A photosetting composition useful as a coating varnish comprising a modified, epoxidized butadiene polymer, at least one photopolymerizable monomer and a photosensitizer, the modified, epoxidized butadiene polymer comprising (1) an epoxidized butadiene polymer backbone group, (2) 5 to 50 aromatic or cyclocyclic polybasic carboxylic ester side chain groups per 100 butadiene units, each having at least one acryloyl or methacryloyl terminal group and a linking group formed by a reaction between a carboxylic acid radical in the polybasic carboxylic ester and an epoxy radical in the epoxidized butadiene polymer and, optionally, (3) 0 to 50 phosphoric ester additional side chain groups per 100 butadiene units, each having a linking group formed by a reaction between a hydroxyl radical attached to a P atom in the phosphoric ester and an epoxy radical in the epoxidized butadiene polymer.

FIELD OF THE INVENTION 
The present invention relates to a photosetting composition. More 
particularly, the present invention relates to a photosetting composition 
which is capable of being cured by exposure to actinic rays, such as 
ultraviolet rays, and which is useful as a coating varnish for metal and 
synthetic resin articles. 
BACKGROUND OF THE INVENTION 
It is known that a metal or synthetic resin article can be coated with a 
thermosetting resin by a process in which a solution of the resin in a 
solvent is applied onto a surface of the article, the applied resin 
solution layer is dried and, then, the dried resin layer is cured at an 
elevated temperature. The above-mentioned conventional thermosetting 
process is disadvantageous in that a large scale drying and curing 
apparatus must be used in order to evaporate the solvent from the resin 
solution layer and thermally cure the dried resin layer, that the solvent 
vapor generated in the drying and curing apparatus may pollute the 
atmosphere, and that a large amount of thermal energy is consumed for 
evaporating the solvent and for curing the resin layer. 
In order to eliminate the above-mentioned disadvantages of the 
thermosetting process, a photosetting process was proposed. In the 
photosetting process, a liquid photosetting composition is applied onto a 
surface of the article and the applied photosetting composition layer is 
cured by the action of actinic rays, such as ultraviolet rays. The 
conventional photosetting composition contains, for example, an epoxy 
resin or a liquid polybutadien as a base component. However, the 
conventional epoxy resin type photosetting composition is disadvantageous 
in such features that the stability of the composition during storage is 
poor, that the photocuring reaction rate of the composition is low, that 
the adhering property of the composition to the article surface to be 
coated is poor, and that the resultant photocured composition exhibits a 
poor flexural strength and impact strength. On the other hand, the 
conventional liquid polybutadiene type photosetting composition exhibits a 
poor photosetting rate and adhering property, and the resultant photocured 
composition exhibits a poor hardness. Accordingly, neither the 
conventional epoxy resin type nor liquid polybutadiene type photosetting 
composition is proper as a coating varnish. 
Japanese Patent Application Laying-Open Nos. 48-29886(1973) 49-98454(1974) 
and 51-37128(1976) disclose photosetting compositions containing, as a 
base component, an epoxidized polybutadiene or modified, epoxidized 
polybutadiene which exhibits both the properties of the epoxy resin and 
the liquid polybutadiene. However, these types of photosetting 
compositions still have the above-mentioned disadvantages of the 
conventional epoxy resin type and liquid polybutadiene type photosetting 
compositions. That is, these types of the photosetting composition have a 
poor storing stability, photocuring reaction rate and adhering property. 
Also, the resultant photocured composition exhibits a poor hardness and 
resistance to water. 
Japanese Patent Application Laying-Open No. 51-37128(1976) discloses a 
photosetting composition containing, as a base component, another type of 
modified epoxidized polybutadiene which is prepared by reacting an 
epoxidized polybutadiene with acrylic or methacrylic acid, a 
photopolymerizable monomer and a photosensitizer. However, this 
photosetting composition has a relatively poor photocuring reaction rate 
and, therefore, a long time required to complete the photocuring reaction. 
Accordingly, this type of photosetting composition is unsuitable for 
practical use. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a photosetting composition 
having an excellent storing stability, photocuring reaction rate and 
adhering property. 
Another object of the present invention is to provide a photosetting 
composition capable of being converted into a photocured composition 
having high flexural and impact strengths, a high hardness and an 
excellent resistance to water. A further object of the present invention 
is to provide a photosetting composition which is useful as a coating 
varnish for metallic and synthetic resin articles. 
The above-mentioned objects can be attained by the photosetting composition 
of the present invention which comprises: 
(A) 100 parts by weight of a modified, epoxidized butadiene polymer which 
comprises (1) a backbone group consisting of a residue of an epoxidized 
butadiene polymer, (2) 5 to 50 side chain groups per 100 butadiene units 
in said backbone group, each of which consists of a residue of a member 
selected from aromatic and cycloaliphatic polybasic carboxylic esters, 
each having at least one terminal group consisting of a member selected 
from the class consisting of acryloyl and methacryloyl radicals and each 
of which is attached to said backbone group through a linking group formed 
by an esterifying reaction between a carboxylic acid radical in said 
polybasic carboxylic ester and an epoxy radical in said epoxidized 
butadiene polymer, and (3) 0 to 50 additional side chain groups per 100 
butadiene units in said backbone group, each of which consists of a 
residue of an acid phosphoric ester compound and is attached to said 
backbone group through a linking group formed by an esterifying reaction 
between a hydroxyl(-OH) group attached to a phosphorus atom in said acid 
phosphoric ester compound and an epoxy radical in said epoxidized 
butadiene polymer; 
(B) 30 to 800 parts by weight of at least one photopolymerizable monomer, 
and; 
(C) 0.5 to 15 parts by weight of a photosensitizer. 
DETAILED DESCRIPTION OF THE INVENTION 
The photosetting composition of the present invention contains, as an 
important component, a special modified, epoxidized butadiene polymer 
which comprises (1) a backbone group consisting of a residue of an 
epoxidized butadiene polymer, (2) 5 to 50 side chain groups per 100 
butadiene units in the backbone group, each consisting of a residue of a 
special acid aromatic or cycloaliphatic polybasic carboxylic ester 
compound and attached to the backbone group, and (3) 0 to 50 additional 
side chain groups per 100 butadiene units in the backbone group, each 
consisting of a residue of a special acid phosphoric ester compound and 
attached to the backbone group. 
The polybasic carboxylic ester side chain group has at least one terminal 
group consisting of a member selected from the class consisting of 
acryloyl and methacryloyl radicals and a linking group through which the 
polybasic carboxylic ester side chain group is attached to the carboxylic 
ester side chain group is attached to the backbone group and which has 
been formed by an esterifying reaction between a carboxylic acid radical 
in the polybasic carboxylic ester compound and an epoxy radical in the 
epoxidized butadiene polymer. The acid phosphoric ester additional side 
chain group has a linking group which has been formed by an esterifying 
reaction between a hydroxyl(--OH) group attached to a phosphorus atom in 
the acid phosphoric ester compound and an epoxy radical in the epoxidized 
butadiene polymer so as to attach the additional side chain group to the 
backbone group. 
The modified, epoxidized butadiene polymer can be prepared by epoxidizing a 
liquid butadiene polymer, and by modifying the epoxidized butadiene 
polymer with the special acid polybasic carboxylic ester compound and, 
optionally, with the special acid phosphoric ester compound. 
In the preparation of the epoxidized butadiene polymer, it is preferable 
that the liquid butadiene polymer have a number average molecular weight 
of from 500 to 5,000, more preferably, from 600 to 3,000. Also, it is 
preferable that the liquid butadiene polymer have a viscosity of from 20 
to 10,000 cps, more preferably, from 30 to 5000 cps, determined at a 
temperature of 30.degree. C. by using a rotation viscometer. The molecular 
structure of the liquid butadiene polymer is not limited to a special 
structure. However, it is preferable that 40% or more of the butadiene 
units in the liquid butadiene polymer have a 1,4-structure. The liquid 
butadiene polymer may be selected from the class consisting of butadiene 
homopolymers and copolymers. The butadiene copolymer preferably comprises 
70% or more butadiene and the balance consisting of one or more comonomer. 
