Positive type 1,2 quinone diazide containing photosensitive resinous composition with acrylic copolymer resin

The invention provides a photosensitive resin composition specifically useful for microfabrication resist films and photosensitive materials for use in lithographic plates because of excellent flexibility and adhesion, and moreover, when developed, non-exposed parts being of extremely less swelling nature.

FIELD OF INVENTION 
The present invention relates to a positive type photosensitive resinous 
composition which is useful in the preparation of microfabrication 
photoresists for printed wiring boards and integrated circuit boards and 
photosensitive materials for lithographic plates and the like. 
BACKGROUND OF THE INVENTION 
Heretofore, positive type photosensitive compositions have been widely used 
in various technical fields as, for example, preparation of semiconductor 
equipments, printed wiring boards, printing plates and the like. As the 
photosensitive composition capable of forming a positive image, i.e. 
positive type photosensitive composition, use has generally been made of 
such composition as being prepared by adding a quinone diazide compound to 
an alkali-soluble novolac resin, thereby rendering the composition hardly 
soluble in a basic aqueous solution to be used as a developer. This system 
is characterized by making the best use of the nature that the quinone 
diazide compound used is inherently insoluble in a basic aqueous solution 
and only soluble in an organic solvent, but when exposed to ultraviolet 
rays, the qunione diazide group contained is decomposed, thereby forming, 
passing through ketene group, a carboxyl group and rendering the compound 
easily soluble in a basic aqueous solution. Examples of such positive type 
photosensitizers are 1,2-quinone diazide compounds described in patents 
and other technical publication's listed at pages 339 to 357, 
"Light-sensitive systems", J. Kosar (John Wiley & Sons Inc.). Such 
positive type photosensitive compositions are, in general, far excellent 
in resolving power than negative type compositions and this is the main 
reason why they have been advantageously used as etching-proof in the 
preparation of printed wiring boards and integrated circuit boards. 
However, in the abovesaid system, there are some problems such that since 
the novolac resins are prepared by a condensation polymerization process, 
the products are subject to wide fluctuations in properties and since the 
softening point is considerably high in despite of a comparatively lower 
molecular weight of the resin, they are, in general, brittle and also poor 
in adhesion to a supporting plate when used as a resist film. Therefore, 
it has long been desired to make up the abovesaid drawbacks. Another 
proposal has also been made in which a 1,2-quinone diazide compound is 
admixed with a copolymer of conjugated diolefinic hydrocarbon, 
monoolefinically unsaturated compound and .alpha.,.beta.-ethylenically 
unsaturated carboxylic acid (Japanese Patent Application Kokai No. 
122031/81). In this system, it is said that flexibility and adhesion to a 
supporting plate is considerably good. However, in order to make this 
system alkali-soluble by photo-irradiation, it is essential that the 
content of .alpha.,.beta.-ethylenically unsaturated carboxylic acid in the 
resin be increased to a considerably higher level, which, in turn, will 
cause additional problem such that at the developing stage, the unexposed 
image area be liable to be swelled, thereby lowering the resolving power 
of the system. It is, therefore, a principal object of the present 
invention to provide a positive-type photosensitive resinous composition 
which is excellent in flexibility and adhesion, and moreover, capable of 
resulting a coating whose parts will give the least undesired swelling at 
the development stage. 
Disclosure of invention 
In accordance with the present invention, the abovesaid object can be 
attained with a positive-type photosensitive resinous composition 
comprising a qunione diazide compound and an acrylic resin bearing at 
least one side chain having the structure of 
##STR1## 
wherein R.sub.2 is a substituted or unsubstituted aliphatic hydrocarbon of 
2 to 10 carbon atoms, alicyclic hydrocarbon of 6 to 7 carbon atoms or 
aromatic hydrocarbon of 6 carbon atoms; A is a repeating unit of the 
formula; 
##STR2## 
wherein R.sub.3 is ethylene or propylene; R.sub.4 is a substituted or 
unsubstituted alkylene of 2 to 7 carbon atoms; R.sub.5 is a substituted or 
unsubstituted alkylene of 2 to 5 carbon atoms; k and 1 each represents an 
average repeating unit number and k is 1 to 10 and 1 is 2 to 50; or 
##STR3## 
wherein R.sub.7 is a substituted or unsubstituted aliphatic hydrocarbon of 
5 to 10 carbon atoms, alicyclic hydrocarbon of 6 to 7 carbon atoms or 
aromatic hydrocarbon of 6 to 13 carbon atoms; R.sub.8 is aliphatic 
hydrocarbon of 1 to 30 carbon atoms or aromatic hydrocarbon of 6 to 13 
carbon atoms optionally substituted with either of vinyl, allyl, ether, 
ester or carbonyl group singularlily or in combination of more than two in 
the main chain, and optionally substituted in the side chain(s); B is 
##STR4## 
wherein m and n are each zero or one independently one another; D is a 
repeating unit represented by 
##STR5## 
R.sub.9 is ethylene or propylene; R.sub.10 is a substituted or 
unsubstituted alkylene of 2 to 7 carbon atoms; R.sub.11 is a substituted 
or unsubstituted alkylene of 2 to 5 carbon atoms; p and q each represents 
an average repeating unit number, and p is 1 to 10 and q 2 to 50; E is 
carboxylic acid, sulfonic acid, phosphoric acid or phosphorus acid group. 
