C. and the pH value thereof was set to 7.0, and in Examples 38 
to 60, the temperature and pH value thereof were set to 40.degree. C. and 
9.0, respectively. The filter-applied phosphor films thus obtained were 
evaluated by the same method as of Example 10. The results of the 
evaluation were summarized in TABLES 11 and 12. TABLE 11 shows the results 
obtained in the case where the temperature and the pH value of the 
developing agent were set to 25.degree. C. and 7.0, respectively, whereas 
TABLE 12 shows the results obtained in the case where the temperature and 
the pH value of the developing agent were set to 40.degree. C. and 9.0, 
respectively. 
Comparative Examples 14 to 31 
In each of the examples, a blue-filter-applied blue phosphor layer was 
obtained by the same method used in Example 10 except that a pigment 
dispersion solution shown in TABLE 9 and a phosphor slurry shown in TABLE 
10 were prepared, and they were combined as listed in TABLE 11 and 12. In 
Comparative Examples 14 to 24, the temperature of the developing agent was 
set to 25.degree. C. and the pH value thereof was set to 7.0, and in 
Comparative Examples 25 to 31, the temperature and pH value thereof were 
set to 40.degree. C. and 9.0, respectively. The results of the evaluation 
were summarized in TABLES 11 and 12. TABLE 11 shows the results obtained 
in the case where the temperature and the pH value of the developing agent 
were set to 25.degree. C. and 7.0, respectively, whereas TABLE 12 shows 
the results obtained in the case where the temperature and the pH value of 
the developing agent were set to 40.degree. C. and 9.0, respectively. 
TABLE 9 
______________________________________ 
Composition 
number 
Material (i) (ii) (iii) (iv) (v) 
______________________________________ 
Blue pigment 
27.0 27.0 27.0 27.0 27.0 
Dispersant 1 
0.5 2.0 3.5 5.0 -- 
Dispersant 2 
-- -- -- -- 3.5 
Dispersant/ 
0.019 0.074 0.130 0.185 0.130 
blue pigment 
Pure water 
72.5 71.0 69.5 68 69.5 
(in weight %) 
______________________________________ 
Blue pigment: cobalt aluminate 
Dispersant 1: ammonium salt of polyacrylic acid copolymer 
Dispersant 2: sodium salt of polyacrylic acid copolymer 
TABLE 10 
______________________________________ 
Composition 
number 
Material A B C D E F 
______________________________________ 
Blue phosphor 
40 40 40 40 40 40 
Ammonium 0.16 0.10 0.06 -- 0.16 0.16 
dichromate 
Sodium -- 0.06 0.10 0.16 -- -- 
dichromate 
Sodium -- -- -- -- 0.03 0.05 
carbonate 
Polyvinyl 
1.4 1.4 1.4 1.4 1.4 1.4 
alcohol 
Pure water 
54 54 54 54 54 54 
(in weight ratio) 
______________________________________ 
TABLE 11 
______________________________________ 
Components for constituting 
two layers 
Pigment disper- 
Phosphor dispersion 
sion solution 
solution 
______________________________________ 
Examples 19 (i) C 
20 (i) D 
21 (i) E 
22 (i) F 
23 (ii) B 
24 (ii) C 
25 (ii) D 
26 (ii) E 
27 (ii) F 
28 (iii) B 
29 (iii) C 
30 (iii) D 
31 (iii) E 
32 (iii) F 
33 (iv) B 
34 (iv) C 
35 (iv) D 
36 (iv) E 
37 (iv) F 
Compara- 14 (i) B 
tive 15 (i) A 
Examples 16 (ii) A 
17 (iii) A 
18 (iv) A 
19 (v) A 
20 (v) B 
21 (v) C 
22 (v) D 
23 (v) E 
24 (v) F 
______________________________________ 
Properties 
Dissolving- 
out Adhesion Peeling 
______________________________________ 
Examples 19 .largecircle. 
.DELTA. 
.largecircle. 
20 .largecircle. 
.largecircle. 
.largecircle. 
21 .largecircle. 
.DELTA. 