The comonomer which can be copolymerized with butadiene, may be selected 
from the group consisting of acrylonitrile, styrene, acrylic esters, 
methacrylic esters, vinyl acetate, isoprene, 1,3-pentadiene and meleic 
anhydride. 
The liquid butadiene polymer may have a terminal group consisting of a 
hydroxyl, carboxyl and other functional radicals. 
If the rotation viscosity and the number average molecular weight of the 
liquid butadiene polymer are smaller than 20 cps and 500, respectively, 
the resultant photosetting composition may sometimes exhibit a low 
photocuring reaction rate. Also, if the rotation viscosity and the number 
average molecular weight of the liquid butadiene polymer are larger than 
10,000 cps and 5,000, respectively, the resultant photosetting composition 
may sometimes have such an excessively large viscosity that the 
composition exhibits a poor coating processability. 
The epoxidation of the liquid butadiene polymer can be effected by any 
processes. However, it is preferable that the epoxidation be carried out 
to an extent that the resultant epoxidized butadiene polymer has at least 
7, more preferably, from 10 to 80, and even more preferably, from 12 to 
60, of epoxy radicals per 100 butadiene units therein. 
The liquid butadiene polymer may be epoxidized, for example, by reacting it 
with hydrogen peroxide and formic acid in an organic medium at a 
temperature of from 30.degree. C. to 40.degree. C. for several hours. In 
this epoxidation procedure, it is preferable that the molar ratio of 
hydrogen peroxide to formic acid used be in a range of from 1 to 10, more 
preferably, 2 to 6. Also, the ratio in weight of the hydrogen peroxide to 
the liquid butadiene polymer used is preferably in a range of from about 2 
to about 5. 
In another epoxidation process, the method disclosed by Charles E. Fielock 
in "Industrial Engineering Chemistry", vol. 50, No. 3, page 299(1958) may 
be used. In this method, the liquid butadiene polymer reacts with 
peracetic acid in an organic medium at a temperature of about 50.degree. 
C. for about 5 hours in the presence of sodium acetate. 
In every epoxidation process, after the epoxidation reaction is completed, 
the reaction mixture is washed with water so as to remove non-reacted 
hydrogen peroxide or peracetic acid and, then, the resultant epoxidized 
butadiene polymer is isolated from the washed reaction mixture by 
distilling away the organic medium. 
The epoxidized butadiene polymer is modified with at least one member 
selected from the special acid aromatic and cycloaliphatic polybasic 
carboxylic ester compounds. The modifying compound has at least one 
terminal group consisting of an acryloyl or methacryloyl radical, and at 
least one free carboxylic acid radical. That is, the acid polybasic 
carboxylic ester compounds may be one of the formula (I): 
##STR1## 
wherein R.sub.1 represents a hydrogen atom or a methyl radical, A.sub.1 
represents a residue of a polyol compound, for example, diol and 
polyhydric alcohol compounds, which residue is exclusive of the number 
(x.sub.1 +1) of hydroxyl radicals, R.sub.0 represents a residue of an 
aromatic or cycloaliphatic polybasic carbocylic acid, exclusive of the 
number (m+a) of carboxyl radicals, the subscripts X.sub.1, is a positive 
number of from 1 to 3, the subscript m is a positive number of from 1 to 3 
and the subscript a is a positive number of from 1 to 3. The acid 
polybasic carboxylic ester compounds usable for the present invention can 
be prepared by the single step reaction of an ester compound selected from 
the class consisting of acrylate and methacrylate compounds each having a 
hydroxyalkyl radical containing 2 to 16 carbon atoms, with a polybasic 
carboxylic anhydride compound selected from the class consisting of 
substituted and unsubstituted aromatic and cycloaliphatic polybasic 
carboxylic acid anhydrides. 
Otherwise, the acid polybasic carboxylic ester compounds usable for the 
present invention can be prepared by the two-step reaction method wherein, 
first, an intermediate acid ester compound having at least one free 
carboxylic acid radical is prepared by reacting an aromatic or 
cycloaliphatic polybasic carboxylic acid with a polyol compound and, then, 
an acid polybasic carboxylic ester compound is prepared by reacting the 
above-resultant intermediate acid ester compound with an acrylic acid or 
methacrylic acid. 
In either of the above-mentioned single and two-step reaction methods, the 
polybasic carboxylic acid is selected from the group consisting of 
unsubstituted and substituted aromatic and cycloaliphatic polybasic 
carboxylic acids having at least two carboxyl radicals, preferably, 2 to 5 
carboxyl radicals, and the corresponding carboxylic anhydrides having at 
least one intermolecular acid anhydride radical. 
The aromatic polybasic carboxylic acid and anhydride may be selected from 
the class consisting of unsubstituted phthalic acid compounds and 
substituted phthalic acid compounds, for example, halogen-substituted, 
alkoxyl-substituted, hydroxyl-substituted, alkyl-substituted, 
alkylthio-substituted and nitro-substituted phthalic acids and anhydrides 
thereof; trimellitic anhydride, pyromellitic dihydride; biphenyl polybasic 
carboxylic acid compounds, for example, 2,3,3',4',-biphenyl 
tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, and mono 
and di esters and anhydrides of the above-mentioned compounds, and; 
polybasic carboxylic acid compounds having two henzene nuclei bonded to 
each other by a --CO--, --CH.sub.2 --, --O-- or --S--bond, for example, 
2,3,3',4'-benzophenone tetracarboxylic acid, 
3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) 
methane, bis(3,4-dicarboxyphenyl) ether, bis(3,4-dicarboxyphenyl) 
thioether, mono and di, esters and acid anhydrides of the above-mentioned 
compounds. 
The unsubstituted and substituted phthalic acid compound may be selected 
from the class consisting of phthalic anhydride, 3-chlorophthalic acid, 
3,6-dichlorophthalic anhydride, 4-chlorophthalic anhydride, 
4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, 
3-fluorophthalic anhydride, 3,6-difluorophthalic anhydride, 3-iodophilatic 
anhydride, 3,6-diidophthalic anhydride, 4-iodophthalic anhydride, 
4,5-diiodophthalic anhydride, tetraiodophthalic anhydride, 3-bromophthalic 
anhydride, 3,6-dibromophthalic anhydride, 4-bromophthalic anhydride, 
4,5-dibromophthalic anhydride, tetrabromophthalic anhydride, 
4-fluorophthalic anhydride, 4,5-difluorophthalic anhydride; 
3,4-dimethoxyphthalic anhydride, 3,6-dimethoxyphthalic anhydride, 
4,5-dimethoxyphthalic anhydride; 3-(dibromomethyl)phthalic, 
3-ethyl-6-(ethylthio) phthalic anhydride, 3-(ethylthio) phthalic 
anhydride, 3,5-dimethoxy-4-methylphthalic anhydride, 
4,6-dimethoxy-3-methylphthalic anhydride, 3,6-dihydroxyphthalic anhydride, 
3,6-dihydroxy-4-methylphthalic anhydride, 3,6-dimethoxy-4,5-methylene 
dihydroxyphthalic anhydride, 3,4-dimethylphthalic anhydride, 
3,6-dimethylphthalic anhydride, 4,5-dimethylphthalic anhydride, 
3-methylphthalic anhydride, 4-methylphthalic anhydride, 3-methoxyphthalic 
anhydride, 4-methoxyphthalic anhydride, 3-methoxy-4,6-dimethylphthalic 
anhydride, 4-isopropyl-3,5,6-trimethoxyphthalic anhydride, 
4-hydroxyphthalic anhydride, 3-hydroxy-4,6-dimethylphthalic anhydride, 
3-(ethylthio)-6-methylphthalic anhydride, 3-hydroxy-4-methoxyphthalic 
anhydride, 3-hydroxy-5-methoxyphthalic anhydride, 
6-hydroxy-4methoxy-3-methylphthalic anhydride, 
6-isobutyl-3,4-dimethylphthalic anhydride, 3-methyl-5-(phenylthio)phthalic 
anhydride, 3-(methylthio)phthalic anhydride, 3-nitrophthalic anhydride, 
4-nitrophthalic anhydride, 3-(phenylthio)phthalic anhydride, 
3-propylphthalic anhydride and 3-(propylthio)phthalic anhydride. 