Best mode of the invention 
The present acrylic resin can be advantageously prepared by polymerizing an 
acrylic monomer of the formula; 
##STR6## 
wherein R.sub.1 is hydrogen or methyl group and R.sub.2 is optionally 
substituted aliphatic hydrocarbon of 2 to 10 carbon atoms, alicyclic 
hydrocarbon of 6 to 7 carbon atoms or aromatic hydrocarbon of 6 carbon 
atoms; A is a repeating unit having the structure 
##STR7## 
wherein R.sub.3 is ethylene or propylene: R.sub.4 is optionally 
substituted alkylene of 2 to 7 carbon atoms; R.sub.5 is optionally 
substituted alkylene of 2 to 5 carbon atoms; k and 1 are each an average 
of the number of the repeating unit respectively and k is a value defined 
within the range from 1 to 10 and 1 within the range from 2 to 50; or 
##STR8## 
wherein R.sub.6 is hydrogen or methyl group and R.sub.7 is optionally 
substituted aliphatic hydrocarbon of 5 to 10 carbon atoms, alicyclic 
hydrocarbon of 6 to 7 carbon atoms or aromatic hydrocarbon of 6 to 13 
carbon atoms; R.sub.8 is aliphatic hydrocarbon of 1 to 30 carbon atoms or 
aromatic hydrocarbon of 6 to 13 carbon atoms optionally substituted with 
either of vinyl, allyl, ether, ester or carbonyl group singularlily or in 
combination of more than two in the main chain, and optionally substituted 
in the side chain(s); B is 
##STR9## 
wherein m and n are each zero or one independently one another; D is a 
repeating unit represented by the structure 
##STR10## 
R.sub.9 is ethylene or propylene; R.sub.10 is unsubstituted or substituted 
alkylene of 2 to 7 carbon atoms; R.sub.11 is unsubstituted or subsutituted 
alkylene of 2 to 5 carbon atoms; p and q are each an average of the number 
of the respective repeating unit, and p is a value from 1 to 10 and q is a 
value from 2 to 50; E is carboxylic acid, sulfonic acid, phosphoric acid 
or phosphorus acid group, and other .alpha.,.beta.-ethylenically 
unsaturated copolymerizable monomer. In general, the weight ratio of the 
acrylic monomers to other monomers is from 3:97 to 80:20. Also, in order 
to control coating characteristics and the dissolution speed to a basic 
aqueous solution, said other monomers may partly include an unsaturated 
monomer(s) having at least one acidic group selected from the group 
consisting of .alpha.,.beta.-ethylenically unsaturated carboxylic acid, 
.alpha.,.beta.-ethylenically unsaturated sulfonic acid, 
.alpha.,.beta.-ethylenically unsaturated phosphoric acid and salts 
thereof, other than reactive acrylic monomers with a comparatively long 
side chain bearing an acidic group represented by the formula [I] or [II]. 
