Polyvinyl alcohol base photosensitive resin, photosensitive composition, and method for pattern-formation using the same

A polyvinyl alcohol base photosensitive resin comprised of a polyvinyl alcohol base polymer compound with the structural units of formulae (I) and (II) ##STR1## as well as a photosensitive resin composition comprising this resin and, optionally, an anionic additive and a method of forming a pattern using this photosensitive composition. R.sup.1 is a residue of a heterocyclic ring with quaternarized aromatic species, R.sup.2 is hydrogen atom or lower alkoxyl group, M is 0 or 1, and n is 1 to 6. X.sup.1, X.sup.2 are hydrogen atom, sodium, potassium or ammonium ion. These resins aid in water solubility, compatibility and sensitivity and are used in forming screen printing plates, black matrix or phosphor pattern formation of color cathode ray tubes, color filters, color printing proofs and etching resists.

BACKGROUND OF THE INVENTION 
The present invention relates to a polyvinyl alcohol base photosensitive 
resin, a photosensitive resin composition, and a method of forming a 
pattern using the resin or the composition. The present invention allows a 
favorable pattern formation on an anionic substrate as a consequence of 
its excellent mutual solubility with an anionic additive. 
As water-soluble polyvinyl alcohol base photosensitive resins, heretofore, 
polyvinyl alcohol base photosensitive resins described in patent documents 
such as Japanese Patent Application Publication No. 56-5761, Japanese 
Patent Application Publication No. 56-5762, Japanese Patent Application 
Laying-open No. 56-11906, Japanese Patent Application Laying-open No. 
59-17550, Japanese Patent Application Laying-open 2-118575, Japanese 
Patent Application Laying-open No. 2-276806, and Japanese Patent 
Application Publication No. 6-43645 have been known. Each of these 
comprises a styryl derivative as a pendant group having a nitrogen 
heterocyclic ring with a quaternary aromatic species. However, these 
resins have the following disadvantages. That is, these photosensitive 
resins show high photo-sensitivities but poor water-resistance. Therefore 
they can be swelled at the stage of development, resulting in an 
insufficient resolution. In addition, these photosensitive resins are 
cationic materials, so that each of them tends to become thicker or to 
become a gel when they are mixed with an anionic additive such as an 
anionic surfactant and an emulsion. Furthermore, when a pattern is formed 
on an anionic surface of the substrate using the above photosensitive 
resin, scum can be generated as a result of ionic interaction. 
In a previous attempt to solve the above disadvantages, a polyvinyl alcohol 
having a styryl derivative as a pendant group having a nitrogen 
heterocyclic ring with a quaternary aromatic species having betaine 
structure as a polyvinyl alcohol base photosensitive resin is disclosed in 
Japanese Patent Application Laying-open No. 2-160807. In this case, 
however, the photosensitive resin has several disadvantages including an 
insufficient water-solubility and a slightly lowered sensitivity. 
Accordingly, all of the conventional polyvinyl alcohol base photosensitive 
resins described above have several disadvantages including poor 
water-resisting properties, poor thermal-resisting properties, and poor 
compatible properties with anionic additives. 
SUMMARY OF THE INVENTION 
The present invention provides a photosensitive resin having the excellent 
properties of water-resistance and thermal-resistance, sufficient 
water-solubility, and sufficient compatibility with an anionic additive, 
together with a photosensitive resin composition and a method of pattern 
formation using the novel resin or composition. 
Specifically, the present invention provides a polyvinyl alcohol base 
photosensitive resin characterized by comprising a polyvinyl alcohol base 
polymer compound having structural units of the following general formula 
(I) and (II): 
##STR2## 
wherein R.sup.1 denotes a residue of a heterocyclic ring having a 
quaternarized aromatic species, R.sup.2 denotes a hydrogen atom or a lower 
alkoxyl group, m is 0 or 1, and n is an integer number selected from 1 to 
6; and 
##STR3## 
wherein each of X.sup.1 and X2 independently denotes a hydrogen atom, a 
sodium ion, a potassium ion, or an ammonium ion, wherein the content of 
the structural unit of the general formula (I) is about from 0.5 to 10 
mole %, while the content of the structural unit of the general formula 
(II) is about from 0.1 to 20 mole %. 