The cycloaliphatic polybasic carboxylic acid compound usable for the 
present invention may be selected from the class consisting of 
methyl-3,6-endomethylene tetrahydrophthalic anhydride, 3,6-endomethylene 
tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, 
hexahydrophthalic anhydride and chlorendic anhydride. 
The more preferable polybasic carboxylic acid compounds for forming the 
group Ro in the formula (I) are phthalic anhydride, trimellitic anhydride, 
pyromellitic anhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 
3,3'4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone 
tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, 
bis(3,4-dicarboxyphenyl) methane dianhydride, methyl-3,6-endomethylene 
tetrahydrophthalic anhydride, 3,6-endomethylene tetrahydrophthalic 
anhydride, and tetrahydrophthalic anhydride. 
In the single step reaction method for producing the acid polybasic 
carboxylic ester compounds, the acrylate or methacrylate compounds having 
a hydroxyalkyl radical may be prepared by esterifying a polyol compounds, 
for example, diol compounds and polyhydric alcohol compounds, with acrylic 
or methacrylic acid. The acrylate and methacrylate compounds having a 
hydroxyalkyl radical may be selected from the group consisting of 
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl 
acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monoacrylate, 
polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, 
polypropylene glycol mono-methacrylate, pentaerythritol triacrylate, 
glycerol diacrylate and glycerol monoacrylate. 
In the first step in the two-step reaction method for producing the acid 
polybasic carboxylic ester compounds, the polyol compounds can be selected 
from the class consisting of glycol compounds, for example, ethylene 
glycol, propylene glycol, diethylene glycol dipropylene glycol, 
triethylene glycol, tripropylene glycol, tetraethylene glycol and 
tetrapropylene glycol; polyester compounds having two hydroxyalkyl 
terminal groups, which compounds are esterification products of 
dicarboxylic acid compounds, for example, phthalic anhydride, maleic 
anhydride, malonic acid and succinic acid with an excessive molar amount 
of glycol compounds, for example, ethylene glycol, propylene glycol, 
diethylene glycol, dipropylene glycol and triethylene glycol, or alkylene 
oxides, for example, ethylene oxide and propylene oxide; polybasic alcohol 
compounds, for example, glycerol, polyglycerol and pentaerythritol. 
In a preferable example of the preparation of the acid polybasic carboxylic 
ester compounds by the single-step reaction method, one molar part of an 
aromatic or cycloaliphatic polybasic carboxylic anhydride is esterified 
with 2 molar parts or more, preferably, 2.5 to 6 molar parts of an 
acrylate or methacrylate having a hydroxyalkyl radical, in an organic 
medium or without using medium, in the presence of an esterification 
catalyst consisting of at least one organic quaternary ammonium salt 
selected from triethylbenzyl ammonium chloride, methyltriethyl ammonium 
chloride, tetraethyl ammonium chloride, methyltriethyl ammonium iodide, at 
a temperature of from 70.degree. to 100.degree. C., for 2 to 10 hours. In 
the above-mentioned example of the single step reaction method, the 
reaction mixture may contain a small amount of any known stabilizer for 
thermal polymerization, for example, hydroquinone, 
2,6-di-tert-butyl-p-cresol, and p-benzoquinone. In the case where the 
acrylate or methacrylate compound having a hydroxyalkyl radical is used in 
a very excessive molar amount than the molar amount of the polybasic 
carboxylic anhydride compound used, in the single step reaction method, 
the acrylate or methacrylate compound serves as an organic medium for the 
esterification reaction. After the esterification reaction is completed, 
the non-reacted acrylate or methacrylate compound serves as an organic 
medium for the esterification reaction between the epoxidized butadiene 
polymer and the acid polybasic carboxylic ester compound. Furthermore, 
after the completion of the esterification reaction, the remaining 
acrylate or methacrylate compound may be used as a polymerizable monomer 
component in the resultant photosetting composition. Accordingly, after 
the esterification of the polyol compound with the polybasic carboxylic 
anhydride is completed, the remaining amount of non-reacted acrylate or 
methacrylate is not required to be removed from the resultant reaction 
mixture. 
The photopolymerizable monomer usable for the photosetting composition of 
the present invention, may be used as an organic solvent for both the 
single step reaction and the esterification of the epoxidized butadiene 
polymer with the acid polybasic carboxylic ester compound. 
The completion of the reaction in the single step reaction method can be 
determined by measuring the infra-red ray absorption spectrum in ranges of 
frequencies of from 1760 to 1780 cm.sup.-1 and from 1840 to 1860 cm.sup.-1 
in which the intermolecular acid anhydride radical exhibits absorption 
peaks. When the single step reaction is completed, no peak in the spectrum 
is found. 
In a preferable example of the two step reaction method for preparing the 
acid polybasic carboxylic ester compound, one molar part of an aromatic or 
cycloaliphatic polybasic carboxylic anhydride compound is reacted with 5 
to 30 molar parts, preferably, 10 to 25 molar parts of a polyol compound 
in an organic medium or without using a medium, at a temperature of from 
150.degree. to 200.degree. C., preferably, from 170.degree. to 190.degree. 
C. for from 1 to 10 hours, preferably, from 2 to 7 hours, in the presence 
of a catalyst, to prepare an intermediate ester compound having 1 to 3 
carboxyl acid radicals, and then, one molar part of the intermediate ester 
compound is brought into reaction with 3 to 30, preferably, 5 to 15, molar 
parts of acrylic acid or methacrylic acid, in the presence of a catalyst, 
in an organic medium or without using a medium, at a temperature of from 
70.degree. to 100.degree. C., for from 2 to 10 hours, preferably, from 5 
to 8 hours, in order to provide the desired acid polybasic carboxylic 
ester compound. 
Every esterification mixture in the two step reaction method may contain a 
small amount of the above-mentioned stabilizer for thermal polymerization. 
Especially, it is preferable that the second step esterification be 
carried out in the presence of the thermal polymerization stabilizer. 
The catalyst for the first step esterification can be selected from dibutyl 
tin oxide, sulfuric acid and p-toluene sulfonic acid. The first step 
esterification can be effected even without using the catalyst. The 
catalyst for the second step esterification can be selected from p-toluene 
sulfonic acid, sulfuric acid and acid ion-exchange resins. 
The epoxidized butadiene polymer can be modified with the acid polybasic 
carboxylic ester compound by any known methods. For example, the 
epoxidized butadiene polymer is brought into reaction with the acid 
polybasic carbocylic ester compound, in the presence of a catalyst 
consisting of the above-described organic quarternary ammonium salt usable 
for the single step reactin method or without using the catalyst, in an 
organic medium or without using the medium, at a temperature of from 
50.degree. to 100.degree. C., for example, from 60.degree. to 90.degree. 
C., for from 3 to 20 hours, preferably, from 5 to 15 hours. By the 
above-mentioned reaction procedure, the cyclic epoxy radicals in the 
epoxidized butadiene polymer are cleaved and each addition reacted with a 
free carboxylic acid radical in the acid polybasic carboxylic ester 
compound to form a linking ester group between the epoxidized butadiene 
polymer backbone group and the polybasic carboxylic ester side chain 
group. The resultant modified epoxidized polymer contains 5 to 50, 
preferably, 6 to 40, polybasic carboxylic ester side chain groups per 100 
butadiene units in the backbone group. 
If the number of the polybasic carboxylic ester side chain groups is less 
than 5 per 100 butadiene units, the resultant photosetting composition 
will exhibit a poor photocuring rate and the photocured composition will 
exhibit a poor impact strength. On the other hand, if the number of the 
polybasic carboxylic ester side chain groups is more than 50 per 100 
butadiene units, the modified epoxidized butadiene polymer will exhibit an 
excessively high viscosity which will cause the handling and coating 
operation of the resultant photosetting composition to be difficult. Also, 
it is very difficult to introduce more than 50 polybasic carboxylic ester 
side chain groups into the epoxidized butadiene polymer. 