The weight ratio of such acidic monomers to the rest of the monomers is 
defined from 0:100 to 15:85. As compared with acrylic resins into which 
hithertofore used .alpha.,.beta.-ethylenically unsaturated acids with 
short side chains are introduced, the abovesaid acrylic resin composition 
into which reactive acrylic monomers having comparatively long side chains 
and acidic groups has higher solubility to a basic aqueous solution at the 
same acidic group equivalent and even when a quinone diazide compound is 
mixed together, light-exposed parts thereof have higher solubility and 
unexposed parts have very low swelling property during the time when the 
abovesaid light-exposed parts are dissolved out, and moreover, the 
introduction of the abovesaid reactive acrylic monomers gives flexibility 
to the resin and there is no problem of brittleness which has been a 
problem with regard to phenol resin compositions. The reactive acrylic 
monomers represented by the formula [I]can be advantageously prepared by 
polymerizing preferably in the presence of a radical polymerization 
inhibitor, an end hydroxyl group containing (meth)acrylate having the 
structure 
##STR11## 
wherein R.sub.1 is hydrogen or methyl group; A is a repeating unit having 
the structure 
##STR12## 
wherein R.sub.3 is ethylene or propylene; R.sub.4 is optionally 
substituted alkylene of 2 to 7 carbon atoms; R.sub.5 is optionally 
substituted alkylene of 2 to 5 carbon atoms; k and 1 are each an average 
of the number of the respective repeating unit and k is a value from 1 to 
10 and 1 from 2 to 50; and an acid anhydride having the structure 
##STR13## 
wherein R.sub.2 is optionally substituted aliphatic hydrocarbon of 2 to 10 
carbon atoms, alicyclic hydrocarbon of 6 to 7 carbon atoms or aromatic 
hydrocarbon of 6 carbon atoms, for instance as described in the 
specification of our Japanese Patent Application "A reactive acrylic 
monomer having end carboxyl group and preparation thereof" (Japanese 
Patent Application No. 001899/86). Also a reactive acrylic monomer 
represented by the formula [II]can be advantageously prepared by reacting 
an end hydroxyl containing (meth)acrylate having the structure 
##STR14## 
wherein R.sub.6 is hydrogen or methyl group; B is 
##STR15## 
provided m and n are each zero or one independently from another; D is a 
repeating unit represented by the structure R.sub.9 is ethylene or 
propylene; R.sub.10 is optionally substituted alkylene of 2 to 7 carbon 
atoms; R.sub.11 is optionally substituted alkylene of 2 to 5 carbon atoms; 
p and q are each an average value of the respective repeating unit, and p 
is a value from 1 to 10 and q is a value from 2 to 50, with an acid 
anhydride having the structure 
##STR16## 
wherein R.sub.7 is optionally substituted aliphatic hydrocarbon of 5 to 10 
carbon atoms, alicyclic hydrocarbon of 6 to 7 carbon atoms or aromatic 
hydrocarbon or 6 to 13 carbon atoms; R.sub.8 is aliphatic hydrocarbon of 1 
to 30 carbon atoms or aromatic hydrocarbon of 6 to 13 carbon atoms 
optionally substituted with either of vinyl, allyl, ether, ester or 
carbonyl group singularly or in combination of more than two in the main 
chain, and optionally substituted in the side chain. 
E is carboxylic acid, sulfonic acid phosphoric acid or phosphorus acid 
group, to obtain a compound having the structure 
##STR17## 
wherein R.sub.6, R.sub.7, B, D, and E are as defined above, and 
furthermore reacting an epoxy compound having the structure 
##STR18## 
wherein R.sub.8 is aliphatic hydrocarbon of 1 to 30 carbon atoms or 
aromatic hydrocarbon of 6 to 13 carbon atoms optionally substituted with 
either of vinyl, allyl, ether, ester or carbonyl group singularlily or in 
combination of more than two in the main chain, and optionally substituted 
with in the side chain(s), with the abovesaid reaction product[VII]. The 
other .alpha.,.beta.-ethylenically unsaturated monomers to be 
copolymerized with thus obtained reactive acrylic monomers having acidic 
groups and comparatively long side chains may be any of the members 
customarily used for the preparation of an acrylic resin, which are 
classified as follows; 
(1) acidic group bearing monomers; 
(a) .alpha.,.beta.-ethylenically unsaturated carboxylic acid: as, for 
example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, 
maleic acid, fumaric acid and the like, 
(b) .alpha.,.gamma.-ethylenically unsaturated sulfonic acid: as, for 
example, 1-acryloxy-1-propanesulfonic acid, 2-acrylamide-2-methyl 
propanesulfonic acid, 3-methacrylamide-1-haxanesulfonic acid and the like, 
(c) .alpha.,.beta.-ethylenically unsaturated phosphoric acid: as, for 
example, acid phosphoxy ethyl methacrylate, acid phosphoxy propyl 
methacrylate and the like, 
(2) hydroxyl bearing monomers: 
as, for example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 
2-hydroxyethyl methacryalte, hydroxypropyl methacrylate, hydroxybutyl 
acrylate, hydroxybutyl methacrylate, allyl alcohol and methallyl alcohol, 
(3) nitrogen containing alkyl acrylates or methacrylates: 
as, for example, dimethylaminoethyl acrylate, dimethylaminoethyl 
methacrylate and the like, 
(4) polymerizable amides; 
as, for example, acrylic amide and methacrylic amide, 
(5) polymerizable nitriles: 
as, for example, acrylonitrile and methacrylonitrile, 
(6) alkyl acrylates or methacrylates: 
as, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, 
ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate and 
2-ethylhexyl acrylate, 
(7) polymerizable aromatic compounds: 
as, for example, styrene, .alpha.-methyl styrene, vinyl toluene and t-butyl 
styrene, 
(8) .alpha.-olefines: 
as, for example, ethylene and propylene, 
(9) vinyl compounds: 
as, for example, vinyl acetate and vinyl propionate, 
(10) diene compounds: 
as, for example, butadiene, isoprene and the like. 