Preferably, the mole ratio represented by the structural unit of the 
general formula (I)/the structural unit of the general formula (II) may be 
less than about 2. 
The present invention further provides a polyvinyl alcohol base 
photosensitive resin composition comprising the above polyvinyl base 
photosensitive resin. 
Preferably, the mole ratio represented by the structural unit of the 
general formula (I)/the structural unit of the general formula (II) in the 
above polyvinyl alcohol base photosensitive resin may be less than about 
2. 
Preferably, the photosensitive resin composition of the present invention 
further comprises anionic additive. 
The present invention still further provides a method of forming a pattern, 
comprising the steps of: forming a photosensitive resin layer on a 
substrate by applying the above polyvinyl alcohol base photosensitive 
resin composition of the present invention; to a substrate performing a 
pattern exposure on said photosensitive resin layer; and subsequently 
developing the resulting exposed layer.

DETAILED DESCRIPTION OF THE INVENTION 
The present invention is based on the discovery that a polyvinyl alcohol 
base polymer compound obtained by suspending a styryl compound having a 
nitrogen heterocyclic ring with a quaternary aromatic species and a phenyl 
compound having two sulfone groups at a predetermined mole ratio satisfies 
the previous deficiencies noted above. Specifically, the polyvinyl alcohol 
base photosensitive resins of the present invention exhibit good 
water-resistance and high-sensitivity. In addition, especially those 
resins in which the mole ratio represented by the structural unit of the 
general formula (I)/the structural unit of the general formula (II) is 
less than about 2 show good compatibility with an anionic additive, and 
hence can be used for forming a pattern on an anionic substrate. 
The polyvinyl alcohol base polymer compound used in the photosensitive 
resin of the present invention can be easily prepared by reacting 
saponified poly (vinyl acetate) or saponified copolymer of vinyl acetate 
with the other vinyl compound with an aldehyde or an acetal represented by 
the following general formula (III) and an aldehyde represented by the 
following general formula (IV) in an aqueous solvent in the presence of an 
acidic catalyst. 
##STR4## 
In the above general formula (III), R.sup.1 is a nitrogen heterocyclic ring 
containing a quaternized aromatic series and it can be exemplified by the 
following formulas. 
##STR5## 
In the above formulas, R.sup.3 is independently selected from a hydrogen 
atom, a lower alkoxyl group, a lower alkoxyl carbonyl alkyl group, or a 
benzyl group; Y denotes an anion ion such as a chloride ion, a bromide 
ion, an iodide ion, a mono-alkyl sulfonate ion, or a p-toluene sulfonate 
ion; and Z denotes O, S, Se, or NR.sup.4 (R.sup.4 is a lower alkyl group). 
Acidic catalysts which can be used in the preparation of the 
polyvinylalcohol base polymeric compound used in the present invention 
include phosphoric acid, hydrochloric acid, sulfuric acid, 
p-toluensulfonic acid, metasulfonic acid, and a resin used for an acidic 
ion-exchange resin. It is noted that the acidic catalyst can be a compound 
represented by the general formula (IV) where X.sup.1 and X.sup.2 are 
independently selected from hydrogen, a sodium ion, a potassium ion, and 
an ammonium ion. 
The above reaction can be conducted in an aqueous solvent, preferably in 
water. There is no restraint on the reaction condition. In general, 
however, the reaction may be performed at about 20.degree.-100.degree. C. 
for about 2-72 hours. 