The modified, epoxidized butadiene polymer may contain 0 to 50 additional 
side chain groups per 100 butadiene units in the backbone group. The 
additional side chain groups each consist of a residue of an acid 
phosphoric ester compound and each is attached to the backbone group 
through a linking group formed by an esterifying reaction between a 
hydroxyl (--OH) radical attached to a phosphorus atom in the acid 
phosphoric ester compound and an epoxy radical in the epoxidized butadiene 
polymer. 
The acid phosphoric ester compound usable for the present invention may be 
selected from the class consisting of the compounds of the formulae (II) 
and (III): 
##STR2## 
wherein R.sub.2 represents a member selected from the group consisting of 
a hydrogen atom and methyl radical, A.sub.2 represents a residue of a 
polyol, exclusive of the number (x.sub.2 +1) of hydroxyl radicals, the 
subscript x.sub.2 is a positive number of from 1 to 3, the subscript n is 
a positive number of from 1 to 2, R represents a member selected from the 
class consisting of alkyl radicals having 1 to 15 carbon atoms, phenyl 
radical and alkylphenyl radical, the alkyl radical of which has 1 to 15 
carbon atoms, and the subscript x.sub.3 is a positive number of from 1 to 
2. 
The acid phosphoric ester compounds of the formula (II) have at least one 
terminal group consisting of an acryloyl or methacryloyl radical and at 
least one free hydroxyl radical attached to the phosphorus atom in the 
compound. This type of compound can be prepared by any known process. For 
example, the compound of the formula (II) can be produced by bringing an 
acrylate or methacrylate compound having a hydroxyalkyl radical into 
reaction with phosphoryl chloride, phosphoric acid or phosphorus 
pentoxide. The acrylate and methacrylate compounds having a hydroxyalkyl 
radical usable for the above-mentioned reaction may be selected from the 
same class as that usable for the preparation of the acid polybasic 
carboxylic ester compounds described hereinbefore. Especially, 
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl 
acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monoacrylate, 
polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate 
and polypropylene glycol monomethacrylate are useful for the preparation 
of the acid phosphoric ester compounds of the formula (II). 
The acid phospheric ester compounds of the formula (III) can be selected 
from the class consisting of monoethyl phosphate, diethyl phosphate, 
monopropyl phosphate, dipropyl phosphate, monobutyl phosphate, dibutyl 
phosphate, monopentyl phosphate, monhexyl phosphate, monophenyl phosphate, 
mono-4-methylphenyl phosphate and mono-4-ethyl-phenyl phosphate. 
Especially mono- and di-alkyl phosphates having 1 to 6 carbon atoms are 
very useful for modifying the epoxidized butadiene polymer. 
The modification of the epoxidized butadiene polymer non-modified or 
previously modified with the acid polybasic carboxylic ester compound with 
the acid phosphoric ester compound may be effected by any conventional 
esterification method. For example, a modified or previously modified 
epoxidized butadiene polymer is brought into reaction with an acid 
phosphoric ester compound in an organic medium or without using the 
medium, at a temperature of from 10.degree. to 80.degree. C., preferably, 
from 20.degree. to 50.degree. C., for 0.5 hours or more, preferably, from 
1 to 5 hours, while the reaction mixture is stirred. During the reaction 
procedure, cyclic epoxy radicals in the epoxidized butadiene polymer are 
cleaved and each addition reacted with a hydroxyl radical attached to a 
phosphorus atom in the acid phosphoric ester compound, so as to form a 
linking group between the backbone group and the additional side chain 
group. 
The number of the additional side chain groups in the modified, epoxidized 
butadiene polymer of the present invention is in a range of from 0 to 50, 
preferably, 5 to 50, per 100 butadiene units in the backbone group. If the 
number of the additional side chain groups is more than 50 per 100 
butadiene units, the resultant modified, epoxidized butadiene polymer will 
exhibit an undesirable excessively high viscosity. Also, it is technically 
difficult and economically disadvantageous to prepare the modified, 
epoxidized butadiene polymer containing more than 50 additional side chain 
groups per 100 butadiene units. 
In the modified, epoxidized butadiene polymer containing both the side 
chain and additional side chain groups, it is preferable that the sum of 
the numbers of the side chain and additional side chain groups be 60 or 
less, more preferably in a range of from 10 to 60 even more preferably, 
from 10 to 50, and most preferably, form 12 to 45, per 100 butadiene 
units. It is technically difficult to produce the modified, epoxidized 
butadiene polymer having a sum of the numbers of the side chain and 
additional side chain groups of more than 60 per 100 butadiene units. Even 
if such type of modified polymer could be produced, the modified polymer 
would cause the resultant photosetting composition to exhibit a tendency 
to easily gelatinize. 
In the preparation of the modified, epoxidized butadiene polymer containing 
both the side chain and additional side chain groups, the additions of the 
acid polybasic carboxylic ester compound and the acid phosphoric ester 
compound to the epoxidized butadiene polymer are not limited to a special 
order. That is, first, either one of the acid polybasic carboxylic 
monoester compound and acid phosphoric ester compound may be added to the 
epoxidized butadiene polymer and, then, the other may be added to the 
first modified epoxidized butadiene polymer. Otherwise, the epoxidized 
butadiene polymer may be modified in a single step reaction with both the 
acid polybasic carboxylic ester compound and the acid phosphoric ester 
compound. However, since the acid phosphoric ester compound has a 
relatively low thermal stability and exhibits a relatively high addition 
reaction rate, it is preferable that, first, the epoxidized butadiene 
polymer be modified with the acid polybasic carboxylic ester compound and, 
then, the first modified epoxidized butadiene polymer be additionally 
modified with the acid phosphoric ester compound. This type of two step 
modification process is effective for preventing undesirable 
gelatinization of the resultant modified, epoxidized butadiene polymer. 
During the two-step modification process, almost all of the cyclic epoxy 
radicals in the epoxidized butadiene polymer are cleaved and addition 
reacted with the free carboxylic acid radicals in the acid polybasic 
carboxylic ester compound and, then, with the hydroxyl radicals attached 
to the phosphorus atom in the acid phosphoric ester compound. Therefore, 
the resultant modified, epoxidized butadiene polymer has an enhanced 
stability to storage. 
In the present invention, it is preferable that the modified, epoxidized 
butadiene polymer contain less than 1 epoxy radical per 100 butadiene 
units in the backbone group. 
In the case where the modified, epoxidized butadiene polymer contains 6 or 
more side chain groups and more than zero of additional side chain groups 
per 100 butadiene units, a small portion of the additional side chain 
groups may be replaced by another side chain group consisting of 
phosphoric acid, phosphorous acid or hydrochloric acid. 
In the photosetting composition, it is preferable that the modified, 
epoxidized butadiene polymer be not gelatinized and colored, and be clear. 
However, the modified, epoxidized butadiene may be slightly colored. On 
the other hand, the modified, epoxidized butadiene polymer preferably 
exhibits a viscosity of from 2,000 to 100,000 cps, more preferably, from 
4,000 to 60,000 cps, determined at a temperature of 30.degree. C. by using 
a rotation viscometer. 
The photosetting composition of the present invention contains at least one 
photopolymerizable monomer as an important component. The 
photopolymerizable monomer may be selected from photopolymerizable acrylic 
and methacrylic ester compounds, preferably having a boiling point of 
200.degree. C. or more under atmospheric pressure. The photopolymerizable 
monomer compounds may involve, for example, 2-hydroxyethyl acrylate and 
methacrylate, 2-hydroxypropyl acrylate and methacrylate, pentaerythritol 
tri-acrylate and tri-methacrylate, 2-ethylhexyl acrylate and methacrylate, 
lauryl acrylate and methacrylate, ethylene glycol di-acrylate and 
di-methacrylate, diethylene di-acrylate and di-methacrylate, di-acrylic 
ester and di-methacrylic ester of polyethylene glycol having a degree of 
polymerization of from 3 to 8, propylene glycol di-acrylate and 
di-methacrylate, di-acrylic ester and di-methacrylic ester of 
polypropylene glycol having a degree of polymerization of from 2 to 6, 
1,3-butylene glycol di-acrylate and di-methacrylate, 1,4-butylene glycol 
di-acrylate and di-methacrylate, 1,6-hexane diol di-acrylate and 
di-methacrylate, neopentyl glycol di-acrylate and di-methacrylate and 
trimethylolpropane tri-acrylate and tri-methacrylate. The 
photopolymerizable monomer compounds may be selected from the acid 
polybasic carboxylic ester compounds of the formula (I) and the acid 
phosphoric ester compounds of the formula (II). 