These monomers are used alone or in combination. The polymerization is 
carried out in a conventional way. At that time, it is preferred to use a 
polymerization initiator as, for example, an organic peroxide (e.g. 
benzoyl peroxide, t-butyl peroxide, cumen hydroperoxide and the like), an 
organic azo compound (e.g. azobiscyanovaleric acid azobisisobutyronitrile, 
azobis (2,4-dimethyl) valeronitrile, azobis (2-amidinopropane) 
hydrochloride and the like), an inorganic water soluble radical initiator 
(e.g. potassium persulfate, ammonium persulfate, sodium persulfate, 
hydrogen peroxide and the like), a Redox type initiator or the like. A 
chain transfer agent as, for example, a mercaptan (e.g. ethyl mercaptan, 
butyl mercaptan, dodecyl mercaptan and the like), a halogenated carbon 
(e.g. carbon tetrabromide, carbon tetrachloride and the like) may also be 
used as desired. 
Thus obtained acrylic resin of the present invention should have a weight 
average molecular weight of 1,000 to 200,000, and preferably 3,000 to 
100,000. If the weight average molecular weight is more than 200,000, the 
dissolving speed would become extremely low and impracticable, since the 
development time would be prolonged. If the weight average molecular 
weight is less than 1,000, the solubility to an alkaline aqueous solution 
would be too high and not only the remaining rate would become too low, 
but so called a pattern-thin-down would occur. 
The 1,2-quinone diazide compounds used in the invention are, for example, 
1,2-benzoquinone diazido sulfonic acid ester, 1,2-naphthoquinone diazido 
sulfonic acid ester, 1,2-benzoquinone diazido sulfonic acid amide, 
1,2-naphthoquinon diazido sulfonic acid amide and the like, and hitherto 
known 1,2-quinone diazide compounds can be directly put into use. More 
specifically, the following quinone diazide compounds which are described 
at page 339 to 352, J. Kosar, "Light-Sensitive Systems," John Wiley & Sons 
Inc. (New York), 1965 and at page 50, W. S. De Forest, Photoresist, McGraw 
Hill Inc. (New York), 1975 can be exemplified. 
That is, 1,2-benzoquinone diazido-4-sulfonic acid phenylester, 
1,2,1',2'-di(benzoquinone diazido-4-sulfonyl)-dihydroxy biphenyl, 
1,2-benzoquinone diazido-4-(N-ethyl-N-.beta.-naphthyl)-sulfonamide, 
1,2-naphthoquinone diazido-5-sulfonic acid cyclohexyl ester, 
1-(1,2-naphthoquinone diazido-05-sulfonyl)-3,5-dimethyl pyrazole, 
1,2-naphthoquinone diazido-5-sulfonic 
acid-4'-hydroxydiphenyl-4,-azo-.beta.-naphthol ester, 
N,N'-di-(1,2-naphthoquinone diazido-5-sulfonyl)-aniline, 2' 
(1,2-naphthoquinone diazido-5-sulfonyloxy)-1-hydroxyanthraquinone, 
1,2-naphthoquinone diazido-5-sulfonic acid-2,3,4-trihydroxybenzophenone 
ester, condensate of 2 moles of 1,2-naphthoquinone diazide-5-sulfonic acid 
chloride and one mol of 4,4'-diaminobenzophenone, condensate of 
1,2-naphthoquinone diazido-5-sulfonic acid chloride and one mol of 
4,4'-dihydroxy-1,1'-diphenylsulfon, condensate of one mol of 
1,2-naphthoquinonew diazido-5-sulfonic acid chloride and one mol of 
purpurogallin, 1,2-naphthoquinone diazido-5-(N-dihydroabietyl)-sulfonamide 
and the like. 