After terminating the reaction, the reaction mixture is poured into an 
abundance of poor solvent such as acetone, ethanol, or dioxane to form a 
precipitate of a desired resin. Then the resin is separated from the 
reaction mixture and then washed and dried to obtain a photosensitive 
resin of the present invention. After terminating the reaction, 
alternatively, the reaction mixture is neutralized using an alkaline 
aqueous solution such as an aqueous sodium hydroxide, an aqueous potassium 
hydroxide, or an aqueous ammonia water, or using a basic ion-exchange 
resin, followed by a filtration of the ion- exchange resin. Consequently, 
an aqueous solution of a desired photosensitive resin can be obtained. 
Saponified poly (vinyl acetate)s which can be used in the above reaction 
include, for example, those having an average degree of polymerization of 
about from 200 to 5,000, preferably about from 300 to 3,000, and also 
ranging in a degree of saponification about from 60 to 100%, preferably 
about from 70 to 99%. 
The reason why the average degree of polymerization should be kept in the 
range of 200 to 5,000 is that a sufficient sensitivity generally cannot be 
obtained when it is less than about 200, and a viscosity of the solution 
of photosensitive composition becomes too high when it is higher than 
about 5,000, resulting in poor applicability of the solution or lower 
water developmentability. In any of these instances, therefore, undesired 
results may be caused. 
The degree of saponification should be in the range of about from 60% to 
100% because sufficient water-solubility and sufficient water- 
developmentability generally cannot be obtained when it is less than about 
60%. 
Instead of saponified poly (vinyl acetate), as described above, it is 
possible to used a saponified copolymer of vinyl acetate with one of the 
other vinyl compounds including N-vinyl pyrolidone, acrylamide, and N,N- 
dimethyl acrylamide. 
In the case of performing the reaction among this kind of saponified poly 
(vinyl acetate), the compound of the above general formula (III) and/or an 
acetal thereof, and the compound of the above general formula (IV) in the 
preference of an acidic catalyst, it is possible to react them together 
with at least one aldehyde such as formaldehyde, acetaldehyde, 
propionaldehyde, butylaldehyde, benzaldehyde, hydroxybenzaldehyde, and 
acetals thereof. 
The introduction rate of the compound of the general formula (III) or the 
acetal thereof to the saponified poly (vinyl acetate) is generally about 
from 0.5 to 10 mole %, and preferably about from 0.8 to 7 mole % per mole 
unit. If less than about 0.5 mole % is used, the sensitivity is lowered 
without practicality while if it is more than about 10 mole % the 
water-solubility is not enough. For attaining a high sensitivity, the rate 
of introduction should be increased when the degree of polymerization of 
the saponified poly (vinyl acetate) is low, while if the degree of 
polymerization is high a sufficient sensitivity can be attained even 
though the introduction rate is low. 
The introduction rate of the compound of the general formula (IV) to the 
saponified poly (vinyl acetate) is about from 0.1 to 20 mole %, preferably 
about from 0.3 to 15 mole % per mole unit. Outside of that range, the 
water resistibility tends to be deteriorated. 
For the photosensitive resin of the present invention, it is preferable 
that a mole ratio represented by a constituent unit of the general formula 
(I)/a constituent unit of the general formula (II) is less than about 2. 
In this case, the resin tends to be an anionic one having the properties 
of good compatibility with anionic additives and avoiding a generation of 
scum in the step of forming a pattern of an anionic substrate, in addition 
to the properties of high-sensitivity and good water-resistance. 
As will be described in the description concerning the third example of the 
synthesis thereof, inner and/or intermolecular salts may be formed in the 
poly (vinyl alcohol) base photosensitive resin because of no detection of 
phosphate ions and methyl sulfate ions under the assaying of anionic ions 
of the obtained resin using an ion chromatography. In Synthesis Example 3, 
for example, the resin has a structure represented by the following 
general formula (V). 