The photosetting composition of the present invention contains the 
photopolymerizable monomer component in an amount of from 30 to 800 parts 
by weight, preferably, from 50 to 600 parts by weight, more preferably, 
from 100 to 500 parts by weight, per 100 parts by weight of the modified, 
epoxidized butadiene polymer. When the amount of the photopolymerizable 
monomer compound is less than the value of the lower limit mentioned 
above, the resultant photosetting composition will exhibit an undesirable 
high viscosity and be improper for use as a coating varnish. On the other 
hand, the photosetting composition containing the photopolymerizable 
monomer component in amount larger than the value of the upper limit 
described above, will cause the photocured composition to exhibit a poor 
impact strength. 
The photosetting composition of the present invention contains, as an 
important component, a photosensitizer. The photosensitizer may be 
selected from conventional photosensitizers, for example, benzoin methyl 
ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 
benzoin, .alpha.-methyl benzoin, .alpha.-chlorodihydroxy benzoin, 
benzophenone, dimethyoxyphenyl acetophenone and benzil. 
The photosetting composition of the present invention contains the 
photosensitizer in an amount of from 0.5 to 15 parts by weight, 
preferably, from 2 to 10 parts by weight, per 100 parts by weight of the 
modified, epoxidized butadiene polymer. When the amount of the 
photosensitizer used is lower than 0.5 parts by weight, an undesirable 
long time will be needed to complete the photocuring operation of the 
resultant photosetting composition. On the other hand, even if the amount 
of the photosensitizer is increased to more than 15 parts by weight, the 
photosensitivity of the resultant photosetting composition is not 
enhanced. That is, only an economical disadvantage results. 
The photosetting composition of the present invention may contain a small 
amount of a thermal polymerization stabilizer, for example, selected from 
hydroquinone, 2,6-di-tert-butyl-p-cresol and p-benzoquinone. However, 
since the addition of the stabilizer causes the resultant photosetting 
composition to exhibit a reduced photocuring rate, the stabilizer should 
be used in a very small amount, that is, 5 parts by weight or less per 100 
parts by weight of the photosetting composition. 
The photosetting composition of the present invention can be prepared by 
any conventional processes. However, since the photopolymerizable monomer 
is not reactive in the modification reaction mixture of the epoxidized 
butadiene polymer with the acid polybasic carboxylic monoester compound 
and the acid phosphoric ester compound, it is preferable that the 
photopolymerizable monomer as a reaction medium be mixed with the 
modification reaction mixture, and after the modification of the 
epoxidized butadiene polymer is completed, the resultant reaction mixture 
which comprises the modified, epoxidized butadiene polymer and the 
photopolymerizable monomer, is mixed with a predetermined amount of the 
photosensitizer or a mixture of a predetermined amount of the 
photosensitizer and an additional amount of the photopolymerizable 
monomer. 
The photosetting composition of the present invention is a transparent or 
semi-transparent, colorless or light yellow liquid, and has a viscosity of 
from 100 to 2,000 cps, preferably, 150 to 1,500 cps, determined at a 
temperature of 30.degree. C. by using a rotation viscometer. 
The photosetting composition is useful as a coating varnish even without 
using any additives. However, in order to enhance slipping property and to 
reduce tackiness of the coating varnish, a small amount of one or more 
additives, for example, a fatty acid amide, such as stearic amide and 
oleic amide, and wax, such as carnauba wax, ozocerite wax and spermaceti 
wax. 
The viscosity of the photosetting composition of the present invention can 
be adjusted by adding the photo-polymerizable monomer. However, the 
viscosity may be controlled by adding a small amount of styrene, vinyl 
toluene, vinyl acetate, methyl methacrylate, acrylic acid, methacrylic 
acid, benzene, toluene, xylene, cumene, hexane, cyclohexane, ethyl 
acetate, kerosene, methylisobutyl ketone or a mixture of two or more of 
the above-mentioned compounds. 
Furthermore, the photosetting composition of the present invention may 
contain a small amount of an inorganic pigment, for example, zinc 
chromate, strontium chromate, iron oxide, zinc oxide, and titanium 
dioxide, or an organic pigment, for example, azo type, triphenylmethane 
type, quinoline type, anthraquinone type or phthalocyamine type pigment. 
The features and advantages of the present invention will be illustrated by 
the following referential examples of the preparations of epoxidized 
butadiene polymers, acid polybasic carboxylic ester compounds and 
modified, epoxidized butadiene polymers, examples of the photosetting 
compositions of present invention and comparative examples of comparative 
photosetting compositions. 
In the referential examples, the number of epoxy radicals in the epoxidized 
butadiene polymer was determined in such a manner that a predetermined 
amount of the epoxidized butadiene polymer was chlorinated with a 
hydrochloric acid-dioxane solution, and then, the amount of the 
non-reacted hydrochloric acid was determined by titrating alcoholic 
potassium in the presence of an indicator consisting of phenolphthalein. 
The number of the polybasic carboxylic ester side chain groups attached to 
the epoxidized butadiene polymer backbone group was determined by 
measuring the difference in acid value of the reaction mixture of the 
epoxidized butadiene polymer and the acid polybasic carboxylic ester 
compound before the start of the reaction and after the completion of the 
reaction. 
In the referentical examples, examples and comparative examples, the 
viscosities of liquid butadiene polymers, epoxidized butadiene polymers, 
reaction mixture containing modified, epoxidized butadiene polymers and 
photosetting compositions were determined at a temperature of 30.degree. 
C. by using a E type rotation viscometer made by Tokyo Keiki K.K., Japan. 
In the examples and comparative examples, the photocuring reaction rate of 
the photosetting composition was determined by the following method. A 
photosetting composition was applied onto a surface of a degreased 
aluminium plate so as to form a coating film of the photosetting 
composition having a thickness of 10 microns. The aluminium plate coated 
with the photosetting composition was placed on a conveyer belt which 
rotated through a horizontal path located 9 cm below a 2 KW high voltage 
mercury lamp 25 cm long and made by Iwasaki Denki K.K., Japan, at a 
predetermined velocity. The photosetting composition coating film was 
exposed to the ultraviolet rays from the mercury lamp and photocured. The 
velocity of the converyer belt was varied to several levels. After the 
completion of the photocuring operation, a polyvinylidene chloride film 
was pressed onto the surface of the photocured coating film and, then, 
removed therefrom. The surface of the pressed coating film was observed. 
The photocuring rate of the photosetting composition was expressed by a 
largest value of the velocity (m/min) of the conveyer belt at which no 
change in gloss of the surface of the coating film was observed. 
The adhering intensity of the photocured coating film was determined by a 
cross-hatch adhesion method as follows. A photocured film adhered onto an 
aluminium plate or alkyd resin board was prepared by the same method as 
that described above. The coating film was cut in a checkerboard pattern 
at intervals of 2 mm so as to form 100 squares separate from each other. 
An adhesive sheet was adhered to the cut coating films, and then peeled 
off therefrom. The adhering intensity of the photocured coating film was 
expressed by the number of the squares remaining on the aluminium plate or 
the alkyd resin board. 
The pencil hardness of the photocured coating film was determined in 
accordance with the method described in paragraph 6.14, of JIS-K 5,400. 
The flexural strength of the photocured coating film was determined as 
follows. 
A photosetting composition was applied onto a surface of a steel plate, as 
described in JIS-K 5,400, so as to form a coating film 30 microns thick. 
The coating film was photocured by using the same mercury lamp as 
described hereinbefore while the conveyer belt was rotated at a velocity 
of 1 m/min. The exposure of the coating film to the ultraviolet rays was 
repeated three times. The flexural strength of the photocured coating film 
was measured in accordance with the method described in paragraph 6.15, in 
JIS-K 5,400. 