.DELTA. 
22 .largecircle. 
.largecircle. 
.largecircle. 
23 .largecircle. 
.DELTA. 
.largecircle. 
24 .largecircle. 
.largecircle. 
.largecircle. 
25 .largecircle. 
.largecircle. 
.largecircle. 
26 .largecircle. 
.largecircle. 
.DELTA. 
27 .largecircle. 
.largecircle. 
.largecircle. 
28 .largecircle. 
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29 .largecircle. 
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30 .largecircle. 
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31 .largecircle. 
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32 .largecircle. 
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33 .largecircle. 
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34 .largecircle. 
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35 .largecircle. 
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36 .largecircle. 
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37 .largecircle. 
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.largecircle. 
Compara- 14 .largecircle. 
.times. 
.DELTA. 
tive 15 .largecircle. 
.times. 
.DELTA. 
Examples 16 .largecircle. 
.times. 
.DELTA. 
17 .largecircle. 
.times. 
.DELTA. 
18 .largecircle. 
.times. 
.largecircle. 
19 .times. .largecircle. 
.largecircle. 
20 .times. .largecircle. 
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21 .times. .largecircle. 
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22 .times. .largecircle. 
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23 .times. .largecircle. 
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24 .times. .largecircle. 
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TABLE 12 
______________________________________ 
Components for constituting 
two layers 
Pigment disper- 
Phosphor dispersion 
sion solution 
solution 
______________________________________ 
Examples 38 (i) B 
39 (i) C 
40 (i) D 
41 (i) E 
42 (i) F 
43 (ii) A 
44 (ii) B 
45 (ii) C 
46 (ii) D 
47 (ii) E 
48 (ii) F 
49 (iii) A 
50 (iii) B 
51 (iii) C 
52 (iii) D 
53 (iii) E 
54 (iii) F 
55 (iv) A 
56 (iv) B 
57 (iv) C 
58 (iv) D 
59 (iv) E 
60 (iv) F 
Compara- 25 (i) A 
tive 26 (v) A 
Examples 27 (v) B 
28 (v) C 
29 (v) D 
30 (v) E 
31 (v) F 
24 (v) F 
______________________________________ 
Properties 
Dissolving- 
out Adhesion Peeling 
______________________________________ 
Examples 38 .largecircle. 
.DELTA. 
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39 .largecircle. 
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40 .largecircle. 
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41 .largecircle. 
.largecircle. 
.DELTA. 
42 .largecircle. 
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.largecircle. 
43 .largecircle. 
.DELTA. 
.DELTA. 
44 .largecircle. 
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45 .largecircle. 
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46 .largecircle. 
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47 .largecircle. 
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48 .largecircle. 
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49 .largecircle. 
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50 .largecircle. 
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51 .largecircle. 
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52 .largecircle. 
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53 .largecircle. 
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54 .largecircle. 
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55 .largecircle. 
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56 .largecircle. 
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57 .largecircle. 
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58 .largecircle. 
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59 .largecircle. 
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60 .largecircle. 
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.largecircle. 
Compara- 25 .largecircle. 
.times. 
.times. 
tive 26 .times. .largecircle. 
.largecircle. 
Examples 27 .times. .largecircle. 
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28 .times. .largecircle. 
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29 .times. .largecircle. 
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30 .times. .largecircle. 
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31 .times. .largecircle. 
.largecircle. 
______________________________________ 
Example 61 
Of the filter-applied phosphor layers, a blue phosphor layer was formed on 
a plate glass. 
As to the pigment dispersion solution and the phosphor slurry, the same 
materials as those in the Example 10 were used. The pigment dispersion 
solution was applied on a plate glass while maintaining the temperature of 
the plate glass at 30.degree. C. Further, the panel was rotated at a speed 
of 100 to 150 rpm, and the excessive portion of the solution was shaken 
off. The pigment solution was dried by a heat wave having a temperature of 
70.degree. C. for 3 to 4 minutes, thus forming a blue pigment layer. 