##STR6## 
The photosensitive resin composition of the present invention comprises the 
above described photosensitive resin of the present invention. In 
particular, the resin shows good compatibility with anionic additives when 
the mole ratio represented by a structural unit of the general formula 
(I)/a structural unit of the general formula (II) is less than about 2, so 
that the composition may comprise an additional anionic additive. 
Among anionic hydrophobic polymer emulsions, the following emulsions (1), 
(2), and (3) can be used as the above additional anionic additive. 
(1) A hydrophobic polymer emulsion comprising an anionic surfactant as an 
emulsifying agent, in which the anionic surfactant may be, for example 
higher fatty acid salt, higher alkyl dicarboxylic acid salt, sulfated 
higher alcohol, alkyl sulfonic acid salt, higher alkyl disulfonic acid 
salt, sulfated oil or fatty acid salt, sulfonated higher fatty acid salt, 
higher alkyl phosphate, sulfate or sulfonate of higher fatty acid, sulfate 
or sulfonate of higher alcohol ether, condensate of higher fatty acid and 
amino acid, alkylolated sulfate of higher fatty amide, alkylated sulfonate 
of higher fatty amide, alkyl carboxylate of sulfonamide, ester of 
sulfosuccinic acid, alkyl benzenesulfonic acid salt, alkyl phenolsulfonic 
acid salt, alkyl naphthalene sulfonic acid salt, formaline condensate of 
alkyl naphthalene sulfonic acid salt, alkyl tetralin sulfonic acid salt, 
alkyl benzimidazole sulfonic acid salt, naphthenic acid salt, or 
naphthenic alcohol sulfate. 
(2) A hydrophobic polymer emulsion comprising an anionic protective colloid 
as an emulsion, in which the anionic protective colloid may be, for 
example, carboxyl or sulfonate denatured polyvinyl alcohol, poly(acryl 
acid salt), or poly(methacryl acid salt). 
(3) A hydrophobic polymer emulsion comprising an unsaturated compound as a 
copolymerized component, in which the unsaturated compound may be, for 
example, acrylic acid, metacrylic acid, itaconic acid, or 2-sulfoethyl 
metacrylate. 
Anionic surfactants include the same chemicals as in the description 
concerning the anionic hydrophobic polymer emulsion. 
Anionic dye stuffs include a substantive dye and an acidic dye. 
Anionic pigments include a pigment having a carboxylic group or a sulfonic 
group, and a pigment treated with an anionic polymer or the like. 
Anionic water-soluble polymers include a water-soluble polymer having a 
carboxyl group or a sulfonic group. 
One of the advantages of the present composition is that it can be used in 
conjunction with the other anionic photosensitive materials such as 
4,4'-diazide stilbene-2,2'-disufonic acid, 4,4'-diazide 
benzalacetone-2,2'-disulfonic acid, 2,5-bis (4'-azide-2'-sulfobenzylidene) 
cyclopentanone, 2,6-bis (4'-azide-2'-sulfobenzylidene) cyclohexane, or one 
of their alkali metal salts, ammonium salts, organic amine salts, and 
organic quaternary ammonium salts. 
For incorporating the above anionic azide base photosensitive material into 
the composition of the present invention, it is preferable to further 
provide a water-soluble polymer having a good reactivity with a 
photoreactive intermediate of the azide group into the composition. The 
water-soluble polymer may be poly (vinyl pirolidone), poly(acrylamide), 
poly (N,N-dimethyl acrylamide), copolymer of acrylamide with diacetone 
acrylamide, copolymer of acrylamide with N,N-dimethylacrylamide, and 
cationic cellulose. 
Characteristics of the present compositions can be further improved by 
adding at least a photopolymerizable unsaturated compound and a 
photopolymerization initiating system. 
The photopolymerizable an unsaturated compound can be either hydrophobic or 
hydryophilic, for example an unsaturated prepolymer or an unsaturated 
polymer comprising at least one polymerizable unsaturated group having an 
acryl group, a methacryl group, an aryl group, a vinylether group, a vinyl 
group, an acrylamide group, or the like. 