The weight ratio of said quinone diazide compound to the abovesaid acrylic 
resin composition should preferably be 5:100 to 150:100 and more 
preferably 10:100 to 100:100. If the ratio is less than 5:100, trouble as 
to patterning would arise, since the amount of carboxyl acids to be 
generated by light absorption is too small and there would be no 
appreciable difference in solubility to an alkaline aqueous solution 
between before and after light exposure. If the ratio is more than 
150:100, development would become difficult, since on short time light 
exposure the most of quinone diazide compounds would remain unreacted 
thereby still possessing high insolubility to an alkaline aqueous 
solution. 
If desired, the positive type photosensitive resin composition of the 
invention may further contain other conventional additives such as 
stabilizers, dyestuffs, pigments and the like. 
A photosensitive layer can be formed by a process wherein the positive type 
photosensitive resin composition of the invention comprising the abovesaid 
constituents is dissolved is an appropriate solvent, then is coated on a 
supporting substrate by a hitherto known coating method such as spinner 
and coater, and finally the coated substrate is dried. Examples of such 
solvents are as follows: glycol ethers as ethyleneglycol monomethyl ether, 
ethyleneglycol ethyl ether, ethyleneglycol monobutyl ether and the like; 
cellosolve acetates as methyl cellosolve acetate, ethyl cellosolve acetate 
and the like; aromatic hydrocarbons as toluence, xylene and the like; 
ketones as methyl ethyl ketone, cyclohexanone and the like; esters as 
ethyl acetate, butyl acetate and the like. 
These solvents are used alone or in combination. Also examples of 
supporting substrates are silicone wafer, aluminum plate, plastic film, 
paper, vitreous plate, copper plate, copper-clad laminate for use in 
printed wiring boards and the like. They are appropriately used in 
accordance with an application of the present photosensitive resin 
composition. 
The positive type photosensitive resinous composition comprising a 
composition comprising a quinone diazide compound and an acrylic resin 
bearing at least one side chain having the structure 
##STR19## 
wherein R.sub.2 is aliphatic hydrocarbon of 2 to 10 carbon atoms with or 
without a substituent(s), alicyclic hydrocarbon of 6 to 7 carbon atoms or 
aromatic hydrocarbon of 6 carbon atoms; A is a repeating unit having the 
structure 
##STR20## 
wherein R.sub.3 is ethylene or propylene; R.sub.4 is alkylene of 2 to 7 
carbon atoms with or without a substituent(s); R.sub.5 is alkylene of 2 to 
5 carbon atoms with or without a substituent(s); k and 1 is each an 
average of the number of the respective repeating unit and k is a value 
from 1 to 10 and 1 from 2 to 50; or having the structure 
##STR21## 
wherein R.sub.7 is aliphatic hydrocarbon of 5 to 10 carbon atoms with or 
without a substituent(s), alicyclic hydrocarbon of 6 to 7 carbon atoms or 
aromatic hydrocarbon of 6 to 13 carbon atoms; R.sub.8 is aliphatic 
hydrocarbon of 1 to 30 carbon atoms or aromatic hydrocarbon of 6 to 13 
carbon atoms with or without either of vinyl, allyl, ether, ester or 
carbonyl group singularly or in combination of more than two in the main 
chain, or with or without a substituent(s) in the side chain(s); B is 
##STR22## 
provided m and n is each an integer from 0 to 1 independently one another; 
D is a repeating unit represented by the structure 
##STR23## 
R.sub.9 is ethylene or propylene; R.sub.10 is substituted or not 
substituted alkylene of 2 to 7 carbon atoms; R.sub.11 is unsubstituted or 
substituted alkylene of 2 to 5 carbon atoms; p and q is each an average of 
the number of the respective repeating unit, and p is a value from 1 to 10 
and q is a value from 2 to 50; E is carboxylic acid, sulfonic acid, 
phosphoric acid or phosphorus acid group, can be used in organic solvent 
systems, or in aqueous dispersions or aqueous solutions which can be 
obtained by partly or perfectly neutralizing carboxyl groups thereof. Such 
aqueous systems can be utilized as a positive type photosensitive resin 
composition which can be subjected to an anode electrodeposition, wherein 
any supporting substrate with an electroconducting film, for example, 
copper-clad laminate, aluminum plate and the like, can be 
electrodeposited. The present invention shall be now more fully explained 
in the following Examples. Unless otherwise being stated, all parts and 
percentages are by weight.