The phosphor slurry was applied on the glass surface on which the blue 
pigment layer was formed in the same manner as above. Then, the panel 10 
was rotated at 150 to 230 rpm so as to shake off the excessive portion of 
the pigment dispersion solution. After that, the application layer was 
dried by a heater at a temperature of 70.degree. C. for 2 to 3 minutes, 
thus obtaining a blue phosphor layer on the blue pigment layer. 
The layers were exposed into a predetermined pattern via a mask by use of a 
high-pressure mercury lamp. A developing agent was sprayed at a developing 
agent pressure of 2 to 10 kg/cm.sup.2 in a mist fashion, thus performing a 
development, and a blue-filter-applied blue phosphor layer having a 
predetermined pattern was formed. 
The filter-applied phosphor layer thus obtained was evaluated by the same 
method as of Example 10, and the results of the evaluation were the same 
as those summarized in TABLE 7. 
Example 62 
Of the filter-applied phosphor layers, a red phosphor layer was formed on 
the inner surface of a face plate of a color cathode ray tube. 
The red pigment dispersion solution was prepared by dispersing 25 weight % 
of fine particles of Fe.sub.2 O.sub.3 (particle diameter: 0.01 .mu.m to 
0.02 .mu.m), and 0.25 weight % of ammonium salt of 
polyoxyethylenealkylethersulfate (Hitenor 08 of Daiichi Kogyo Seiyaku Co. 
Ltd.) into pure water. The ratio of the polymer electrolyte 
concentration/the pigment concentration was set to 0.01. 
The phosphor suspension solution (phosphor slurry) was prepared by mixing 
40 g of red phosphor substance (Y.sub.2 O.sub.2 S:Eu), 0.16 g of sodium 
dichromate (SDC), 1.4 g of polyvinyl alcohol (average molecular weight: 
2400, 88% of saponification) and 54 g of pure water, all of which were 
weighed. 
A red-filter-applied red phosphor layer was obtained by the same method 
used in Example 10 by use of the above pigment dispersion solution and 
phosphor slurry. 
The filter-applied phosphor layer thus obtained was evaluated by the same 
method as of Example 10, and the results of the evaluation were summarized 
in TABLE 13. 
Examples 63 to 67 
In each of these examples, a filter-applied phosphor layer was obtained 
with the same material and by the same method used in Example 62 except 
that the mixture ratio of the pigment dispersion solution was varied, and 
each phosphor layer was evaluated by the same method as that of Example 
10. 
The mixture ratios of the pigment dispersion solution and the results of 
the evaluation were summarized in TABLE 13. 
Comparative Examples 32 to 33 
In each of these examples, a red filter-applied red phosphor layer was 
obtained with the same material and by the same method used in Example 62 
except that the mixture ratio between the polymer electrolyte 
concentration/the pigment concentration in the pigment dispersion solution 
was set to 0.003 (Comparative Example 32) and to 1.5 (Comparative Example 
33. 
Each of the filter-applied phosphor layer was evaluated by the same method 
as that of Example 10. 
The mixture ratios of the pigment dispersion solution and the results of 
the evaluation were summarized in TABLE 13. 
TABLE 13 
______________________________________ 
Composition of pigment 
dispersion solution 
Red Dis- Pure 
pigment 
persant water Ratio 
______________________________________ 
Examples 62 25.0 0.25 74.75 
0.01 
63 25.0 0.13 74.87 
0.005 
64 25.0 1.3 73.7 0.05 
65 25.0 25.0 50.0 0.10 
66 25.0 12.5 62.5 0.50 
67 25.0 25.0 50.0 1.00 
Compara- 32 25.0 0.08 74.92 
0.003 
tive 33 25.0 37.5 37.5 1.50 
Examples 
______________________________________ 
Properties 
Dissolving-out 
Adhesion Peeling 
property property property 
______________________________________ 
Examples 62 .largecircle. 
.largecircle. 
.largecircle. 
63 .largecircle. 
.largecircle. 
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64 .largecircle. 
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65 .largecircle. 
.largecircle. 
.largecircle. 
66 .DELTA. .DELTA. 
.largecircle. 
67 .DELTA. .DELTA. 