The photopolymerization initiating system can be a system responsible for 
generating free radicals having photopolymerizing activities by 
irradiating light, for example an .alpha.-bond cleavage type initiator 
such as benzoin ether, hydroxyl alkylketone, dialkoxyacetophenone, benzoyl 
phosphine oxide, or benzoin oxime ketone; aromatic ketone such as 
benzophenone, benzyl, thioxanthone, or keto-coumarin; a system of the 
aromatic ketone and a hydrogen donator such as amine; a system of organic 
peroxide, onium salt, triphenyl alkyl borate, or an iron/arene complex, 
and an electron donator such as thioxanthene dye, or keto-coumarin; a 
system of N-aryl glycine and an electron acceptor; and polyhalide 
compound. 
In general, furthermore, it is preferable that a heat polymerization 
inhibitor is added in those photopolymerization systems. 
The composition of the present invention may further comprise a non-ionic 
hydrophobic polymer emulsion, a surfactant, a dye, a pigment, an inorganic 
filler, an emulsion stabilizer, a plasticizer, a leveling agent, and so 
on, excepting any one of the above components. A cationic additive may 
also be used in the above composition in an acceptable amount thereof 
without thickening or gelating a solution of the composition. The 
composition may further comprise any of the phosphors for forming a 
phosphor pattern or any of the known light absorption materials such as 
graphite for forming a black matrix. 
The composition of the present invention may be prepared by adding the 
above cationic additive and the other various additives as needed into the 
above polyvinyl alcohol base polymer compound and dissolving or dispersing 
the mixture in a water base solvent. Water is generally used as the 
solvent. However, it is possible to add a water-soluble solvent into the 
water at the concentration of less than about 50 wt. %. The water-soluble 
solvent can be selected from a variety of known water-soluble agents such 
as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, 
tetrahydrofuran, dioxan, dimethyl formamide, or N-methyl pyrrolidinone, 
ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the 
like. 
The photosensitive resin composition of the present invention obtained by 
the way as described above can be coated and dried on a substrate so as to 
obtain a coating film with a dry thickness of about from 0.5 to 1, 000 
.mu.m, for example. The substrate can be selected from a metal plate made 
of aluminum, stainless steel, or the like, a screen mesh, a sheet of 
paper, a glass plate, a semiconductor substrate, and so on, with reference 
to the uses. 
A patterning image can be formed on the coating film by the steps of 
irradiating the coating film with ultra-violet, for example an active beam 
of about from 300 to 500 nm in wavelength to cure an irradiated portion of 
the coating film and removing a non-irradiated portion of the coating film 
using water or the like. Therefore, it can be used as a screen printing 
plate, a black matrix or a phosphor pattern formation of a color 
cathode-ray tube (CRT), a color filter of CCD or LCD, a color printing 
proof, any one of various kinds of etching resists, or the like. 
A pattern formation particularly suited for using the composition of the 
present invention is to form a pattern on a substrate having an anionic 
surface. The pattern with the remaining scum on the non-irradiated portion 
can be obtained when the pattern is formed on the substrate having the 
anionic surface using the conventional cationic polyvinyl alcohol base 
photosensitive resin. On the other hand, a clean pattern without any scum 
can be obtained when the pattern is formed on the substrate using the 
composition of the present invention. 
The following concrete examples show pattern formation on the substrate 
having the anionic surface using the present composition. In these 
examples, a color CRT comprises strips or dot patterns of red, green, and 
blue phosphors and non-luminescent light-absorbing materials such as 
graphite that fills spaces among the phosphors, in which the latter is 
designated as a black matrix. It can be prepared by the following steps. 
First, each color phosphor pattern is formed after forming the black 
matrix which is provided as a graphite-dispersed liquid. A dispersant to 
be used in the step of dispersing the graphite is selected from anionic 
chemicals such as a sodium salt of carboxymethyl cellulose (Japanese 
Patent Application Laying-open No. 46- 218), a lithium salt of 
carboxymethyl cellulose (Japanese Patent Application Laying-open No. 