EXAMPLE 1 
Into a 1 liter glass flask fitted with a stirrer, a Dimroth condenser, a 
thermometer and an air inlet tube, were placed 150 parts of succinic 
anhydride, 385 parts of Placcel FM-1 (1:1 mol adduct of 
.epsilon.-caprolactone and 2-hydroxyethyl methacrylate, trademark of 
Daicel Chem. Co.) and 500 ppm to the total charged amount of hydroquinone 
monomethyl ether. While introducing air, the mixture was reacted under 
stirring at 150.degree. C. (inner temperature) for 40 minutes. After 
completion of the reaction, the mixture was allowed to cool to a room 
temperature and the formed crystals of unreacted acid anhydride were 
filtered off to obtain the desired reactive acrylic monomer product(F), 
whose acid value was 72 and viscosity (25.degree. C.) was 250 cp. The 
reaction percentage calculated from the measured acid value was 96%. Into 
a 1 liter glass flask fitted with a stirrer, a Dimroth condenser, a 
thermometer, a dropping funnel and a nitrogen gas inlet tube, were placed 
beforehand 200 parts of ethylene glycol monobutyl ether. Then, the mixture 
of 100 parts of reactive acrylic monomer product(F), 75 parts of methyl 
methacrylate, 75 parts of n-butyl acrylate and 10 parts of t-butyl 
peroxy-2-ethyl hexanoate as a polymerization initiator was dropwise added 
to the solution through the dropping funnel under stirring at 120.degree. 
C. for 3 hours to obtain an acrylic resin composition. The acid value of 
the resultant resin product was 43 and the weight average molecular 
weight was 30,000. 
Then 20 grams of thus obtained resin solution (the solid content of 56% by 
weight) and 3 grams of 1,2-naphthoquinone diazido-5-sulfonic acid ester of 
2,3,4-trihydroxy benzophenone were dissolved in the mixed solvent of 60 
grams of ethylene glycol monoethyl ether acetate and 17 grams of methyl 
ethyl ketone and the resulting solution was filtered through a microfilter 
of 0.5.mu. in diameter to obtain a sensitizing solution. Upon application 
of this sensitizing solution over a silicone oxide film wafer by a 
spinner, the coated wafer was dried in an oven at 80.degree. C. for 30 
minutes. The film thickness thereof was 1.5 .mu.m. 
Thus obtained sensitized layer was closely contacted with a line-and-space 
pattern and the assembly was exposed to the ultraviolet light with the 
light intensity of 3.5 mW/cm.sup.2 at 365nm for 30 seconds. 
Upon development with 1% aqueous solution of sodium metasilicate at 
30.degree. C. for 30 seconds, it was found that 1.0 .mu.m line-and space 
was resolved and the resist had no peeling and cracking. 
Example 2 
Into a similar reaction vessel as used in Example 1, were placed 148 parts 
of phthalic anhydride, 400 parts of Blenmer PP-1000 (5.5:1 mol addition 
product of propylene oxide and methacrylic acid, trademark of Nippon 
Yushi), and 500 ppm to the total charged amount of hydroquinone monomethyl 
ether. While introducing air, the mixture was reacted, under stirring, at 
150.degree. C. (inner temperature) for 60 minutes. Thus obtained reactive 
acrylic monomer product(G) had an acid value of 108 and a viscosity 
(25.degree. C.) of 300 cp. The reaction percentage was 95%. Following the 
procedures stated in Example 1, an acrylic resin composition was prepared 
by employing the following formulation: 
______________________________________ 
monomer (G) 75 parts 
n-butyl acrylate 75 parts 
acrylonitrile 25 parts 
ethylene glycol monobutyl ether 
180 parts 
______________________________________ 
Thus obtained reaction product had an acid value of 40.2 and a weight 
average molecular weight of 32,000. 
Then 20 grams of thus obtained resin solution (the solid content of 58% by 
weight) and 7 grams of 1,2-naphthoquinon diazido-5-sulfonic acid ester of 
2,3,4-trihydroxy benzophenone were dissolved in the mixed solvent of 80 
grams of ethylene glycol monoethyl ether acetate and 25 grams of methyl 
ethyl ketone and the resulting solution was filtered through a microfilter 
of 0.5.mu. in diameter to obtain a sensitizing solution. 