In the determination of impact strength of the photocured coating film, the 
same procedures for preparing the photocured coating film as those 
mentioned above were repeated, and the resultant photocured coating film 
was subjected to a measurment of Du Pont impact strength, in accordance 
with the method described in paragraph 6.13, of JIS-K 5,400. 
The resistance of the photocured coating film to water was determined by 
applying a photosetting composition onto a surface of a glass plate to 
form a coating film 30 micron thick, by photocuring the coating film using 
the same method as mentioned above, by immersing the photocured coating 
film in water at a temperature of 40.degree. C., for 1 hour, and by 
observing the changes in the appearance of the film surface. Especially, 
it was checked whether or not wrinkles and cracks were formed in the film 
surface, volume of the film altered and the gloss of the film surface 
altered.

REFERENTIAL EXAMPLE 1 
(Preparations of epoxidized butadiene polymers) 
Six types of epoxidized butadiene polymers were prepared from the liquid 
butadiene polymers each having a number average molecular weight, 
viscosity and molecular structure as shown in Table 1, respectively, in 
Experiments E-1 through E-6. 
In each experiment, 500 parts by weight the liquid butadiene polymer was 
mixed with 1,300 parts by weight of benzene. A 30% hydrogen peroxide 
solution in an amount shown in Table 1 was added to the mixture. Next, 
formic acid in an amount shown in Table 1 was added dropwise to the 
resultant slurry, at a temperature of 20.degree. C., for 30 minutes. The 
reaction mixture was maintained at a temperature of approximately 
35.degree. C. for 5 hours, so as to epoxidized the liquid butadiene 
polymer. After completion of the reaction, the reaction mixture was washed 
with water to remove the non-reacted hydrogen peroxide and formic acid 
and, then, benzene was removed from the washed reaction mixture by means 
of distillation. 
Table 1 also shows the numbers of the epoxy radicals per 100 butadiene 
units, viscosities and yields of the resultant epoxidized butadiene 
polymers. 
TABLE 1 
__________________________________________________________________________ 
Epoxidized butadiene polymer 
Liquid butadiene polymer Amount of 
Amount 
Number of 
Content (%) 30% hydrogen 
of epoxy 
cis- 
trans- 
Number peroxide 
formic 
radical Yield 
1,2- 
1,4- 
1,4- 
average 
Viscosity 
solution 
acid per 100 
Viscosity 
(part 
Experiment 
struc- 
struc- 
struc- 
molecular 
(cp) (part by 
(part by 
butadiene 
(cp) by 
No. ture 
ture 
ture 
weight 
(at 30.degree. C.) 
weight) weight) 
units (at 30.degree. C.) 
weight) 
__________________________________________________________________________ 
E-1 58 33 9 1270 500 700 28 8 1020 510 
E-2 " " " " " " 50 12 2100 518 
E-3 " " " " " " 83 19 5200 528 
E-4 " " " " " 1500 132 26 45600 536 
E-5 " " " " " 2000 264 41 150000 556 
E-6 43 48 " 2340 1280 1500 132 29 76000 542 
__________________________________________________________________________ 
REFERENTIAL EXAMPLE 2 
(Preparations of acid polybasic carboxylic ester compounds) 
Six types of acid polybasic carboxylic ester compounds were respectively 
prepared in Experiments R-1 through R-6. 
EXPERIMENT R-1 
(From phthalic anhydride) 
A reaction mixture consisting of 98.8 g (about 0.67 moles) of phthalic 
anhydride, 116 g (about 1.0 moles) of 2-hydroxyethyl acrylate, 0.3 g of 
2,6-di-tert-butyl-p-cresol and 0.45 g of triethylbenzyl ammonium chloride, 
was subjected to an esterification reaction at a temperature of 95.degree. 
C. for 8 hours while the mixture is stirred. Next, the non-reacted 
2-hydroxyethyl acrylate was removed by means of distillation. 181 g of a 
viscous liquid acid phthalic monoester compound, which exhibited no peaks 
in the frequencies of 1,770 cm.sup.-1 and 1,850 cm.sup.-1 in the infra-red 
ray spectrum, were obtained. The resultant compound had an acid value of 
208 and a viscosity of 15,000 cps at 30.degree. C. 
EXPERIMENT R-2 
(From phthalic anhydride) 
The same procedures as those described in Experiment R-1 were repeated, 
except that the esterification reaction was carried out for 5 hours. 162 g 
of the resultant viscous liquid acid phthalic monoester compound, which 
exhibited no peaks in frequencies of 1,770 cm.sup.-1 and 1,850 cm.sup.-1 
in the infra-red ray spectrum, were obtained. The resultant compound 
exhibited an acid value of 215 and a viscosity of 16,000 cps at 30.degree. 
C. 
EXPERIMENT R-3 
(From 2,3,3',4-biphenyltetracarboxylic dianhydride) 
A reaction mixture containing 250 g (about 0.85 moles) of 
2,3,3',4'-biphenyltetracarboxylic dianhydride, 390 g (about 3.4 moles) of 
2-hydroxyethyl acrylate, 0.77 g of benzyltriethyl ammonium chloride 
(catalyst) and 0.57 g of 2,6-di-tert-butyl-p-cresol, was subjected to an 
esterification reaction, at a temperature of about 80.degree. C., for 7 
hours, while air was flowed through the mixture. Next, the non-reacted 
2-hydroxyethyl acrylate was eliminated by way of distillation under a 
reduced pressure. About 467 g of the resultant acid biphenyl 
tetracarboxylic diester compound were obtained. The resultant compound 
exhibited an acid value of 204 and a viscosity of 23,000 cps at 50.degree. 
C. The compound contained approximately two carboxyl radical per molecule. 
EXPERIMENT R-4 
(From trimellitic anhydride) 
The same procedures as those mentioned in Experiment R-1 were repeated, 
except that the phthalic anhydride was replaced by 129 g (about 0.67 
moles) of trimellitic anhydride. 198 g of the resultant acid trimellitic 
monoester compound, which exhibited no peaks at 1,770 cm.sup.-1 and 1,850 
cm.sup.-1, were obtained. The compound exhibited an acid value of 345 and 
a viscosity of 21,000 cps at 30.degree. C., and contained about two 
carboxyl radical per molecule. 
EXPERMENT R-5 
(From tetrahydrophthalic anhydride) 
The same procedures as those described in Experiment R-1 were carried out, 
except that the phthalic anhydride was replaced by 102 g (about 0.67 
moles) of tetrahydrophthalic anhydride, and the reaction temperature was 
about 95.degree. C. 184 g of acid tetrahydrophthalic monoester compound 
were obtained. The compound exhibited no peaks at 1,770 cm.sup.-1 and 
1,850 cm.sup.-1, and had an acid value of 204 and a viscosity of 16,000 
cps at 30.degree. C. 
EXPERIMENT R-6 
(From 4-nitrophthalic anhydride) 
Procedures identical to those used in Experiment R-1 were carried out, 
except that the phthalic anhydride was replaced by 129 g (about 0.67 
moles) of 4-nitrophthalic anhydride. 186 g of acid 4-nitrophthalic 
monoester compound were obtained. The compounds exhibited no peaks at 
1,770 cm.sup.-1 and 1,850 cm.sup.-1, and had an acid value of 175 and a 
viscosity of 37,000 cps at 30.degree. C. 
REFERENTIAL EXAMPLE 3 
(Preparations of modified, epoxidized butadiene polymers) 
Eight types of modified, epoxidized butadiene polymers were prepared in 
Experiment M-1 through M-8 by modifying epoxidized butadiene polymers with 
acid polybasic carboxylic ester compounds only. 
In each of Experiments M-1 through M-8, a reaction mixture containing 280 
parts by weight of benzene, 142 parts by weight of an epoxidized butadiene 
polymer shown in Table 2, a type and amount of acid polybasic carboxylic 
ester compound respectively indicated in Table 2, 0.8 parts by weight of 
2,6-di-tert-butyl-p-cresol and 0.8 parts by weight of 
triethylbenzylammonium chloride, was subjected to a modification reaction 
at a temperature of 75.degree. C., for 8 hours, except that in Experiment 
M-3, the reaction time was 4 hours. After the reaction was completed, the 
benzene was removed from the reaction mixture by way of distillation under 
a reduced pressure. The obtained liquid contained a modified, epoxidized 
butadiene polymer, non-reacted acid polybasic carboxylic ester compound. 