4-82140), and sodium .beta.- naphthalene sulfonate. Consequently, the 
surface of the black matrix is provided as an anionic one on which a 
photosensitive composition comprising dispersed phosphors is applied and 
then developed after light exposure. If the photosensitive composition is 
cationic, the development cannot be performed perfectly and scum remains 
on the surface. It results in the remaining phosphor on the black matrix 
at the non-illuminating portion. Using the anionic composition of the 
present invention in the photosensitive composition comprising the 
dispersed phosphors, on the other hand, a clean pattern of each phosphor 
without any color mixtures can be obtained as a result of the perfect 
development. 
SYNTHESIS EXAMPLE 1 
Polyvinyl alcohol (PVA) GH-17 (manufactured by Nippon Synthetic Chemical 
Industry, the degree of polymerization of 1,700 and the degree of 
saponification of 88%) in an amount of 10 g was dissolved in 90 g of pure 
water. Then 0.581 g of N-methyl-4-formylstyryl pyridinium methasulfate 
(hereinafter abbreviated as SbQ; the ratio to a unit mole of PVA was 0.85 
mole %) and 0. 25 g of phosphoric acid were added in the dissolved 
solution and stirred at 30.degree. C. for 3 hours. Furthermore, 0.783 g of 
sodium benzaldehyde-2,4-disulfonate (hereinafter abbreviated as diBAS; 
purity=84.7%; concentration=1.235-fold mole of SbQ) was added and stirred 
at 30 .degree. C. for 20 hours to obtain a reaction mixture. In the 
reaction mixture, 2.5 g of Amberlite IR-45 (Ion-exchange resin 
manufactured by Rohm & Hass) was added and then stirred for 2 hours. After 
completion of the reaction, the pH of the mixture was checked to be 
neutral and then the mixture was filtered through 400-mesh screen to 
obtain a light-yellowish polymer aqueous solution. 
Measuring with an ultraviolet spectrophotometry, introduction rates of SbQ 
and iBAS to polyvinyl alcohol molecules were 0.72 mole % and 0.76 mole %, 
respectively. 
SYNTHESIS EXAMPLE 2 
Polyvinyl alcohol (PVA) GH-17 (manufactured by Nippon Synthetic Chemical 
Industry, the degree of polymerization of 1,700 and the degree of 
saponification of 88%) in an amount of 10 g was dissolved in 90 g of pure 
water. Then 0.581 g of SbQ (the ratio to a unit mole of PVA was 0. 85 mole 
%) and 0.25 g of acid were added in the dissolved solution and stirred at 
30.degree. C. for 3 hours. Subsequently, 0.286 g of diBAS 
(concentration=0.54-molar equivalent of SbQ) was added and stirred at 
30.degree. C. for 20 hours to obtain a reaction mixture. In the reaction 
mixture, 2.5 g of Amberlite IR-45 (Ion-exchange resin manufactured by Rohm 
& Haas) was added and then stirred for 2 hours. After completion of the 
reaction, the pH of the mixture was checked to be neutral and then the 
mixture was filtered through 400-mesh screen to obtain a light-yellowish 
polymer aqueous solution. 
Measuring with an ultraviolet spectrophotometry, the introduction rates of 
SbQ and iBAS to polyvinyl alcohol molecules were 0.72 mole % and 0.33 mole 
%, respectively. 