Thus obtained sensitizing solution was evaluated following the procedures 
stated in Example 1. 
Example 3 
Into a similar reaction vessel as used in Example 1, were placed 77 parts 
of trimellitic anhydride, 300 parts of Placcel FM-5 (5:1 mol addition 
product of .epsilon.-caprolactone and 2-hydroxyethyl methacrylate, 
trademark of Daicel Chem. Co.) and 500 ppm to the total charged amount of 
hydroquinone monomethyl ether. While introducing air, the mixture was 
stirred at 165.degree. C. for 30 minutes to proceed the reaction. 
Thereafter the reaction mixture was subjected to a hot filtration to 
remove a small quantity of unreacted materials. 
Thus obtained intermediate product(H) had an acid value of 125 and was a 
semi-solid product at 25.degree. C. Then, 100 parts of Cardura E-10 
(glycidyl versatate, trademark of Shell Chemical Co.) were added to the 
intermediate product(H) obtained by the abovesaid preparation procedure. 
While introducing air again, the mixture was stirred at 150.degree. C. 
(inner temperature) for 40 minutes to proceed the reaction. 
Thus obtained reactive acrylic monomer(I) had an acid value of 52 and a 
viscosity of 400 cp (25.degree. C.). The reaction percentage determined 
from the acid value was found to be 95%. 
Following the procedures stated in Example 1, an acrylic resin composition 
was prepared by employing the following formulation: 
______________________________________ 
monomer [I] 77.0 parts 
methacrylic acid 6.2 parts 
methyl methacrylate 80.0 parts 
n-butyl acrylate 36.8 parts 
ethyleneglycol monobutyl ether 
164.0 parts 
______________________________________ 
Thus obtained reaction product had an acid value of 40.5 and a weight 
average molecular weight of 27,000. 
Then 20 grams of thus obtained resin solution (the solid content of 55% by 
weight) and 3 grams of 1,2-naphthoquinone diazido-5-sulfonic acid ester of 
2,3,4-trihydroxy benzophenone were dissolved in the mixed solvent of 60 
grams of ethylene glycol monoethyl ether acetate and 17 grams of methyl 
ethyl ketone and the resulting solution was filtered through a microfilter 
of 0.5.mu. in diameter to obtain a sensitizing solution. 
Thus obtained sensitizing solution was evaluated following the procedures 
stated in Example 1. 
Example 4 
Into a similar reaction vessel as used in Example 1, were placed 92 parts 
of sulfophthalic anhydride, 388 parts of 10:1 mol addition product of 
tetrahydrofuran and methacrylic acid and 500 ppm to the total charged 
amount of hydroquinone monomethyl ether. While introducing air, the 
mixture was stirred at 170.degree. C. for 30 minutes to proceed the 
reaction. Thereafter the reaction mixture was subjected to a hot 
filtration to remove a small quantity of unreacted materials. 
Thus obtained intermediate product(J) had an acid value of 108 and was a 
semi-solid product at 25.degree. C. 
Into a similar reaction vessel as used in Example 1, were placed 94 parts 
of glycidyl-p-tertiarybutyl benzoate (Fuso Chemical Co.) in addition to 
the intermediate product(J) obtained by the abovesaid preparation 
procedure. While introducing air again, the mixture was stirred at 
150.degree. C. (inner temperature) for 40 minutes to proceed the reaction. 
Thus obtained reactive acrylic monomer(K) had an acid value of 48 and a 
viscosity of 350 cp (25.degree. C.). The reaction percentage determined 
from the acid value was found to be 90%. 
Following the procedures stated in Example 1, an acrylic resin composition 
was prepared by employing the following formulation: 
______________________________________ 
monomer [K] 40.6 parts 
methacrylic acid 6.2 parts 
methyl methacrylate 60.0 parts 
ethyl acrylate 92.2 parts 
ethyleneglycol monobutyl ether 
164.0 parts 
______________________________________ 
Thus obtained reaction product had an acid value of 31.0 and a weight 
average molecular weight of 25,000. 
Then 20 grams of thus obtained resin solution (the solid content of 55% by 
weight) and 7 grams of 1,2-naphthoquinone diazide-5-sulfonic acid ester of 
2,3,4-trihydroxy benzophenone were dissolved in the mixed solvent of 80 
grams of ethylene glycol monoethyl ether acetate and 25 grams of methyl 
ethyl ketone and the resulting solution was filtered through a microfilter 
of 0.5.mu. in diameter to obtain a sensitizing solution. 