.largecircle. 
Compara- 32 .largecircle. 
.largecircle. 
.times. 
tive 33 .times. .DELTA. 
.largecircle. 
Examples 
(in weight %) 
______________________________________ 
Red pigment: Fe.sub.2 O.sub.3 
Dispersant: Ammonium salt of polyoxyethylenealkylether sulfate 
Ratio: Ratio between dispersant/red pigment 
Example 68 
In this example, a red-filter-applied red phosphor layer was prepared with 
the same materials and method as those of Example 62 except that Y.sub.2 
O.sub.3 :Eu was used as the red phosphor substance. 
The filter-applied phosphor layer thus obtained was evaluated by the same 
method as of Example 62, and substantially the same results as those of 
Example 62 were obtained. Further, red-filter-applied red phosphor layers 
were prepared with various amounts of dispersant as in Examples 63 to 67, 
and they were evaluated. The results of the evaluation were the same as 
those summarized in TABLE 13. 
Example 69 
Of the filter-applied phosphor layers, a green phosphor layer was formed on 
the inner surface of a face plate of a color cathode ray tube. 
The pigment dispersion solution was prepared by dispersing 30 weight % of 
TiO.sub.2 -NiO-CoO-ZnO (Dypyroxide TM-Green #3320, particle diameter: 0.01 
.mu.m to 0.02 .mu.m, DAINICHI SEIKA Inc.) and 0.3 weight % of ammonium 
salt of polyacrylic acid copolymer (Dispex GA-40, Allied Colloid Inc.) 
into pure water. The ratio of the polymer electrolyte concentration/the 
pigment concentration was set to 1/100. 
The phosphor suspension solution (phosphor slurry) was prepared by mixing 
40 g of green phosphor substance (Y.sub.2 O.sub.2 S:Eu), 0.16 g of sodium 
dichromate (SDC), 1.4 g of polyvinyl alcohol (average molecular weight: 
2400, 88% of saponification) and 54 g of pure water, all of which were 
weighed. 
A green-filter-applied green phosphor layer was obtained by the same method 
used in Example 10 by use of the above pigment dispersion solution and 
phosphor slurry. 
The filter-applied phosphor layer thus obtained was evaluated by the same 
method as of Example 10, and the results of the evaluation were the same 
as of Example 10. 
Example 70 
In this example, on the inner surface of the face plate of a color cathode 
ray tube, a blue-filter-applied blue phosphor layer was formed by the same 
method as that of Example 10, followed by the formation of a 
red-filter-applied red phosphor layer by the same method as that of 
Example 62 and a green-filter-applied green phosphor layer by the same 
method as that of Example 69. These layers were patterned, thus obtaining 
a blue/red/green filter-applied phosphor two-layer pattern. In the 
formation of each color pattern, and at an intermediate portion between 
colors, two-layer pattern having a good dissolving property was obtained 
in a wide range of work. Further, the color cathode ray tube thus obtained 
exhibited a good contrast and color purity. 
As is clear from Examples 10 to 70, according to the present invention, in 
the step of forming or developing, for example, a phosphor layer, which is 
obtained by applying a solution of salt of polymer electrolyte, containing 
pigment particles, on a substrate, and dissociating at least the salt of 
the polymer electrolyte salt partially, followed by drying, another 
solution containing a substance which can form a salt with a partially 
dissociated polymer electrolyte salt, is used. With this constitution, in 
the case where patterning is carried out on a multi-layer by one exposure, 
the two contradicting properties, namely, the dissolving out property and 
the developing property, can be satisfied at the same time. 
Consequently, a cathode ray tube and a filter-applied phosphor layer of a 
color image receiving apparatus, each of which has a good contrast and a 
color purity, can be obtained at a wide range of work condition. 
Additional advantages and modifications will readily occur to those skilled 
in the art. Therefore, the invention in its broader aspects is not limited 
to the specific details, and illustrated examples shown and described 
herein. Accordingly, various modifications may be made without departing 
from the spirit or scope of the general inventive concept as defined by 
the appended claims and their equivalents.