SYNTHESIS EXAMPLE 3 
Polyvninylalcohol (PVA) GH-17 (manufactured by Nippon Synthetic Chemical 
Industry, the degree of polymerization of 1,700 and the degree of 
saponification of 88%) in an amount of 10 g was dissolved in 90 g of pure 
water. Then 0.581 g of SbQ (the ratio to a unit mole of PVA was 0.85 mole 
%) and 0.25 g of phosphoric acid were added in the dissolved solution and 
stirred at 30.degree. C. for 3 hours. Subsequently, 0.783 g of diBAS 
(concentration=1.235-molar equivalent of SbQ) was added and stirred at 
30.degree. C. for 20 hours to obtain a reaction mixture. An excess amount 
of acetone was poured into the reaction mixture to obtain a white polymer 
precipitate. The precipitate was washed with methanol sufficiently and 
then dried in a vacuum, resulting in 9.5 g of polyvinyl alcohol 
derivative. 
Measuring with an ultraviolet spectrophotometry, the introduction rates of 
SbQ and iBAS to polyvinyl alcohol molecules were 0.72 mole % and 0.76 mole 
%, respectively. 
In addition, methyl sulfate ions derived from SbQ and phosphate ions 
derived from the catalyst were detected in extremely small quantities by 
ion-chromatographic analysis. Consequently, the results give support to 
the internal salt structure represented by the general formula (V), so 
that it reveals that the polymer is anionic one. 
SYNTHESIS COMATIVE EXAMPLE 1 
A polyvinyl alcohol derivative comprising the above PVA (GH-17) reacted 
with 0.72 mole % of SbQ was obtained according to the process disclosed in 
Japanese Patent Laying-open No. 55-23163. There was no anionic composition 
in the product, so that it was a perfect cationic polymer. 
Example 1 
10 wt. % of the polymer aqueous solution of Synthesis Example (I) was mixed 
with Finetex ES-650 (manufactured by Dai Nippon Ink, Co., Ltd. ; polyester 
emulsion, a dry solids content of 29 wt. %) at a solids ratio of one to 
two. A clear photosensitive composition was obtained except for an 
extremely small amount of thickening. 
Then the above photosensitive composition was applied on a 250-mesh screen 
printing plate through a screen to make a coating film of 15 .mu.m in 
thickness. Subsequently, the coating film was developed with a 
water-spray. The coating film was exposed for 90 seconds by means of an 
extra-high pressure mercury-vapor lamp (2kw) positioned at a distance of 
60 cm from the surface of the film. Making visual observations, there was 
no substantial swelling in the resulting film. In addition, a good 
resolution was attained. 
SYNTHESIS COMATIVE EXAMPLE 2 
10 wt. % of an aqueous solution was prepared by dissolving the polymer 
obtained in Comparative Example 1 as is the case with Example 1. Using the 
same procedure as that of Example 1, the aqueous solution was mixed with 
ES-200 at a solids ratio of 1 to 2, resulting in extremely high 
thickening. Consequently, the same test on the screen as that of Example 1 
could not be performed. 
Example 2 
10 wt. % of the polymer aqueous solution of Synthesis Example (II) was 
mixed with a vinyl acetate emulsion (Mowinyl MA6 manufactured by Hoechst 
Synthesis, Co., Ltd.) at a solids ratio of one to two. Then the mixture 
was applied on a 250-mesh screen printing plate through a screen to make a 
coating film of 15 .mu.m in thickness. Subsequently, the coating film was 
developed with a water-spray. The coating film was exposed for 110 seconds 
by means of an extra-high pressure mercury-vapor lamp (2kw) positioned at 
a distance of 60 cm from a surface of the film. According to visual 
observations, therefore, there was no substantial swelling in the 
resulting pattern. In addition, a good resolution was attained. 
COMATIVE EXAMPLE 2 
10 wt. % of the polymer aqueous solution of Synthesis Comparative Example 
(II) was mixed with a vinyl acetate emulsion (Mowinyl MA6 manufactured by 
Hoechst Synthesis, Co., Ltd.) at a solids ratio of one to two. Then the 
mixture was applied on a 250-mesh screen printing plate through a screen 
to make a coating film of 15 .mu.m in thickness. Subsequently, the coating 
film was developed with a water-splay. The coating film was exposed for 
110 seconds by means of an extra-high pressure mercury-vapor lamp (2 kw) 
positioned at a distance of 60 cm from the surface of the film. Comparing 
with the results of Example 2, there was observed a lager amount of 
swelling in the resulting pattern. In addition, a poor resolution was 
obtained. 