The compositions and viscosities of the liquids obtained in Experiments 
M-1 through M-8 are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Modification process Product 
Component Component 
Acid polybasic Non-reacted acid 
carboxylic ester 
Modified, epoxidized 
polybasic carbonylic 
Type of compound butadiene polymer 
ester compound 
epoxidized Amount 
Number of side 
Amount Amount 
Experiment 
butadiene 
Type of 
(part by 
chain group per 100 
(part by 
Type of 
(part by 
Viscosity 
No. polymer 
compound 
weight) 
butadiene units 
weight) 
compound 
weight) 
(cp) 
__________________________________________________________________________ 
M-1 E-1 PHEA 53 4 164 PHEA 25 3500 
M-2 E-2 " 135 8 197 " 80 5500 
M-3 E-3 " 177 7 188 " 130 5000 
M-4 E-3 " 177 10 212 " 106 12000 
M-5 E-3 THEA 210 11 232 THEA 120 25000 
M-6 E-3 NHEA 211 10 225 NHEA 128 35000 
M-7 E-4 PHEA 281 15 242 PHEA 181 45000 
M-8 E-5 " 199 18 217 " 110 22000 
__________________________________________________________________________ 
Note: 
PHEA reaction product of phthalic anhydride with 2hydroxyethyl acrylate 
(Experiment R1) 
THEA reaction product of trimellitic anhydride with 2hydroxyethyl 
acrylate (Experiment R4) 
NHEA reaction product of 4nitrophthalic anhydride with 2hydroxyethyl 
acrylate (Experiment R6) 
The modified, epoxidized butadiene polymer obtained in Experiment M-1 is 
useless for the photosetting composition of the present invention, because 
only 4 side chain groups per 100 butadiene units were attached to the 
epoxidized butadiene polymer backbone group. 
In Experiments M-9 through M-19, modified, epoxidized butadiene polymers 
containing not only polybasic carboxylic ester side chain groups but also 
phosphoric ester additional side chain groups were produced. 
In each of Experiments M-9 through M-19, a first reaction mixture 
comprising a type and amount of an epoxidized butadiene polymer, and a 
type and amount of an acid polybasic carboxylic ester compound, 
respectively indicated in Table 4, 60 g of 2-hydroxyethyl acrylate as a 
medium, 0.4 g of triethylbenzyl ammonium chloride as a catalyst, and 0.8 g 
of 2,6 -di-tert-butyl-p-cresol as an antigelatinizing agent, was brought 
into a first modification process at a temperature of 85.degree. C., for 8 
hours, except that in Experiment M-13, the reaction time was 4 hours. 
After the modification process was completed, the reaction mixture was 
cooled to atmospheric temperature. 
Next, the cooled first reaction mixture was mixed with the amount shown in 
Table 3 of acid phosphoric dimethacrylate, except that in Experiments 
M-14, 8.2 g of acid butyl phosphoric monoester was used, to prepare a 
second reaction mixture. The second reaction mixture was subjected to a 
second modification process at a temperature of 40.degree. C. for 3 hours 
while stirring. 
Table 2 shows compositions and viscosities of the resultant liquids of 
Experiments M-9 through M-19. 
TABLE 3 
__________________________________________________________________________ 
Product 
Composition 
Modification Modified, epoxidized 
Component butadiene polymer 
Acid polybasic 
Amount 
Number of groups 
Epoxidized carboxylic 
of acid 
per 100 butadiene 
Non-reacted poly- 
butadiene ester phosphoric 
units basic carboxylic 
A- Vis- 
polymer compound ester side 
Additional compound mount 
cos- 
Experiment 
Amount Amount 
compound 
chain 
side chain 
Amount 
Type of 
Amount 
of ity 
No. Type 
(g) Type (g) (g) group 
group (g) compound 
(g) 2-HEA 
(cp) 
__________________________________________________________________________ 
M-9 E-1 
20 PHEA 7.8 4.7 0.04 
0.04 28.6 PHEA 3.9 60 2800 
M-10 E-2 
20 " 11.7 8.2 0.05 
0.07 33.1 " 6.8 " 3000 
M-11 E-3 
20 " 18.5 22.4 0.08 
0.19 50.1 " 10.7 60 3200 
M-12 E-4 
20 " 25.4 23.8 0.05 
0.21 48.5 " 20.7 60 2700 
M-13 E-4 
20 " 25.4 18.8 0.10 
0.16 64.6 " 15.6 60 3400 
M-14 E-4 
20 " 25.4 8.2* 0.10 
0.16 37.9 " 15.6 60 3100 
M-15 E-5 
20 " 39.9 30.6 0.15 
0.26 65.2 " 25.3 60 5300 
M-16 E-6 
20 " 28.3 20.4 0.10 
0.19 51.8 " 16.9 60 4500 
M-17 E-4 
20 BHEA 50.5 15.3 0.13 
0.13 60.8 BHEA 25.0 60 6100 
M-18 E-4 
20 THEA 29.6 17.7 0.11 
0.15 50.2 THEA 17.1 60 4300 
M-19 E-4 
20 TPHEA 
25.8 16.5 0.12 
0.14 48.2 TPHEA 14.1 60 3200 
__________________________________________________________________________ 
Note: 
BHEA reaction product 2,3,3',4biphenyltetracarboxylic dianhydride with 
2hydroxyethyl acrylate (Experiment R3) 
TPHEA reaction product of tetrahydrophthalic anhydride with 2hydroethyl 
acrylate (Experiment R5) 
2HEA 2hydroxyethyl acrylate 
* acid butyl phosphoric monoester 
The modified, esterified butadiene polymer obtained by Experiment M-9 is 
useless for the photosetting composition of the present invention, because 
the number of the polybasic carboxylic ester side chain groups falls 
outside of the scope of the present invention. 
EXAMPLES 1 THROUGH 8 
In each of Examples 1 through 8, a photosetting composition was prepared by 
mixing the type and amount of a modified, epoxidized butadiene polymer and 
the type and amount of a photopolymerizable monomer, respectively shown in 
Table 4, and 5 parts by weight of benzoin methyl ether per 100 parts by 
weight of the sum of the modified, epoxidized butadiene polymer and the 
photopolymerizable monomer. 
The viscosities, photocuring rates and stabilities for storage of the 
photosetting compositions of Examples 1 through 8, and the pencil 
hardnesses, adhering intensities, flexural strengths, Du Pont impact 
strengths and resistances to water of the photocured compositions are 
indicated in Table 4. The stability for storage of the photosetting 
composition was expressed in terms of viscosity of the photosetting 
composition determined at a temperature of 30.degree. C., after the 
composition was stored at a temperature of 30.degree. C. for 90 days. 
TABLE 4 
__________________________________________________________________________ 
Photosetting composition 
Composition 
Modification 
reaction product Stability 
(containing for Photocured composition 
modified, epoxi- storage Du pont 
dized butadiene 
Photopolymeri- Photo- 
(viscosity impact 
polymer zable monomer curing 
after Adhering strength 
Resis- 
Amount Amount rate 
90 day 
Pencil 
in- Flexural 
(500g 
tances. 
Example (part by (part by 
Viscosity 
(m/ store) 
hard- 
tensity 
strength 
1/2" .times. 
to 
No. Type 
weight) 
Type weight) 
(cp) min) 
(cp) ness 
(%) (mm.phi.) 
cm) water 
__________________________________________________________________________ 
1 M-2 
141 2-HEA 
100 360 25 375 H 100 2 120 excellent 
2 M-3 
170 2-HEA 
100 350 27.5 
360 H 100 2 110 " 
3 M-4 
151 2-HEA 
100 450 30 470 H 100 2 150 " 
4 M-4 
151 1,6-HDA 
100 450 25 465 H 100 2 120 " 
5 M-5 
155 2-HEA 
100 760 30 790 H 100 2 110 " 
6 M-6 
157 2-HEA 
100 470 25 480 H 100 2 120 " 
7 M-7 
175 2-HEA 
100 1100 40 1150 H 100 2 150 " 
8 M-8 
155 2-HEA 
100 630 40 660 H 100 2 140 " 
__________________________________________________________________________ 
Note: 
1,6HDA 1,6hexanediol diacrylate 
COMATIVE EXAMPLE 1 
Procedures identical to those described in Example 1 were carried out, 
except that 146 parts by weight of the modification reaction product of 
Experiment M-1 was used instead of that of Experiment M-2. 