Thus obtained sensitizing solution was evaluated following the procedures 
stated in Example 1. 
Example 5 
20 grams of acrylic resin composition obtained from Example 1 and 13 grams 
of 1,2-naphthoquinone diazido-5-sulfonic acid ester of 2,3,4-trihydroxy 
benzophenone were dissolved in the mixed solvent of 80 grams of ethylene 
glycol monoethyl ether acetate and 48 grams of methyl ethyl ketone and the 
resulting solution was filtered through a microfilter of 0.5.mu. in 
diameter to obtain a sensitizing solution. 
Thus obtained sensitizing solution was evaluated following the procedures 
stated in Example 1. 
Example 6 
20 grams of acrylic resin composition obtained from Example 1 and 0.6 grams 
of 1,2-naphthoquinone diazido-5-sulfonic acid ester of 2,3,4-trihydroxy 
benzophenone were dissolved in the mixed solvent of 50 grams of 
ethyleneglycol monoethyl ether acetate and 14 grams of methyl ethyl ketone 
and the resulting solution was filtered through a microfilter of 0.5.mu. 
in diameter to obtain a sensitizing solution. 
Thus obtained sensitizing solution was evaluated following the procedures 
stated in Example 1. 
Example 7 (Evaluated as an electrodeposition composition) 
The solution of 15 parts of 1,2-naphthoquinone diazido-5-sulfonic acid 
ester of 2,3,4-trihydroxy benzophenone dissolved in 60 parts of methyl 
ethyl ketone was added to 100 parts of acrylic resin composition solution 
prepared in Example 1 and furthermore 3.7 parts of triethyl amine was 
added thereto and the mixture was dissolved in the solution and was 
gradually diluted with 1500 parts of deionized water to make up an 
electrodeposition composition. 
Thereafter an insulating base plate with 0.6 mm through-holes was dipped 
into the electrodeposition bath and was non-electrolytic and electrolytic 
copper plated respectively. That is, a two-sided circuit base plate with 
copper thickness 35 .mu.m was dipped into the electrodeposition bath, the 
base plate was connected to an anode and the metallic wall of the bath to 
a cathode. Thereafter, 100 V direct was impressed for 2 minutes. 
The plate was then washed with water and dried in an oven maintained at 
100.degree. C. for 5 minutes to form a coating of the positive type 
photosensitive resin in 8 .mu.m thickness. This coating has no pinhole, a 
uniform coating thickness and the walls of the through-holes were 
perfectly covered. On said photosensitive resin composition coatings were 
placed a positive type photo-tool mask with a circuit pattern, and the 
circuit base plate was exposed from both sides by the ultraviolet light 
with the light intensity of 3.5 mW/cm.sup.2 at 365 nm for one minute. 
Upon development with 1% aqueous solution of sodium metasilicate at 
30.degree. C. for one minute, it was found that line widths with high 
fidelity were reproduced and there was no resist peeling and cracking. 
Thereafter copper at exposed parts was etched by ferric chloride solution, 
washed by water, and the resin coating on the circuit resin plate was 
removed with 3% sodium hydroxide aqueous solution at 50.degree. C. to 
obtain the desired circuit pattern with the minimum circuit line width of 
3.mu.m. At this time, unexposed copper on the wall of the through-holes 
remained perfectly unetched, and it accounts for the fact that the 
conductivity on both sides was secured and the resin coverage was perfect. 
Possibility of industrial application 
As stated above, the positive type photosensitive resin composition of the 
present invention is useful for microfabrication resist films and 
photosensitive materials for use in lithographic plates because of 
excellent flexibility and adhesion, and moreover, when developed, 
non-exposed parts being of extremely less swelling nature. 
TABLE 1 
__________________________________________________________________________ 
Examples 1 2 3 4 5 6 
__________________________________________________________________________ 
Adhesion to 
excellent 
excellent 
excellent 
excellent 
excellent 
excellent 
the wafer *1 
resolving power (.mu.m) 
1.0 0.9 1.1 1.0 0.9 0.7 
__________________________________________________________________________ 
*1 The photosensitive coating film formed and dried was cut with a cutter 
to give a scar, and cracks and peels of the coating film thereby giver 
rise to were observed.