Example 3 
A photosensitive solution consisting of polyvinylpyrolidone and 
4,4'-diazidestilbene-2,2'-sodium disulfonate, Electroduck 1530 
(manufactured by Achison Japan, Co., Ltd.; a graphite fluid dispersion), 
and a shadow mask with a hole size of 135 .mu.m were used according to the 
general process disclosed in Japanese Patent Laying-open No. 48-90815 and 
so on. As a result, the black matrix of the CRT with a hole size of 105 
.mu.m was prepared on a soda glass plate of 10 cm square. 
Then a so-called phosphor slurry of the following formula was applied on 
the above glass plate and then dried to make the film with 8 to 10 .mu.m 
in thickness. Subsequently, a phosphor pattern was prepared according to 
the following conditions. According to the observations on the resulting 
pattern, the packing density of the phosphor was excellent. In addition, 
an excellent resolution was also observed and the remaining phosphor was 
not detected on the black matrix. 
______________________________________ 
(Composition of Phosphor Slurry) 
______________________________________ 
Green phosphor 10 gr. 
10 wt. % polymer aqueous solution 
10 gr. 
of Synthesis Example 1 
Pure water 15 gr. 
5% Tamol 731 aqueous solution 
1 gr. 
(manufactured by Rohm & Haas, 
Co., Ltd.; an anionic surfactant) 
10% LT-221 aqueous solution 
0.05 gr. 
(manufactured by Nippon Oil & 
Fats, Co., Ltd.; a nonionic surfactant) 
______________________________________ 
(Condition of Pattern Formation) 
Shadow mask: a hole diameter of 135 .mu.m 
Distance between shadow mask and glass plate: 10 mm Distance between 
light-source and glass plate: 30 cm light-source: Ultra-high pressure 
mercury lamp, 350 nm, 
an intensity of illuminance of 0.15 mW/cm 2 Exposure time: 40 sec. 
Development: Water-spray development 
COMATIVE EXAMPLE 3 
In an analogous fashion, furthermore, the polymer of Comparative Example 2 
was evaluated. In this example, however, a phosphor slurry was prepared 
from the formula of Example 3 except Tamol 731 as a surfactant because 
there was an insufficient compatibility between them. 
A phosphor pattern was prepared under the same conditions as that of 
Example 3 and using the above phosphor slurry. According to the 
observations on the resulting pattern, the packing density of the phosphor 
was excellent and also an excellent resolution was observed just as in the 
case of Example 3. In this case, however, the remaining phosphor was not 
detected on the black matrix. A large amount of phosphor remained on the 
black matrix after the development. 
According to such results, the polymer of Comparative Example 1 is a 
cationic polymer and thus it tends to remain as a result of ionic 
interaction with an anionic surface of the black matrix. Consequently, it 
is presumed that the phosphor tends to remain on the surface of the black 
matrix. 
According to the present invention, as described above, a photosensitive 
resin is provided as a polyvinyl alcohol base polymer compound obtained by 
suspending a styryl compound having a nitrogen heterocyclic ring with a 
quaternary aromatic species and a phenyl compound having two sulfone 
groups, so that it has the effects of the excellent properties of 
water-resistance and heat-resistance, and sufficient water-solubility. In 
addition, it also has the effect of excellent compatibility to an anionic 
additive by appropriately selecting the ratio of components. 
The present invention has been described in detail with respect to 
preferred embodiments, and it will now be that changes and modifications 
may be made without departing from the invention in its broader aspects, 
and it is the intention, therefore, in the appended claims to cover all 
such changes and modifications as fall within the true spirit of the 
invention.