The resultant comparative photosetting composition exhibited a relatively 
low viscosity of 250 cps at 30.degree. C. and a very low photocuring rate 
of 10 m/min in terms of the rotation velocity of conveyor belt. Also, the 
photocured comparative composition exhibited a relatively low pencil 
hardness of HB, a low adhering intensity of 80%, a flexural strength of 2 
mm .phi. and a poor Du Pont impact strength of 80 (500 gx1/2"xcm). Also, 
as a result of the test of the resistance to water, a number of wrinkles 
and cracks were created on the surface of the coating film, the coating 
film was swollen and the gloss of the coating film surface was remarkably 
reduced. 
COMATIVE EXAMPLE 2 
A liquid polybudiene having a number average molecular weight of 1530, a 
viscosity of 800 cps at 30.degree. C. and containing 54% of 1,2 structure, 
37% of cis-1,4 structure and 9% of trans-1,4 structure, was epoxidized by 
the same method as that described in Experiment E-1. The resultant 
epoxidized polybutadiene contained 6 epoxy radicals per 100 butadiene 
units. 100 parts by weight of the epoxidized polybutadiene were mixed with 
12 parts by weight of methacrylic acid, 0.1 parts by weight of 
hydroquinone and 200 parts by weight of benzene. The resulting reaction 
mixture was subjected to a modification process at a temperature of 
60.degree. C. for 3 hours. After the completion of the modification 
process, the benzene and the non-reacted methacrylic acid were removed 
from the reaction mixture by applying a process of distillation under a 
reduced pressure. 105 parts by weight of the modification product were 
obtained. 
A comparative photosetting composition was prepared by mixing 100 parts by 
weight of the above modification product, 10 parts by weight of 
1,3-butylene glycol diacrylate and 1 part by weight of benzil. The 
composition had a viscosity of 400 cps at 30.degree. C. and exhibited such 
a very poor photocuring rate that, even at a rotating velocity of the 
conveyor belt of 5 m/min., the composition did not harden. 
COMATIVE EXAMPLE 3 
A polybasic carboxylic ester compound was prepared by bringing a mixture of 
58 parts by weight of 2-hydroxyethyl acrylate, 74 parts by weight of 
phthalic anhydride, 2 parts by weight of triethylbenzyl ammonium chloride, 
0.1 part of hydroquinone and 0.1 part of anthraquinone into a reaction 
process at a temperature of 110.degree. C. for 5 hours. 132 parts by 
weight of the above-obtained ester compound were mixed with 95 parts by 
weight of an epoxy resin (of the trademark DER-33IJ, made by Dow Chemical 
Co. and having an epoxy equivalent of 190) and (7 parts by weight of 
trialkyl isocyanate. The mixture was heated at a temperature of from 
100.degree. to 120.degree. C. for 3 hours, to prepare a varnish. 
A comparative photosetting composition was provided by mixing 7.8 parts by 
weight of the above-prepared varnish with 2 parts by weight of 
trimethylolpropane triacrylate and 0.2 parts of benzoinethyl ether. The 
composition had a viscosity of 1500 cps at 30.degree. C. and a poor 
photocuring rate of 7.5 m/min, in terms of the rotating velocity of the 
conveyer belt. Also, when photocured, the resultant hardened coating film 
exhibited a pencil hardness of 2H, a very poor adhering intensity of 0, a 
very poor flexural strength of 4 mm .phi. and a very poor Du pont impact 
strength of 5 or less (500 gx1/2"xcm). However, the photocured coating 
film exhibited a relatively high resistance to water. 
EXAMPLES 9 THROUGH 18 
In each of Examples 9 through 18, a photosetting composition was prepared 
by mixing the type and amount of a modification reaction product 
containing a modified, epoxidized butadiene polymer, and the type and 
amount of acid polybasic carboxylic ester compound, respectively shown in 
Table 5, and the amounts of 2-hydroxyethyl acrylate, pentaerythritol 
triacrylate and benzoin methyl ether respectively indicated in Table 5. 
The viscosities, photocuring rates and stabilities for storage of the 
photosetting compositions of Examples 9 through 18, and pencil hardnesses, 
adhering intensities, flexural strengths and Dupont impact strengths of 
the photocured compositions are indicated in Table 6. 
COMATIVE EXAMPLE 4 
Procedures identical to those described in Example 9 were carried out, 
except that the modification reaction product of Experiment M-9 was used 
in place of that of Experiment M-10, and the acid polybasic carboxylic 
ester compound, the 2-hydroxyethyl acrylate, the pentaerythritol 
triacrylate and the benzoinmethyl ether were used, respectively, in the 
amounts indicated in Table 5. 
The results of Comparative Example 4 are also shown in Table 6. 
TABLE 5 
__________________________________________________________________________ 
Photosetting Composition 
Photopolymerizable monomer 
Modified, 
Acid polybasic 
epoxidized 
carboxylic Photosensitizer 
polybutadiene 
ester compound 
Amount of 
Amount of 
Amount of 
Amount Amount 
2-HEA PETA benzoinmethyl 
Example (part by (part by 
(part by 
(part by 
ether (part 
No. Type 
weight) 
Type weight) 
weight) 
weight) 
by weight) 
__________________________________________________________________________ 
Comparative 
Example 4 
M-9 100 PHEA 13.6 130 20 13.2 
Example 9 
M-10 
100 PHEA 20.5 150 20 14.5 
Example 10 
M-11 
100 PHEA 21.3 180 20 16.1 
Example 11 
M-12 
100 PHEA 42.7 180 20 17.1 
Example 12 
M-13 
100 PHEA 24.2 200 20 17.2 
Example 13 
M-14 
100 PHEA 41.1 150 20 15.6 
Example 14 
M-15 
100 PHEA 38.8 400 20 27.9 
Example 15 
M-16 
100 PHEA 32.6 380 20 26.6 
Example 16 
M-17 
100 BHEA 36.7 400 20 27.8 
Example 17 
M-18 
100 THEA 34.1 380 20 26.7 
Example 18 
M-19 
100 TPHEA 29.2 180 20 16.5 
__________________________________________________________________________ 
Note: 
PETA pentaerythritol triacrylate 
TABLE 6 
__________________________________________________________________________ 
Property of photosetting 
Property of Photocured 
composition coating film 
Stability for 
Adhering intensity to 
Dupont 
storage (vis- Alkyd impact 
Photocuring 
cosity after 
Pencil Aluminium 
resin 
Flexural 
strength 
Example 
Viscosity 
rate 90 day store) 
hard- 
Tinplate 
plate board 
strength 
(500g 
Resistance 
No. (cp) (m/min) 
(cp) ness 
(%) (%) (%) (mm.phi.) 
1/2" .times. cm) 
to 
__________________________________________________________________________ 
water 
Comparative 
210 10 213 HB 90 100 100 2 90 poor 
Example 4 
Example 9 
210 30 215 H 100 100 100 2 130 excellent 
Example 10 
215 35 218 2H 100 100 100 2 135 excellent 
Example 11 
235 30 238 2H 100 100 100 2 135 excellent 
Example 12 
230 40 237 2H 100 100 100 2 140 excellent 
Example 13 
220 30 227 2H 100 100 100 2 135 excellent 
Example 14 
250 45 255 2H 100 100 100 2 130 excellent 
Example 15 
260 40 269 2H 100 100 100 2 140 excellent 
Example 16 
290 50 303 2H 100 100 100 2 110 excellent 
Example 17 
270 40 275 2H 100 100 100 2 105 excellent 
Example 18 
210 30 213 2H 100 100 100 2 130 excellent 
__________________________________________________________________________